KR20140011506A - Gas barrier film, method for preparing thereof and display display member comprising the same - Google Patents
Gas barrier film, method for preparing thereof and display display member comprising the same Download PDFInfo
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Abstract
The gas barrier film of the present invention is in contact with the base film, and includes a hydrogenated polysiloxane. The gas barrier film is excellent in gas barrier properties, non-vacuum wet coating is possible, the production time is short, excellent flexibility and transparency, excellent adhesion to the substrate, it is possible to prevent damage to the substrate by heating. .
Description
The present invention relates to a gas barrier film, a method of manufacturing the same, and a display member including the same. More specifically, the present invention includes a hydrogenated polysiloxane residue in the gas barrier film, excellent gas barrier properties, non-vacuum wet coating is possible short production time, excellent flexibility and transparency, excellent adhesion to the substrate and The present invention relates to a gas barrier film capable of preventing damage to a substrate due to heating, a method of manufacturing the same, and a display member including the same.
Plate glass has conventionally been used as a display substrate of 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, plate glass is not easy to be broken, has no flexibility, has a specific gravity, and is thin and light. In order to solve such a problem, plastic film is attracting attention as a material instead of flat glass. Since plastic films are light and difficult to break, and thin films are easily formed, they are effective materials that can cope with the increase in size of display elements.
However, since the plastic film has a higher gas permeability than glass, the display device using the plastic film as a substrate has a problem in that the light emitting performance of the display device is easily degraded due to oxygen or water vapor permeation.
Accordingly, attempts have been made to minimize the effects of oxygen or water vapor by forming a gas barrier film of an organic or inorganic material on a plastic film. In general, inorganic materials such as silicon oxide (SiOx), aluminum oxide (AlxOy), tantalum oxide (TaxOy), titanium oxide (TiOx) and the like are mainly used as the gas barrier film. These gas barrier thin films are coated on the surface of the plastic film by a vacuum deposition method such as plasma enhanced chemical vapor deposition (PECVD), sputtering, or the sol-gel method in a high vacuum state.
In the form of such a gas barrier thin film, one layer composed of an inorganic material, a two-layer structure of an organic layer and an inorganic layer, or a three-layer structure of an organic layer, an inorganic layer, an organic layer, or an inorganic layer, an organic layer, and an inorganic layer, The structure is repeated several times, and the like, and it is common that there is usually more than one inorganic layer in the gas barrier thin film. Here, the organic layer serves to prevent the defect of the thin film, which may occur in the inorganic layer, rather than the gas barrier property, from propagating to the next inorganic layer.
Japanese Patent Nos. 1994-0031850 and 2005-0119148 disclose the case where the inorganic layer is directly coated on the surface of the plastic film by sputtering. However, since the elastic film, the coefficient of thermal expansion, the bending radius, etc. of the plastic film and the inorganic layer are greatly different, if heat or repetitive force is applied or bent from the outside, cracks are generated due to stress at the interface, which causes easy peeling. Can be. Japanese Patent No. 2004-0082598 discloses a method of using a multilayer gas barrier thin film composed of an organic layer and an inorganic layer. However, the presence of several layers having different physical properties may cause cracking or peeling of the thin film at each interface. It resulted in a further increase. In addition, since the formation of the gas barrier thin film used in the prior art requires a deposition process performed under high vacuum, an expensive device is required, and it takes a long time to reach a high vacuum, which is not economical.
As a method of forming a barrier layer in addition to high vacuum deposition, Korean Patent No. 2005-0068025 discloses a conventional plastic substrate surface coated with a nanocomposite solution in which polyimide or its precursor and nano-sized layered silicate are uniformly dispersed, followed by drying and By forming a polyimide nanocomposite film by heat treatment, a display substrate is disclosed in which gas barrier properties are greatly improved in addition to mechanical properties including heat resistance. However, the polyimide nanocomposite membrane has a moisture permeability of 3.36 g / m 2 / day, which is not suitable for use as a gas barrier film.
Japanese Patent No. 2007-237588 discloses a technique of forming a polysilazane film by a wet method and applying atmospheric pressure plasma to change a part of the polysilazane film to silica and to form a barrier layer. However, when the polysilazane film is changed to silica, cracks are generated well, making it difficult to make an appropriate gas barrier film.
