KR102328878B1 - Gas barrier film and preparation method thereof - Google Patents

Abstract

The present invention relates to a gas barrier film having a gas barrier layer having excellent gas barrier properties and a small amount of outgas generated, a member for an electronic device comprising the gas barrier film, and an electronic device including the member for the electronic device will be.

Description

Gas barrier film and preparation method thereof

The present invention relates to a gas barrier film having a gas barrier layer having excellent gas barrier properties and a small amount of outgas generated, a member for an electronic device comprising the gas barrier film, and an electronic device including the member for the electronic device will be.

A plastic film is widely used as a packaging material. In recent years, there is a demand to extend shelf life as much as possible in terms of distribution and cost, and also, display devices such as organic light emitting diodes (OLEDs), semiconductor devices, and solar cells. In various device fields, development of a flexible device using a lightweight and flexible plastic film as a substrate instead of a conventional plate glass is being actively developed.

Since the plastic film substrate has inferior gas barrier performance compared to the inorganic substrate such as a glass substrate, research on a high-performance gas barrier film for suppressing the incorporation of air or water vapor on the plastic film substrate is being actively conducted.

In order to satisfy such high performance, various methods have been developed, and among them, the method of alternately stacking organic and inorganic thin films on a base film is the most applied.

An inorganic thin film with a dense structure, such as aluminum oxide, silicon oxide, or silicon nitride, is used as an important material for blocking gas. By itself, the gas barrier performance is partially improved.

Among them, a gas barrier film including a silicon nitride film is mainly formed by a TFE (Thin Film Encapsulation) process through an in-line deposition method of organic and inorganic materials in a manufacturing process such as OLED. When forming a silicon nitride film, batch type sputtering or PECVD (Plasma Enhanced Chemical Vapor De position) equipment is used.

However, this conventional method of forming an encapsulation film by the TFE process can be applied to a device on a glass substrate, but cannot be applied to a roll-to-roll continuous process using a flexible substrate such as a plastic film substrate. There is a problem that not only changes significantly, but also decreases flexibility.

Accordingly, it is necessary to develop a technology in which a film can be formed by a low-temperature process that does not put a strain on the plastic film substrate, and at the same time, the silicon nitride film formed has excellent gas barrier properties.

In addition, there is a need for a new manufacturing method capable of overcoming limitations in which expensive equipment is used in the manufacturing process, which increases the manufacturing price and makes large-area production difficult.

Korean Patent Publication No. 10-2019-0127086 (2019.11.13)

One object of the present invention is to solve the problems of the prior art, and as a polysilazane layer is formed by a simple solution coating using a polysilazane material, expensive equipment is not required to form the polysilazane layer, and also , to provide a gas barrier film with better gas barrier properties by converting the surface by performing ultraviolet ozone treatment after forming the polysilazane layer. In addition, one object of the present invention is to provide a gas barrier film having excellent optical properties such as flexibility and transparency as well as excellent gas barrier properties.

In addition, an object of the present invention is to enable stable film formation without changing the physical properties of the silicon nitride film and the plastic substrate at a low temperature, and to form a silicon nitride film with excellent performance as described above by utilizing a large-area roll-to-roll process on the plastic film substrate. An object of the present invention is to provide a method for manufacturing a gas barrier film.

As a result of research in order to solve the above problem, it was found that the target problem can be solved by manufacturing a film having a specific laminate structure. More specifically, a polysilazane layer is formed on the surface that is in direct contact with the gas to be blocked, and the polysilazane layer is subjected to UV ozone treatment and conversion treatment to provide a film with improved gas barrier properties, more specifically moisture barrier properties. Found that it can be done, the present invention was completed.

In one aspect of the present invention, when a layer containing a polysilazane compound is converted to ultraviolet ozone treatment at room temperature and normal pressure, and a spectrum is analyzed by infrared spectroscopy (FT-IR), Si-O peak in the wavelength region of ^{1060 cm -1} a polysilazane layer having an absorbance (AU) of and an absorbance (AU) of a Si-N peak in a wavelength region of 840 cm ^{-1 ;}

an organic film layer containing a nanopore body and a binder resin; and

base film;

includes,

It provides a gas barrier film having high transparency in which the polysilazane layer is formed on the outermost layer with respect to the gas permeation direction.

In one aspect of the present invention, the gas barrier film may include a polysilazane layer from a gas permeation direction; organic film layer; and a base film; may be sequentially stacked.

In addition, the gas barrier film may include a polysilazane layer from a gas permeation direction; base film; and an organic film layer; may be sequentially stacked.

In one aspect of the present invention, a bonding enhancing coating layer may be further included between the polysilazane layer and the organic film layer or between the polysilazane layer and the base film, and the bonding enhancing coating layer may be formed by applying a curable resin composition. have.

In one aspect of the present invention, a protective coating layer may be further included on the polysilazane layer, and the protective coating layer may be formed by applying a curable resin composition.

In an aspect of the present invention, the polysilazane layer may satisfy Equation 1 below.