Japanese Patent No. 2000-246830 forms a polysilazane layer and treats it by contact with a gas containing water vapor in the presence of amines or acids, and then promotes the hydrolysis reaction by heat treatment and gas discharge treatment. Disclosed is a technique for changing silica of a polysilazane component. However, it was found that the hydrolysis reaction of the polysilazane component proceeds by gas contact treatment and heat treatment, but it becomes a silica film containing much Si-OH, which also shows that cracks are generated and sufficient barrier performance is not obtained. .
An object of the present invention is to provide a gas barrier film excellent in gas barrier properties and a coating liquid for a gas barrier film.
Another object of the present invention is to provide a coating liquid for a gas barrier film and a gas barrier film having a non-vacuum wet coating and a short manufacturing time and excellent flexibility and transparency.
Another object of the present invention is to provide a coating solution for a gas barrier film and a gas barrier film which is excellent in adhesion to a substrate and can prevent damage to the substrate by heating.
It is still another object of the present invention to provide a gas barrier film and a coating solution for a gas barrier film which do not crack.
Still another object of the present invention is to provide a method for producing a gas barrier film, which is simple in production and can prevent damage to the substrate.
Still another object of the present invention is to provide a display member to which the gas barrier film is applied.
One aspect of the invention relates to a gas barrier film. The gas barrier film is in contact with the base film and includes a hydrogenated polysiloxane residue.
In an embodiment, the hydrogenated polysiloxane may have a unit represented by Formula 1 and a unit represented by Formula 2 below, and a terminal part represented by Formula 3 below:
[Formula 1]
(2)
(3)
In Formulas 1 and 2, R1 to R7 are each independently 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 group , Substituted or unsubstituted C3 to C30 arylalkyl group, substituted or unsubstituted C3 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 heterocyclic alkyl group, substituted or unsubstituted C3 to C30 alkenyl group, Substituted or unsubstituted alkoxy group, substituted or unsubstituted carbonyl group, hydroxy group, or a combination thereof.
The hydrogenated polysiloxane may have an oxygen content of 0.2% to 3% by weight.
The terminal group represented by Chemical Formula 3 may be included in an amount of 15 to 35 wt% based on the total content of Si—H bonds in the structure.
The hydrogenated polysiloxane may have a weight average molecular weight (Mw) of 1000 to 5000 g / mol.
The gas barrier film may have a moisture permeability of 0.0001 to 0.1 g / m 2 / day as measured by ASTM F-1249.
The gas barrier film may have a temperature of 25 ° C. modulus of 40 to 60 GPa and a film thickness of 0.01 to 3 μm measured by a nano indenter.
Another aspect of the present invention relates to a coating liquid for the gas barrier film. The coating solution for a gas barrier film includes a hydrogenated polysiloxane having a unit represented by Formula 1, a unit represented by Formula 2 below, and a terminal portion represented by Formula 3 below; And a coating liquid for a gas barrier film comprising a solvent:
[Formula 1]
(2)
(3)
In Formulas 1 and 2, R1 to R7 are each independently 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 group , Substituted or unsubstituted C3 to C30 arylalkyl group, substituted or unsubstituted C3 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 heterocyclic alkyl group, substituted or unsubstituted C3 to C30 alkenyl group, Substituted or unsubstituted alkoxy group, substituted or unsubstituted carbonyl group, hydroxy group, or a combination thereof.
The coating solution may include 0.1 to 50% by weight of hydrogenated polysiloxane.
The hydrogenated polysiloxane may have an oxygen content of 0.2% to 3% by weight.
The terminal group represented by Chemical Formula 3 may be included in an amount of 15 to 35 wt% based on the total content of Si—H bonds in the structure.
The hydrogenated polysiloxane may have a weight average molecular weight (Mw) of 1000 to 5000 g / mol.
Another aspect of the invention relates to a method for producing a gas barrier film. The method comprises coating the coating solution on at least one side of the base film to form a coating layer; And curing the coating layer comprises the step of setting the moisture permeability measured by ASTM F-1249 to 0.0001 to 0.1 g / m 2 / day.
In embodiments the curing may be cured by ultraviolet radiation, plasma treatment, heat treatment or a combination thereof.
The ultraviolet irradiation may be irradiated at 100 to 6000mJ / ㎠ for 0.1 to 5 minutes at a irradiation intensity of 10 to 200mW / ㎠ using a vacuum ultraviolet ray of 100 to 200nm.
The plasma treatment may be at atmospheric pressure plasma at a gas amount of 0.01 to 100 L / min, substrate movement speed of 0.1 to 1000 m / min, or vacuum plasma at a power of 100 W to 5000 W in a vacuum of 20 Pa to 50 Pa.
The heat treatment may be appropriately adjusted according to the heat resistance of the base film, and may be performed, for example, at 40 to 350 ° C. In this case, the relative humidity can be treated with 50 to 100% humidity.
The coating may be a roll coating, a spin coating, a dip coating, a flow coating or a spray coating.
The coating thickness may be 0.01㎛ ~ 3㎛.
Another aspect of the invention relates to a display member comprising the gas barrier film. The display member is a base film; And a gas barrier film laminated on at least one surface of the base film. In one embodiment, a buffer layer may be further formed between the base film and the gas barrier film. In another embodiment, an organic-inorganic hybrid layer including silica nanoparticles, silica sol, siloxane, silazane, or siloxazane may be further formed on the other surface of the gas barrier film not in contact with the base film.
The present invention is excellent in gas barrier properties, non-vacuum wet coating is possible short production time, excellent flexibility and transparency, excellent adhesion to the substrate, can prevent damage to the substrate by heating, cracks This invention has the effect of providing the gas barrier film, the coating liquid for a gas barrier film, the manufacturing method of a gas barrier film, and the display member to which the said gas barrier film is applied.
1 is a schematic cross-sectional view of a display member to which a gas barrier film according to an 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.
Hereinafter, exemplary embodiments of the present application will be described in detail with reference to the accompanying drawings. However, the technology disclosed in the present application is not limited to the embodiments described herein and may be embodied in other forms. However, the embodiments introduced herein are provided to ensure that the disclosed contents are thorough and complete, and that the spirit of the present application is sufficiently conveyed to those skilled in the art. In the drawings, the width, thickness, and the like of the components are enlarged in order to clearly express 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 can easily grasp the rest of the components. When described in the drawings as a whole, at the point of view of the observer, when one element is referred to as being positioned on top of another, this means that one element may be placed directly on top of another or that additional elements may be interposed between them. Include. 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 addition, in the drawings, the same reference numerals refer to substantially the same elements.
Coating solution for gas barrier film
Coating liquid for a gas barrier film of the present invention is a hydrogenated polysiloxane; And solvents.
The hydrogenated polysiloxane includes a silicon-oxygen-silicon (Si-O-Si) bonding unit in addition to the silicon-nitrogen (Si-N) bonding unit in the structure. Such silicon-oxygen-silicon (Si-O-Si) bonding units can alleviate stress upon curing to reduce shrinkage.
In embodiments, the hydrogenated polysiloxane may have a unit represented by Formula 1, a unit represented by Formula 2, and a terminal portion represented by Formula 3 below:
[Formula 1]
(2)
(3)
In Formulas 1 and 2, R1 to R7 are each independently 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 group , Substituted or unsubstituted C3 to C30 arylalkyl group, substituted or unsubstituted C3 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 heterocyclic alkyl group, substituted or unsubstituted C3 to C30 alkenyl group, Substituted or unsubstituted alkoxy group, substituted or unsubstituted carbonyl group, hydroxy group, or a combination thereof.
In the present invention, "substituted" means hydrogen, halogen atom, hydroxyl group, nitro group, cyano group, amino group, azido group, amidino group, hydrazino group, carbonyl group, carbamyl group, thiol group, ester group, Carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphate groups or salts thereof, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and carbon atoms An aryl group having -30, an aryloxy group having 6-30 carbon atoms, a cycloalkyl group having 3-30 carbon atoms, a cycloalkenyl group having 3-30 carbon atoms, a cycloalkynyl group having 3-30 carbon atoms, or a combination thereof is meant.
The hydrogenated polysiloxane may have an oxygen content of 0.2% to 3% by weight. When contained in the above range, the stress relaxation due to the silicon-oxygen-silicon (Si-O-Si) bond in the structure is sufficient, so that shrinkage can be prevented during heat treatment and cracks are prevented from being generated in the formed gas barrier layer . Preferably the oxygen content of the hydrogenated polysiloxane is 0.4 to 2.5% by weight, more preferably 0.5 to 2% by weight.