[Equation 1]

0.2 < [Si-O] ₁₀₆₀ /[Si-N] ₈₄₀ < 2

In the formula 1, [Si-O] ₁₀₆₀ is an absorbance (AU) of Si-O peak in the wavelength range of ^{1060cm -1, [Si-N]} 840 is a Si-N peak at a wavelength range of 840 cm ^-1 Absorbance (AU).

In one aspect of the invention, the gas barrier film was produced after 7 days of measurement of _{[Si-O] 1060 / [} Si-N] 840 , and the initial measurement of _{[Si-O] 1060 / [} Si-N] 840 may have a difference of 2 or less.

In one aspect of the present invention, the polysilazane layer may be converted by irradiating a low pressure mercury lamp of 184 nm for 10 minutes to 2 hours under nitrogen and ozone atmosphere.

In one aspect of the present invention, the base film may be a polymer film.

In one aspect of the present invention, the nanoporous body is a micropore having a pore size of 2 nm or less, a mesopore having a level of 2 to 50 nm, and an ultraporous hybrid nanoporous body having both pore size regions. and specifically, for example, it may be a zeolite or an organic-inorganic hybrid nanoporous body.

In one aspect of the present invention, the polysilazane layer has a thickness of 10 to 1000 nm,

The bond enhancing coating layer has a thickness of 1 to 50 μm,

The organic film layer has a thickness of 1 to 300 μm,

The base film may have a thickness of 30 to 500 μm.

In one aspect of the present invention, the difference between the water permeability (WVTR) of the gas barrier film and the water permeability (WVTR) compared to the gas barrier film having a polysilazane layer not treated with ultraviolet ozone is 1 × 10 ¹ g/m 2 ·day or less it could be

In one aspect of the present invention, the gas to be blocked may be moisture.

In one aspect of the present invention, the gas barrier film may have a transmittance of 90% or more at 550 nm and a surface roughness of 0.1 μm or less.

Another aspect of the present invention is a method for producing a gas barrier film,

a) forming an organic film layer containing nanopores and a binder resin on a base film;

b) forming a bonding enhancing coating layer on the organic film layer or on the other surface of the base film;

c) Forming a layer containing a polysilazane compound on the bond-promoting coating layer, and performing ultraviolet ozone treatment at room temperature and atmospheric pressure to analyze the spectrum by infrared spectroscopy (FT-IR), Si-O in a wavelength region of ^{1060 cm -1} Converting the polysilazane layer having the absorbance (AU) of the peak and the absorbance (AU) of the Si-N peak in the wavelength region of 840 cm ^{-1 ;}

includes

In one aspect, the conversion treatment in step c) may be conversion treatment by irradiating a low pressure mercury lamp of 184 nm for 10 minutes to 2 hours under nitrogen and ozone atmosphere. More preferably, it may be a conversion treatment by irradiation for 20 minutes to 1 hour.

The gas barrier film according to the present invention has excellent gas barrier properties as well as flexibility, high transparency, and low surface roughness, so that it can be applied to displays and various fields.

In addition, it is possible to provide a gas barrier film with little change with time for gas barrier properties.

Hereinafter, the present invention will be described in more detail through embodiments or examples including the accompanying drawings. However, the following specific examples or examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention.

Also, the singular forms used in the specification and appended claims may also be intended to include the plural forms unless the context specifically dictates otherwise.

In addition, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated.

In this specification, when a part of a layer, film, region, plate, etc. is “on” or “on” another part, it is not only in the case of being “directly on” another part, but also in the case where there is another part in the middle. include

Throughout this specification, "A to B" means A or more and B or less, unless otherwise defined.

One aspect of the present invention provides a gas barrier film having excellent gas barrier properties as well as excellent optical properties such as mechanical flexibility and transparency, and low surface roughness.

Specifically, the first aspect of the present invention from the gas permeation direction, a polysilazane layer; organic film layer; and a base film; provides a gas barrier film having high transparency laminated in this order.

A second aspect of the present invention, from the gas permeation direction, a polysilazane layer; base film; and an organic film layer; provides a gas barrier film having high transparency stacked sequentially.

A third aspect of the present invention is a polysilazane layer from a gas permeation direction; bonding-promoting coating layer; organic film layer; and a base film; provides a gas barrier film having high transparency laminated in this order.

A fourth aspect of the present invention is a polysilazane layer from a gas permeation direction; bonding-promoting coating layer; base film; and an organic film layer; provides a gas barrier film having high transparency stacked sequentially.

A fifth aspect of the present invention provides a gas barrier film further comprising a protective coating layer on the polysilazane layer in any one selected from the first to fourth aspects.

The above first to fifth aspects are for describing the present invention in more detail, but are not limited thereto.

As in the first to fourth aspects, by first contacting the polysilazane layer with respect to the gas permeation direction, a film having better gas barrier properties can be provided, and also, the polysilazane layer is treated with ultraviolet ozone. and performing the conversion processing by infrared spectroscopy (FT-IR) absorption spectrum (AU) of the analysis when, Si-O peak in the wavelength range of 1060cm ^-1 due to the absorbance of the Si-N peak at a wavelength range of 840 cm ^-1 By forming the polysilazane layer having (AU), it is possible to provide not only excellent gas barrier properties despite a thin film, but also excellent optical properties such as transparency and low surface roughness to provide a gas barrier film. have.