In addition, the hydrogenated polysiloxane may have a structure in which the terminal is capped with hydrogen, and the terminal group represented by Formula 3 may be included in an amount of 15 to 35 wt% based on the total content of Si—H bonds in the structure of the hydrogenated polysiloxane. When included in the above range, the oxidation reaction occurs during curing, but the SiH3 portion during curing prevents from scattering due to SiH4 to prevent shrinkage and the gas barrier layer formed therefrom may prevent cracking. Preferably, the terminal group of Chemical Formula 3 may be included in an amount of 20 to 30 wt% based on the total content of Si—H bonds in the hydrogenated polysiloxane residue structure.
The hydrogenated polysiloxane of the present invention may have a weight average molecular weight (Mw) of 1000 to 5000 g / mol. In the above range, it is possible to form a dense gas barrier layer with a thin film coating while reducing the components that evaporate during heat treatment. Preferably the weight average molecular weight (Mw) may be 1500 to 3500 g / mol.
The hydrogenated polysiloxane may be included in about 0.1 to 50% by weight relative to the total content of the coating liquid. If included in the above range can maintain a suitable viscosity and can be formed flat and evenly without bubbles and voids (Void).
The solvent may be used as long as it is not reactive with the hydrogenated polysiloxane and can dissolve the hydrogenated polysiloxane. However, when OH is contained, a solvent that does not contain an -OH group is preferable because it is reactive with hydrogenated polysiloxane. For example, ethers such as hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers can be used. Specifically, hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, sorbetso, and taben, halogen hydrocarbons such as methylene chloride, tricholoethane, dibutyl ether, dioxane, tetra hybrido furan and the like Ryu. The solubility of the hydrogenated polysiloxane, or the evaporation rate of the solvent may be appropriately selected and a plurality of solvents may be mixed.
The coating liquid of the present invention may further include a thermal acid generator (TAG). The thermal acid generator is an additive for improving the developability of the hydride polysiloxane and the contamination by uncuring, so that the hydride polysiloxane may be developed at a relatively low temperature. The thermal acid generator is not particularly limited as long as it is a compound capable of generating acid (H +) by heat, but it can be activated at about 90 캜 or higher to generate sufficient acid to select a low volatility. Such thermal acid generators can be selected, for example, from nitrobenzyl tosylate, nitrobenzyl benzenesulfonate, phenol sulfonate and combinations thereof. The thermal acid generator may be included in 25% by weight or less, for example 0.01 to 20% by weight based on the total content of the coating liquid. When included in the above range, the hydrogenated polysiloxane may be developed at a relatively low temperature. However, in order to have more excellent gas barrier properties, it is preferable that the organic component is not included.
The coating solution of the present invention may further include a surfactant. The said surfactant is not specifically limited, For example, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene ether, polyoxyethylene rail ether, polyoxyethylene nonyl phenol ether, etc. Polyoxyethylene sorbitan such as polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate Nonionic surfactants such as fatty acid esters, F-top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Megapack F171, F173 (manufactured by Dainippon Ink, Inc.). Fluorine-based surfactants such as Prorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Saffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) Kano siloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), etc., etc. are mentioned. The surfactant may be included in an amount of 10 wt% or less, for example, 0.001 to 5 wt% based on the total content of the coating liquid. In order to have more excellent gas barrier properties, it is preferable that an organic component is not included.
gas Barrier Film and its manufacturing method
A gas barrier film may be manufactured using the corout liquid. In embodiments, the coating liquid is coated on at least one surface of the base film to form a coating layer; In addition, the coating layer may be cured to prepare a gas barrier film such that the moisture permeability measured by ASTM F-1249 is 0.0001 to 0.1 g / m 2 / day. The gas barrier film of the present invention can be directly in contact with the base film without the formation of an inorganic layer.
In the present invention, the "substrate film" is an object to which the coating liquid is coated in order to impart gas barrier properties, and is not limited in form, thickness and material.
Methods of applying the coating solution to the base film include a roll coating, a spin coating, a dip coating, a flow coating, a spray coating, and the like, but are not necessarily limited thereto. .
The coating thickness of the coating solution is not particularly limited, but may be preferably 0.01 μm to 3 μm. No crack is generated 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 a combination thereof. Here, the "curing" process is a process of converting the hydrogenated polysiloxane to silica to ceramicize.
In one embodiment, the coating layer may be heat treated. In this case, the heating temperature is set according to the heat resistance of the substrate film, but in the case of a material having a relatively low heat resistance such as PET or PEN, the temperature is set to 120 ° C. or less. When a plastic film is coated with a planarization layer or a buffer layer, Consider the heat resistance and set the temperature.
According to such heating, the hydrogenated polysiloxane is ceramicized, but it is difficult to achieve sufficient ceramicization only by heating below 150 ° C.
Accordingly, in order to increase the rate of change to silica, ultraviolet irradiation, plasma treatment, and drying at high humidity may be applied.
Among the ultraviolet ray irradiation treatment, vacuum ultraviolet ray treatment is more preferable. Specifically, vacuum ultraviolet rays of 100 to 200 nm are used. Irradiation intensity and irradiation amount of vacuum ultraviolet ray can be set suitably. In one embodiment, the vacuum ultraviolet process is preferably 0.1 to 5 minutes, the irradiation intensity is 10 to 200mW / ㎠, the irradiation amount can be irradiated at 100 to 6000mJ / ㎠, preferably 1000 to 5000 mJ / ㎠.
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 atmospheric plasma, nitrogen gas, oxygen gas, or a mixture of such gases, preferably oxygen gas, is used to plasma the gas between two electrodes and irradiates the substrate, or the substrate is irradiated between the two electrodes. And plasma-forming through gas. As plasma conditions, gas amount is 0.01-100 L / min. The moving speed of the substrate is 0.1 to 1000 m / min. In the case of a vacuum plasma, nitrogen gas, oxygen gas, or such a mixed gas is preferably disposed in an airtight space in which the electrode or waveguide is placed in a sealed space maintained at a vacuum degree of about 20 Pa to 50 Pa by oxygen gas, and the electric power such as DC, AC, radio wave or microwave is applied to the electrode. Alternatively, an arbitrary plasma can be generated by using and applying a waveguide. The output of the plasma treatment is 100W to 5000. The plasma treatment time is 1 to 30 minutes.
In addition, the hydrogenated polysiloxane may be cured by heat treatment at high humidity and low temperature. In this case, the heat treatment can be performed at a temperature of 40 to 350 DEG C and a relative humidity of 50 to 100%. In the above range, no cracking occurs and sufficient ceramicization can be obtained.
The gas barrier film may have a moisture permeability measured by ASTM F-1249 of 0.0001 to 0.1 g / m 2 / day, preferably 0.0001 to 0.08 g / m 2 / day.
In addition, the gas barrier film may have a room temperature modulus measured by a nanoindenter of 40 GPa to 60 GPa, preferably 50 to 59 GPa. Modulus in the present invention is a value measured at 25 ℃ using a nanoindenter Ti 750 Ubi (manufactured by Hysitron).
Display member
The display member of the present invention includes the gas barrier film.
1 is a schematic cross-sectional view of a display member to which a gas barrier film according to an embodiment of the present invention is applied. As shown, the
The base film may be coated with 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
In addition, a buffer layer may be coated on the
There is no particular limitation as the
The thickness of the
The
The material and the method of forming the buffer layers 15 and 25 may be easily implemented by those skilled in the art.
For example, an organic-inorganic hybrid layer may be formed as the buffer layers 15 and 25. In an embodiment, the organic-inorganic hybrid layer is formed by blending silica nanoparticles, silica sol, siloxane, silazane, or siloxazane with an acrylic compound to cure or curing the siloxane, silazane, or siloxazane modified acrylic copolymer. Can be. In addition, a urethane hybrid poly silazane may be applied as the organic-inorganic hybrid layer. The curing method may be applied by heat curing or uv curing, preferably uv curing method may be preferably applied.
When the organic-inorganic hybrid layer including the silica nanoparticles, silica sol, siloxane, silazane or siloxanexazan is applied, the film is prevented from cracking and deformation, and more excellent thermal stability, fairness, gas permeability, surface hardness, and gas permeation are obtained. Affinity with the barrier membrane.
The organic-inorganic hybrid layer may have a thickness of 5 μm or less, for example, in the range of 1 to 3 μm. In the above range, cracks and deformations are prevented, and the processability, gas permeability, surface hardness and affinity with the gas permeation barrier film are excellent.
Since the gas barrier film of the present invention has excellent gas barrier properties, it is conventionally formed by repeating a two-layer structure of an organic layer and an inorganic layer, or a structure having a three-layer structure of an organic layer, an inorganic layer, an organic layer, or an inorganic layer, an organic layer, and an inorganic layer. The multilayer gas barrier layer can be implemented with only a single 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. Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.