In one aspect of the present invention, the polysilazane layer means a layer including polysilazane as a main component, and the main component is, for example, in the polysilazane layer or polysilazane-containing composition, the ratio of polysilazane is It means 55% or more and 100% or less by weight. That is, unavoidable impurities mixed in during the film formation process may be further included.

The polysilazane refers to a polymer in which a silicon atom (Si) and a nitrogen atom (N) are repeated to form a basic backbone.

Such polysilazane may be converted through a predetermined treatment, for example, ultraviolet ozonation described below to form silicon oxide and/or silicon oxynitride having barrier properties. Accordingly, the cured product of the polysilazane layer, that is, the cured layer, contains Si, N and/or O, and has a barrier property to the external environment.

That is, the layer containing the polysilazane compound represented by the following formula (1) is subjected to UV ozone treatment at room temperature and normal pressure, and the outermost layer is converted into a polysilazane layer represented by the following formula (2), and thus the gas barrier properties are further improved It is excellent, exhibits a light transmittance of 90% or more, and has a lower surface roughness, so that a film having excellent optical properties can be provided.

[Formula 1]

SixNyHz

[Formula 2]

SiOxNyHz

In Formulas 1 and 2, x, y, and z are each a ratio according to the number of atoms, and x+y+z = 1.

In one embodiment, the specific type of polysilazane is not particularly limited as long as it includes the unit represented by Formula 1 above.

More specifically, for example, perhydropolysilazane may be used.

In one embodiment, the polysilazane layer may be formed by applying a composition prepared by dissolving polysilazane in an organic solvent. The organic solvent is not limited as long as it is non-reactive with polysilazane and can dissolve it, for example, hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, sorbetso, taben, methylene chloride, tri Halogen hydrocarbons such as coroloethane, dibutyl ether, dioxane, and ethers such as tetrahybridrofuran may be used as the solvent.

For example, a commercially available polysilazane or a composition including the same may be used. For example, Aquamica (registered trademark) NN120-10, NN120-20, NAX120-10, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, manufactured by AZ Electronic Materials Co., Ltd. Commercially available polysilazane products such as NP140 or SP140, such as Merck's DURAZANE 2400, etc. may be used, but are not limited thereto.

In addition, in the present invention, UV ozone treatment is performed after coating the polysilazane layer, and the polysilazane layer is a spectrum by infrared spectroscopy (FT-IR) (equipment name: IFS-66/S, manufacturer: Bruker). and the Si-O absorbance (AU) of the peak in the wavelength range of the assay when, 1060cm ^-1, may be one having an absorbance (AU) of the Si-N peak at a wavelength range of 840 cm ^-1.

In addition, it is possible to provide a film having excellent transparency, lower surface roughness, and more excellent gas barrier properties by treating under specific conditions during the UV ozone treatment. Specifically, for example, it may be a conversion treatment by irradiating a low-pressure mercury lamp of 184 nm for 10 minutes to 2 hours under nitrogen and ozone atmosphere at room temperature and normal pressure, and under such conditions, the polysilazane layer may satisfy Equation 1 below. have. More specifically, nitrogen may be supplied at a flow rate of 5 to 15 L/min, and ozone may be in a range of 700 to 900 ppm/min.

[Equation 1]

0.2 < [Si-O] ₁₀₆₀ /[Si-N] ₈₄₀ < 2

In the formula 1, [Si-O] ₁₀₆₀ is an absorbance (AU) of Si-O peak in the wavelength range of ^{1060cm -1, [Si-N]} 840 is a Si-N peak at a wavelength range of 840 cm ^-1 Absorbance (AU).

In addition, in Equation 1, it may be 0.2 to 2, preferably 0.3 to 1.95, and more preferably 0.5 to 1.5, and in the above range, an excellent gas barrier effect even when the polysilazane layer is formed on the outermost layer in direct contact with the gas. It was confirmed that it can be expressed. In addition, it was confirmed that an excellent gas barrier effect could be achieved despite the thin film.

In addition, the gas barrier film that satisfies the above range had an [Si-O] ₁₀₆₀ / [Si-N] ₈₄₀ measured after 7 days of manufacture and an initial [Si-O] ₁₀₆₀ / [Si-N] _{840 measured} The difference may be 2 or less, more specifically 0.1 to 2, more specifically 0.2 to 1.8, and it was confirmed that the difference in the gas barrier effect was small even for long-term storage in the above range.

The thickness of the polysilazane layer including the UV ozone-treated conversion layer may be 10 to 1000 nm, preferably 20 to 800 nm, more preferably 30 to 700 nm, even more preferably 100 to 500 nm. It is possible to form a uniform coating layer within the above range, and it is preferable because it is possible to provide a film having excellent gas barrier properties even though it is a thin film.