Example
Specific specifications of the components used in the following examples and comparative examples are as follows.
1. Preparation of Coating Solution 1
Dry nitrogen was substituted inside the reactor of 2 L with agitator and temperature controller. Then, 2.0 g of pure water was injected into 1,500 g of dry pyridine, and the mixture was sufficiently mixed. Subsequently, 100 g of dichlorosilane was slowly added thereto over 1 hour. Then, while stirring, 70 g of ammonia was slowly injected over 3 hours. Next, dry nitrogen was injected for 30 minutes to remove ammonia remaining in the reactor.
The obtained white slurry product was filtered using a 1 μm Teflon filter in a dry nitrogen atmosphere to obtain 1,000 g of a filtrate. After adding 1,000 g of dried xylene, the operation of replacing the solvent from pyridine to xylene using a rotary evaporator was repeated three times, adjusting the solid content concentration to 20%, and finally, a pore size of 0.03 μm. It filtered with the filter made of Teflon. Oxygen content measured using FlashEA 1112 (manufactured by Thermo Fisher Scientific Inc.) for the obtained hydrogenated polysiloxane was measured using Proton NMR: AC-200 (manufactured by Bruker) at 0.5 MHz and 00 MHz (total). ) Was 0.20, GPC (HPLC Pump 1515, RI Detector 2414 (manufactured by Waters)) and Colum: KF801, KF802, KF803 (manufactured by Shodex), the weight average molecular weight was 2,000 g / mol.
2. Preparation of Coating Solution 2
Dry nitrogen was substituted inside the reactor of 2 L with agitator and temperature controller. Then, 1.1 g of pure water was injected into 1,500 g of dry pyridine, and the mixture was sufficiently mixed. Subsequently, 100 g of dichlorosilane was slowly added thereto over 1 hour. Then, while stirring, 70 g of ammonia was slowly injected over 3 hours. Next, dry nitrogen was injected for 30 minutes to remove ammonia remaining in the reactor.
The obtained white slurry product was filtered using a 1 μm Teflon filter in a dry nitrogen atmosphere to obtain 1,000 g of a filtrate. After adding 1,000 g of dried xylene, the operation of replacing the solvent from pyridine to xylene using a rotary evaporator was repeated three times, adjusting the solid content concentration to 20%, and finally, a pore size of 0.03 μm. It filtered with the filter made of Teflon.
Oxygen content of the obtained hydrogenated polysiloxane residue was 2.1%, SiH3 / SiH (total) was 0.19, and the weight average molecular weight was 2,700 g / mol.
3. Preparation of Coating Liquid 3
Dry nitrogen was substituted inside the reactor of 2 L with agitator and temperature controller. Then, 0.3 g of pure water was injected into 1,500 g of dry pyridine, and the mixture was sufficiently mixed. Subsequently, 100 g of dichlorosilane was slowly added thereto over 1 hour. Then, while stirring, 70 g of ammonia was slowly injected over 3 hours. Next, dry nitrogen was injected for 30 minutes to remove ammonia remaining in the reactor.
The obtained white slurry product was filtered using a 1 μm Teflon filter in a dry nitrogen atmosphere to obtain 1,000 g of a filtrate. After adding 1,000 g of dried xylene, the operation of replacing the solvent from pyridine to xylene using a rotary evaporator was repeated three times, adjusting the solid content concentration to 20%, and finally, a pore size of 0.03 μm. It filtered with the filter made of Teflon.
Oxygen content of the obtained hydrogenated polysiloxane residue was 0.4%, SiH3 / SiH (total) was 0.30, and the weight average molecular weight was 2,600 g / mol.
4. Preparation of Coating Liquid 4
25.62 g of tetraethyl silicate (TEOS, manufactured by Sigma-Aldrich Co., Ltd.) was added to 100 g of distilled water mixed with 0.3 g of 95% acetic acid, and methyltrimethoxysilane (MTMS, Shin Etsu KBM503) was stirred. Was added to prepare an organic / inorganic hybrid solution at room temperature. At this time, the molar ratio of tetraethyl silicate and methyl methoxy silane added is 1: 2.
5. Preparation of Coating Solution 5
20 wt% xylene solution of polysilazane NL110A (manufactured by AZ Electric Materials) was used.
Example One
Coating solution 1 was spin coated on a 125 μm PEN film (TEONEX PQDA5, manufactured by Teijin Dupont). Spin coating is applied at 1000rpm for 20 seconds and dried in convection oven at 80 ℃ for 3 minutes, vacuum UV irradiator uses Model CR403 from SMT, and exposed to irradiation intensity of 14mW / cm 2 for 143 seconds at 2000mJ / cm 2 It was irradiated with and dried in a convection oven at 120 ℃ for 1 hour.
Example 2
Coating solution 1 was spin coated on a 125 μm PEN film (TEONEX PQDA5, manufactured by Teijin Dupont). Spin coating is applied at 1000rpm for 20 seconds and dried in convection oven at 80 ℃ for 3 minutes. Then spin coating at 1000rpm for 20 seconds and dry in convection oven at 80 ℃ for 3 minutes. Spin coating 5 times in the same way and dried in convection oven at 80 ℃ for 3 minutes to form a film with 3㎛. And vacuum UV irradiation was investigated with 2000mJ / cm 2 and the exposure for 143 seconds at irradiation intensity of 14mW / cm 2 was used for SMT Co. Model CR403, and dried at 120 ℃, 1 sigan convection oven.
Example 3
Vacuum UV irradiator was used as SMT Model CR403 and was carried out in the same manner as in Example 1 except for irradiating at 4000mJ / cm 2 by exposure for 286 seconds at a radiation intensity of 14mW / cm 2 .
Example 4
The same procedure as in Example 1 was carried out except that coating solution 2 was used instead of coating solution 1.
Example 5
Except for using the coating solution 3 instead of the coating solution 1 was carried out in the same manner as in Example 1.
Comparative Example One
Coating solution 4 was spin coated on a 125 μm PEN film (TEONEX PQDA5, manufactured by Teijin Dupont). Spin coating was applied for 20 seconds at 1000rpm and dried in a convection oven at 80 ℃, 3 minutes. And dried in a convection oven at 120 ° C. for 1 hour.
Comparative Example 2
Coating solution 4 was spin coated on a 125 μm PEN film (TEONEX PQDA5, manufactured by Teijin Dupont). Spin coating was applied for 20 seconds at 1000rpm and dried in a convection oven at 80 ℃, 3 minutes. Then spin coating at 1000rpm for 20 seconds and dry in convection oven at 80 ℃ for 3 minutes. Spin coating 5 times in the same way and dried in convection oven at 80 ℃ for 3 minutes to form a film with 3㎛. And dried in a convection oven at 120 ° C. for 1 hour.
Comparative Example 3
Coating solution 5 was spin coated on a 125 μm PEN film (TEONEX PQDA5, manufactured by Teijin Dupont). Spin coating was applied for 40 seconds at 3000rpm and dried in a convection oven at 80 ℃ for 3 minutes, and a vacuum UV irradiator was used with Model CR403 of SMT, and it was exposed for 1000 seconds at 14mW / cm 2 and 1000mJ / cm 2. It was irradiated with and dried in a convection oven at 120 ℃ for 1 hour.
Comparative Example 4
Vacuum UV irradiation was and is carried out in the same manner as Comparative Example 3 except that the exposure for 143 seconds at irradiation intensity of 14mW / cm 2 was irradiated using the SMT Co. Model CR403 to 2000mJ / cm 2.
Comparative Example 5
Coating solution 5 was spin coated on a 125 μm PEN film (TEONEX PQDA5, manufactured by Teijin Dupont). Spin coating and drying the coating for 20 seconds to 1000rpm, and the 80 ℃, 3 bun convection oven, vacuum UV irradiation is exposed in the irradiation intensity 14mW / cm 2 was used for SMT Co. Model CR403 for 72 seconds 1000mJ / cm 2 And dried in a convection oven at 120 ° C. for 1 hour.
Comparative Example 6
Vacuum UV irradiation was performed, and is the same as Comparative Example 5 except that the exposure for 143 seconds at irradiation intensity of 14mW / cm 2 was irradiated using the SMT Co. Model CR403 to 2000mJ / cm 2.
Physical properties of the gas barrier films prepared in Examples and Comparative Examples were measured based on the following criteria, and the results are shown in Table 2 below.
How to measure property
1. Water permeability (WVTR): Measured according to ASTM F-1249 standard using Aquatran Model1 (manufactured by Mocon). The specimen size is 100 * 100mm.