In one aspect of the present invention, the base film may be a polymer film. The present invention has an effect that can be applied to polymer films as the conversion treatment is possible at room temperature and pressure as described above. Examples of the polymer film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), polystyrene (PS), polymethyl methacrylic (poly(methyl methacrylate), PMMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyamide (PA) , polycarbonate (PC), polysulfone (PSF), polyether sulfone (PES), polyarylate (PAR), polyimide (PI), cyclic polyolefin ), ethylene vinyl alcohol copolymer (ethylene vinyl alcohol copolymer, EVAL), and the like, may be any one or a combination thereof.

In addition, the base film may be a single-layer or multi-layer film.

The thickness of the base film is not particularly limited, but may be 30 to 500 μm, more preferably 30 to 200 μm.

In one aspect of the present invention, the organic film layer may serve to block the gas that is not blocked in the polysiloxane layer and is transmitted through the second layer. That is, it is possible to block gas permeation more densely than when the polysiloxane layer is formed alone. Accordingly, it is possible to provide a film having a thinner overall film thickness compared to forming the polysiloxane layer alone, and to provide a more excellent gas barrier effect compared to a film in which the polysiloxane layer is formed alone even though it is a thin film. Specifically, the gas barrier effect can be improved by 2 times or more, more specifically, by 2 to 1000 times or more, and long-term storage stability, that is, it is possible to provide a film with little decrease in the gas barrier effect even if the film is supplemented for a long time.

In addition, since the organic film layer contains a binder resin, it may exhibit a planarization effect of lowering the surface roughness of the base film during application, and thus an effect of enhancing the bonding between the base film and the polysilazane layer.

The organic film layer includes a nanoporous body capable of blocking gas and a binder.

Specifically, the nanoporous body may be a zeolite or an organic-inorganic hybrid nanoporous body.

Zeolite is a generic term for crystalline aluminosilicate. Various zeotype molecular sieves are known in which silicon or aluminum is partially or entirely replaced with silicon (Si) and aluminum (Al), which are elements constituting the framework structure of zeolite. For example, porous silicalite from which aluminum is completely removed and alpo (AlPO ₄ )-based zeolite analogs in which silicon is replaced with phosphorus (P), and Ti, Mn, Co, Fe in the framework of these zeolites and zeolite analogs and zeolite analogues obtained by partially substituting various metal elements such as Zn. On the other hand, examples of the MFI structure zeolite or its analogs include ZSM-5, silicalite-1, TS-1, AZ-1, Bor-C, borlite C, encilite, FZ-1, LZ-105, monoclinic H-ZSM-5, Mutinite, NU-4, NU-5, TSZ, TSZ-Ⅲ, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B and the like. Here, ZSM-5 is a zeolite having an MFI structure in which silicon and aluminum are formed in a certain ratio, silicalite _{-1 is a zeolite having a structure consisting only of silica (SiO 2} ), and TS-1 is titanium (Ti) in some aluminum sites. It is a zeolite with an MFI structure. As described above, since the adsorption and desorption properties are opposite to each other, in the case of zeolite, the adsorption is good, but it is difficult to desorb in the process of applying the laminated film for gas barrier to the article, and it is easy to desorb under high temperature conditions. For this reason, when high-temperature heat treatment is difficult due to the characteristics of the article, it may be limited to use of zeolite.

When organic-inorganic hybrid nanoporous materials are contained as the nanoporous body, the organic-inorganic hybrid nanoporous body is well dispersed in the resin as primary particles without agglomeration to provide a film with better transparency. can In addition, it is possible to provide a film having a more excellent gas barrier effect.

The organic-inorganic hybrid nanoporous body is generally referred to as "porous coordination polymers" [Angew. Chem. Intl. Ed., 43, 2334. 2004], or also referred to as “metal-organic frameworks (MOFs)”.

The organic-inorganic hybrid nanoporous body is a porous organic-inorganic high molecular compound formed by combining a central metal ion with an organic ligand through a molecular coordination bond. It is a crystalline compound. An organic-inorganic hybrid nanoporous body in which a polar metal ion and a carboxylate oxygen anion are contained in a crystalline backbone and a non-polar aromatic compound group coexist can have both hydrophilicity and hydrophobicity.

Since the organic-inorganic hybrid nanoporous body has a high surface area and molecular or nano-sized pores, it can be used to collect guest molecules smaller than the pore size or to separate molecules according to the size of the molecules using pores.

In this case, the pore size of the organic-inorganic hybrid nanoporous body may be adjusted by adjusting the length and/or the type of the ligand.

The organic-inorganic hybrid nanoporous body may have a dicarboxylic acid anion of a heterocyclic ring as a ligand. Preferably, the ligand is selected from the group consisting of terephthalate anion, furandicarboxylic acid anion, pyridinedicarboxylic acid anion, benzenetricarboxylic acid, thiophenedicarboxylic acid anion and pyrazoledicarboxylic acid anion. It may be one or more selected.

In addition, the organic-inorganic hybrid nanoporous body may be an organic-inorganic hybrid nanoporous body having an unsaturated metal coordination site in a skeleton, a surface, or a pore. The organic-inorganic hybrid nanoporous body is at least one selected from the group consisting of chromium ions, iron ions, nickel ions, cobalt ions, molybdenum ions, manganese ions, copper ions, magnesium and zinc ions, and zirconium ions as central metal ions. It may contain metal ions.

The unsaturated metal coordination site may be formed in the skeleton, or it may be formed in a metal ion or an organometallic compound present on the surface or in the pores of the organic-inorganic hybrid nanoporous body. Unsaturated metal coordination site is a ligand coordinated to the metal ion of the organic-inorganic hybrid nanoporous body, typically a coordinating site of a metal from which water or an organic solvent has been removed, which means a position where other ligands can form a coordination bond again. do. The unsaturated metal coordination site may be formed by removing some or all of water and solvent molecules or ligands other than water contained in the organic-inorganic hybrid nanoporous body. In order to secure the unsaturated metal coordination site of the organic-inorganic hybrid nanoporous body, it may be preferable to perform a pretreatment step of removing water or solvent components bound to the unsaturated metal coordination site.

The pretreatment can be performed by any method as long as water or solvent components can be removed without causing deformation of the organic-inorganic hybrid nanoporous body, for example, it can be achieved by heating to a temperature of 100° C. or higher under reduced pressure, preferably It may be achieved by heating to a temperature of 150° C. or higher, but is not limited thereto. Alternatively, it may be carried out using methods such as vacuum treatment, solvent exchange, ultrasonic treatment, etc. known in the art for removing solvents without limitation. As described above, representative examples of organic-inorganic hybrid nanoporous bodies that can secure unsaturated metal sites through heat treatment include MIL-100, MIL-101, MOF-74, Cu-BTC, MIL-127, CPO-27, etc. .

In addition, the organic-inorganic hybrid nanoporous body may be an organic-inorganic hybrid nanoporous body containing a hydrophilic hydroxyl group (OH) or hydroxide anion (OH-) group ligand in a ratio of 0.5 to 3 moles per 1 mole of the central metal ion in the pores. . The organic-inorganic hybrid nanoporous body has an adsorption capacity of 0.15 g or more per 1 gram or 1 milliliter of the organic-inorganic hybrid nanoporous body with respect to moisture. Specifically, representative examples of the organic-inorganic hybrid nanoporous body include aluminum fumarate, zirconium fumarate, CAU-10, MIL-160, MIL-53, UiO-66, and analogs thereof.

The organic-inorganic hybrid nanoporous body containing a hydrophilic OH group ligand, although weaker than that of the unsaturated coordination metal ion site in the backbone, exhibits not very strong interaction with polar molecules such as water, so it is effective as a moisture adsorbent and at low temperature. It has the advantage of being able to regenerate water by desorption from it.

When the content of the hydrophilic hydroxyl group (OH) or hydroxide anion (OH-) group in the organic-inorganic hybrid nanoporous body is less than 0.5 mol per 1 mol of the central metal ion, the hydrophilicity is weak and the moisture adsorption amount at low relative humidity is not high, and per 1 mol In the case of more than 3 moles, the hydrophilicity is too strong, so the desorption of moisture is not easy, and the regeneration temperature may be increased.

The ligand is not important in terms of the amount of moisture adsorption of the organic-inorganic hybrid nanoporous body, and the central metal ion is preferably at least one selected from the group consisting of aluminum ions, calcium, gallium, indium, magnesium ions, and zirconium ions.

The binder resin of the organic film layer may be an organic binder resin, an inorganic binder resin, or an organic/inorganic binder resin.

The organic binder resin may be a resin serving as a binder and at the same time a gas barrier resin or a gas (eg, moisture) adsorbing resin. The gas barrier resin is a polyolefin-based resin (PO) such as polyethylene and polypropylene; amorphous polyolefin resins (COP) such as cyclic polyolefins such as cyclopentadiene, dicyclopentadiene, or norbornadiene; polyester resins such as polyethylene terephthalate (PET) and polyethylene 2,6-naphthalate (PEN); polyamide-based resins such as nylon 6 and nylon 12; polyvinyl alcohol resin (PVA); polyimide resin (PI); polyetherimide resin (PEI); polysulfone resin (PS); polyethersulfone resin (PES); polyetheretherketone resin (PEEK); polycarbonate resin (PC); polyvinyl butyrate resin (PVB); polyarylate resin (PAR); polytetrafluoroethylene resin (PTFE); vinylidene fluoride resin (PVDF); vinyl fluoride resin (PVF); polyvinyl chloride resin (PVC); It may be polyvinylidene chloride resin (PVDC) or the like. The moisture-absorbing resin is polyacrylic acid (polyacrylic acid, polymethacrylic acid, etc.), polyalkylene oxide (polyethylene oxide, polypropylene glycol, polypropylene oxide, etc.), cellulose (methylcellulose, ethylcellulose, hydroxyethyl) Cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, etc.), starch (carboxymethyl starch, dialdehyde starch, corn starch, wheat starch, soluble starch such as dextrin, etc.), polyacrylic acid amides (polyacrylamide, polymethacrylic) amides), gelatins (gelatin, phthalated gelatin, etc.), alginic acids (alginic acid, sodium alginate, etc.), vinyl alcohols (polyvinyl alcohol, ethylene-vinyl alcohol copolymer), poly2-hydroxyethyl methacrylate , polyvinyl pyrrolidone, polyvinylimidazole, polyoxazoline, isobutylene maleic anhydride copolymer, sepiolite, silica gel, carrageenan, agarose, kaolin, polystyrene sulfonic acid, agar, xanthan gum, etc. It may be one or more selected. For example, the organic binder resin may be a polyalkylene oxide having a weight average molecular weight of 30,000 to 1,500,000.