2. Crack: Visually judged whether or not.
3. Modulus: Measured at 25 ° C. using a nanoindenter Ti 750 Ubi (manufactured by Hysitron).
(g / m 2 / day)
(g / m 2 / day)
As shown in Tables 1 and 2, it can be seen that the gas barrier films of Examples 1 to 5 have excellent gas barrier properties and no cracks. On the other hand, Comparative Examples 1 to 6 showed higher moisture permeability than in Examples, and in particular, Comparative Examples 4 to 6 confirmed that cracks occurred.
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:
20: gas barrier film
100, 200, 300: display member
Claims (22)
[Chemical Formula 1]
(2)
(3)
In Formulas 1 and 2, R1 to R7 are each independently 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 group , Substituted or unsubstituted C3 to C30 arylalkyl group, substituted or unsubstituted C3 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 heterocyclic alkyl group, substituted or unsubstituted C3 to C30 alkenyl group, Substituted or unsubstituted alkoxy group, substituted or unsubstituted carbonyl group, hydroxy group, or a combination thereof.
menstruum;
Coating liquid for a gas barrier film comprising:
[Chemical Formula 1]
(2)
(3)
In Formulas 1 and 2, R1 to R7 are each independently 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 group , Substituted or unsubstituted C3 to C30 arylalkyl group, substituted or unsubstituted C3 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 heterocyclic alkyl group, substituted or unsubstituted C3 to C30 alkenyl group, Substituted or unsubstituted alkoxy group, substituted or unsubstituted carbonyl group, hydroxy group, or a combination thereof.
Curing the coating layer to obtain a water permeability of 0.0001 to 0.1 g / m 2 / day as measured by ASTM F-1249;
Method of producing a gas barrier film comprising the step.
The gas barrier film of any one of claims 1 to 7, laminated on at least one surface of the base film;
Display member comprising a.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
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| KR20120066281A KR20140011506A (en) | 2012-06-20 | 2012-06-20 | Gas barrier film, method for preparing thereof and display display member comprising the same |
| CN201380026333.5A CN104379347B (en) | 2012-05-21 | 2013-05-21 | Display element and manufacture method thereof |
| PCT/KR2013/004437 WO2013176459A1 (en) | 2012-05-21 | 2013-05-21 | Display member and method for manufacturing same |
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| Application Number | Priority Date | Filing Date | Title |
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| KR20120066281A KR20140011506A (en) | 2012-06-20 | 2012-06-20 | Gas barrier film, method for preparing thereof and display display member comprising the same |
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| KR20140011506A true KR20140011506A (en) | 2014-01-29 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10020185B2 (en) | 2014-10-07 | 2018-07-10 | Samsung Sdi Co., Ltd. | Composition for forming silica layer, silica layer, and electronic device |
| KR101880210B1 (en) * | 2015-04-10 | 2018-07-20 | 주식회사 엘지화학 | Barrier film |
| US10093830B2 (en) | 2014-12-19 | 2018-10-09 | Samsung Sdi Co., Ltd. | Composition for forming a silica based layer, method for manufacturing silica based layer, and electronic device including the silica based layer |
| US10106687B2 (en) | 2015-07-31 | 2018-10-23 | Samsung Sdi Co., Ltd. | Composition for forming silica layer, method for manufacturing silica layer and silica layer |
| US10427944B2 (en) | 2014-12-19 | 2019-10-01 | Samsung Sdi Co., Ltd. | Composition for forming a silica based layer, silica based layer, and electronic device |
-
2012
- 2012-06-20 KR KR20120066281A patent/KR20140011506A/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10020185B2 (en) | 2014-10-07 | 2018-07-10 | Samsung Sdi Co., Ltd. | Composition for forming silica layer, silica layer, and electronic device |
| US10093830B2 (en) | 2014-12-19 | 2018-10-09 | Samsung Sdi Co., Ltd. | Composition for forming a silica based layer, method for manufacturing silica based layer, and electronic device including the silica based layer |
| US10427944B2 (en) | 2014-12-19 | 2019-10-01 | Samsung Sdi Co., Ltd. | Composition for forming a silica based layer, silica based layer, and electronic device |
| KR101880210B1 (en) * | 2015-04-10 | 2018-07-20 | 주식회사 엘지화학 | Barrier film |
| US10106687B2 (en) | 2015-07-31 | 2018-10-23 | Samsung Sdi Co., Ltd. | Composition for forming silica layer, method for manufacturing silica layer and silica layer |
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