Examples of the inorganic binder resin include polysiloxane such as polydimethylsiloxane and polysilane.

In addition, as the organic-inorganic binder resin, a mixture of 0.1 to 150 parts by weight of an organic binder resin with respect to 100 parts by weight of the colloidal inorganic particles may be exemplified. The colloidal inorganic particles may be any one of silica, alumina, magnesium oxide, titania, zirconia, tin oxide, zinc oxide, barium titanate, zirconium titanate, and strontium titanate, or a mixture thereof. The organic binder resin may be the same as the organic binder resin described above.

The laminated film for gas barrier according to the present invention contains a binder resin and nanopores dispersed in the resin, but the nanopores are dispersed in the form of primary particles without aggregation in the binder resin to provide a transparent organic film layer.

In the laminated film for gas barrier according to the present invention, the binder resin used for the organic film layer has a space sized for gas to pass therein when the film is formed, and has a particle size that can be accommodated in the space. By selecting and dispersing the pore body in the binder resin, an organic film layer having a dense film structure may be formed.

In the present invention, the nanoporous body has a micropore size of 2 nm or less (eg, zeolite), a mesoporous body with a pore size of 2 to 50 nm (eg, mesoporous carbon and nanosilica), both having a pore size region. It may be a hybrid nanoporous body that is superporous. The average particle diameter of the primary particles of the nano-porous body may be 10 nm to 1,000 nm, and may vary depending on the type of the nano-pore body. By including the nanoporous body, the barrier performance of the entire film can be improved by 2 to 5 times.

In one aspect of the present invention, the thickness of the organic film layer may be 1 to 300 μm, preferably 2 to 48 μm, more preferably 2 to 30 μm, but is not limited thereto.

In one aspect of the present invention, the bonding strength between the polysilazane layer and the base film or the bonding strength between the polysilazane layer and the organic film layer is further improved, and the composition for forming the polysilazane layer is applied more uniformly and transparently. It may further include a bonding enhancing coating layer to. In addition, by further including a bonding-promoting coating layer, the mechanical properties of the entire film may be further improved, and light transmittance may be further improved.

In one aspect of the present invention, the bonding enhancing coating layer may be formed by applying a curable resin composition. Specifically, for example, it may be formed by coating a curable resin composition in which a polyfunctional acrylate monomer selected from epoxy acrylate and urethane acrylate is dissolved. In addition, additives such as antioxidants, ultraviolet absorbers, and plasticizers may be included as needed.

The coating method is not particularly limited, but it can be formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, a dip method, or a dry coating method such as a vapor deposition method.

The thickness of the bonding enhancing coating layer is not limited, but may be, for example, 1 to 50 μm, more preferably 2 to 45 μm, and even more preferably 2 to 30 μm.

In addition, in one aspect of the present invention, by further including a protective coating layer on the polysilazane layer, if necessary, oxidation and change in physical properties of polysilazane can be prevented, surface scratches, etc. can be prevented, and barrier properties are further improved can do it The protective coating layer may be formed by applying a curable resin composition. More specifically, for example, a photocurable composition including a photocurable acrylate-based polymer and a photoinitiator may be used as the organic layer. In addition, as long as it is a photocurable composition commonly used for surface protection, it may be used without limitation.

The thickness of the protective coating layer may be 1 to 20 μm, more specifically 2 to 10 μm, but is not limited thereto.

In the laminated film for gas barrier according to the present invention, the gas to be blocked may be moisture, oxygen, nitrogen, carbon dioxide, and/or HF. More preferably, it may be a film for blocking moisture.

The laminated film for gas barrier according to the present invention may be flexible.

The laminated film for gas barrier according to the present invention may be used for packaging, packaging, or encapsulation. As a preferred embodiment, the gas barrier laminated film according to the present invention may be for packaging, packaging, or sealing food packaging, pharmaceutical packaging, organic devices, and electrical and electronic devices.

The gas barrier laminated film according to the present invention may have a difference in water permeability (WVTR) of 1 × 10 ¹ g/m 2 ·day or less compared to a gas barrier film having a polysilazane layer that is not subjected to UV ozone treatment.

In addition, the transmittance at 550 nm can achieve physical properties of 90% or more, more specifically, 90 to 95%, and thus has an effect that can be applied to optical fields requiring transparency. In addition, it is possible to provide a film having excellent surface smoothness having excellent surface smoothness and surface roughness of 0.1 µm or less, more specifically 0.08 µm or less.

Next, a method for manufacturing a gas barrier film according to an embodiment of the present invention will be described.

In one aspect of the present invention, the manufacturing method is

a) forming an organic film layer containing nanopores and a binder resin on a base film;

b) forming a bonding enhancing coating layer on the organic film layer or on the other surface of the base film;

c) Forming a layer containing a polysilazane compound on the bond-promoting coating layer, and performing ultraviolet ozone treatment at room temperature and atmospheric pressure to analyze the spectrum by infrared spectroscopy (FT-IR), Si-O in a wavelength region of ^{1060 cm -1} Converting the polysilazane layer having the absorbance (AU) of the peak and the absorbance (AU) of the Si-N peak in the wavelength region of 840 cm ^{-1 ;}

includes

In one embodiment, the base film may be a polymer film as described above.

In one aspect, the conversion treatment in step c) may be a conversion treatment by irradiating a low pressure mercury lamp of 184 nm for 10 minutes to 2 hours, more preferably 20 minutes to 1 hour under nitrogen and ozone atmosphere.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the following Examples and Comparative Examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

Hereinafter, the physical properties were measured as follows.

1. Absorbance

The absorbance of the polysilazane layer was measured by infrared spectroscopy (FT-IR) (equipment name: IFS-66/S, manufacturer: Bruker).

2. Water permeability (WVTR)

The water permeability of the entire film was measured according to ISO 15106-5.

The Deltaperm equipment of Technolox, UK, was used, and the measurement sample was placed in the equipment and the film specimen was left for 1 hour under vacuum conditions at 40 ° C. Water permeability (WVTR) was measured by uniformly supplying water gas to the surface of the polysilazane film under the condition of 90%.

3. Permeability

The transmittance of the entire film was measured as follows.

The transmittance of the film was measured using a spectrophotometer (Spectrophotomerter, model name: U-4100, Hitachi) using a tungsten filament and a deuterium lamp as light sources in the measurement wavelength range from 240 to 2,600 nanometers.

4. Surface roughness

The roughness of the film surface was measured by a three-dimensional microscope (VK-X, Keyence).

5. Haze

The haze of the film was measured by NDH 5000W from Nippon Deshoku.

[Example 1]

A 75 μm thick polyethylene terephthalate (PET) film was prepared as a base film, and an organic film layer was formed on one surface of the base film.

The organic film layer uses a mixed solvent of PGME (Propylene Glycol Methyl Ether) and Toluene, and MIL-100 (Fe) is added in an amount of 3% by weight based on the weight of the total coating solution as MOF, and as an organic binder resin, cyclo Aliphatic epoxy resin and acrylate resin were added in an amount of 45% by weight based on the weight of the total coating solution, and uniformly mixed to prepare an organic film layer coating solution. The prepared organic film layer coating solution was coated by the Mayer Bar coating method and dried for 10 minutes at 100° C. using a mobile dry oven to form an organic film layer. The coating thickness was 5 μm.

Next, a bonding enhancing coating layer was formed on the organic film layer.

The bonding enhancement coating layer is a UV-curable organic/inorganic hybrid hard coating material OPSTAR Z7501 manufactured by JSR Corporation, applied with a wire bar so that the film thickness after drying is 4 μm, and then dried at 70° C. for 5 minutes, and a high-pressure mercury lamp under an air atmosphere. was used to cure at 1.0 J/cm ^{2 .} The coating thickness was 6 μm.

Next, after applying the polysilazane composition on the bonding enhancing coating layer, ultraviolet ozone treatment was performed to form a polysilazane layer having a conversion layer.

The polysilazane layer was coated with a polysilazane solution (10wt% polysilazane/xylene solution from DNF Co., Ltd.) with a thickness of 400 nm using a Meyer bar (No. 4), and each After drying for 1 minute, it was further dried at 80 °C for 30 minutes. After drying, UV ozone treatment was performed by irradiating ^{5 mW/cm 2} of 184 nm low pressure mercury lamp for 20 minutes under nitrogen and ozone atmosphere.

Infrared Spectroscopy (FT-IR) of (Instrument: Bruker: IFS-66 / S , manufacturer) during spectral analysis, Si-O peak absorbance (AU) and, 840 cm ^-1 in a wavelength range of 1060cm ^-1 by It was confirmed to have an absorbance (AU) of the Si-N peak in the wavelength region, and the physical properties are shown in Tables 1 and 2 below.

[Example 2]

In Example 1, the polysilazane layer was prepared in the same manner except that it was carried out for 40 minutes during the UV ozone treatment.

The results are shown in Tables 1 and 2 below.

[Example 3]

In Example 1, the polysilazane layer was prepared in the same manner except that it was carried out for 60 minutes during the UV ozone treatment.

The results are shown in Tables 1 and 2 below.

[Example 4]

In Example 1, UV ozone treatment was performed for 20 minutes when the polysilazane layer was formed, and the same was prepared except that microwave plasma treatment was further performed in a vacuum state.

For plasma treatment, PECVD equipment (Roth & Rau AG, Roll Coat 500 system) was used, and Ar:N ₂ O gas was supplied at a ratio of 1:1 at 400sccm (1500W driving).

The results are shown in Tables 1 and 2 below.

[Example 5]

The polysilazane layer was prepared in the same manner except that it was performed for 200 minutes during UV ozone treatment.

The results are shown in Tables 1 and 2 below.

[Example 6]

In Example 1, it was prepared in the same manner, except that the bonding promoting coating layer was not formed.

The results are shown in Tables 1 and 2 below.

[Comparative Example 1]

In Example 1, it was prepared in the same manner except that the organic film layer was not formed.

The results are shown in Tables 1 and 2 below.

[Comparative Example 2]

In Example 1, the polysilazane layer was prepared in the same manner except that UV ozone treatment was not performed.

The results are shown in Tables 1 and 2 below.

Initial film properties After 7 days [Si-O] ₁₀₆₀ /[Si-N] ₈₄₀ Absorbance (AU) of 1060 cm ^-1 Absorbance (AU) of 840 cm ^-1
[Si-O] ₁₀₆₀ /[Si-N] ₈₄₀ Example 1 0.0684 0.1037 0.66 1.95 Example 2 0.0716 0.1019 0.70 1.18 Example 3 0.0817 0.0933 0.88 1.25 Example 4 0.0905 0.0913 0.99 0.99 Example 5 0.0931 0.3052 0.32 3.75 Example 6 0.0735 0.1692 0.43 1.8 Comparative Example 1 0.0615 0.0989 0.62 1.93 Comparative Example 2 0.0086 0.1635 0.05 0.31

As shown in Table 1, embodiments according to the invention examples 1 to 4 the absorption of the Si-N peak in the wavelength region of the Si-O peak absorbance (AU) and, 840 cm ^-1 in a wavelength range of 1060cm ^-1 (AU), it was confirmed that _{0.2 < [Si-O] 1060} / [Si-N] ₈₄₀ < 2 as UV ozone treatment was performed at room temperature and normal pressure. In addition, as shown in Table 2 below, as the above range was satisfied, it was confirmed that the initial moisture permeability was low and the change in the moisture permeability was small for 7 days. In addition, it was confirmed that the transmittance was high and the surface roughness was low.

As shown in Example 5, it was confirmed that when the ultraviolet morning treatment was excessively treated for 200 minutes or more, the water transmittance and surface roughness increased, and the light transmittance decreased.

As shown in Example 6, it was confirmed that the light transmittance was lowered compared to Example 1, and the water transmittance and surface roughness were increased in the case where the bonding-enhancing coating was not applied.

Comparative Example 1 did not include an organic film layer, and as shown in Table 2 below, it was confirmed that the moisture permeability was increased by 3 times or more compared to Example 1. In addition, it was confirmed that the light transmittance was lowered.

Comparative Example 2 is a case in which UV ozone treatment is not performed. As a result, as shown in Table 2 below, the initial moisture permeability was significantly increased compared to Example 1, and after 7 days, WVTR was almost increased to the level of the base film. did.

WVTR
(g/m² day) WVTR after 7 days
(g/m² day) Transmittance (%) at 550nm Surface roughness (nm) Example 1 1.85 × 10 ^-1 1.2 × 10 ⁰ 91.2 0.5 Example 2 9.44 × 10 ^-2 9.5 × 10 ^-1 91.3 0.6 Example 3 7.58 × 10 ^-2 7.4 × 10 ^-1 90.7 0.6 Example 4 2.62 × 10 ^-1 1.9 × 10 ⁰ 91.0 0.6 Example 5 2.4 × 10 ⁰ 4.2×10 ⁰ 88.1 2.5 Example 6 7.6 × 10 ^-1 2.9×10 ⁰ 87.2 3.3 Comparative Example 1 6.4 × 10 ^-1 5.1 × 10 ⁰ 90.2 0.8 Comparative Example 2 4.7 × 10 ⁰ 9.1 × 10 ⁰ 89.5 1.5

As described above, the present invention has been described with specific details and limited examples and drawings, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is not limited to the above embodiments. Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (19)

The absorbance (AU) of the Si-O peak in the wavelength region of ^{1060 cm -1} was obtained by converting the layer containing the polysilazane compound to ultraviolet ozone treatment at room temperature and atmospheric pressure, and analyzing the spectrum by infrared spectroscopy (FT-IR). , a polysilazane layer having an absorbance (AU) of a Si-N peak in a wavelength region of 840 cm ^{-1 ;}
an organic film layer containing a nanopore body and a binder resin; and
base film;
includes,
The polysilazane layer is formed on the outermost layer with respect to the gas permeation direction,
Further comprising a bonding enhancing coating layer between the polysilazane layer and the organic film layer or between the polysilazane layer and the base film,
The gas barrier film has a gas barrier in which the difference between [Si-O] ₁₀₆₀ / [Si-N] ₈₄₀ measured 7 days after manufacture and the initially measured [Si-O] ₁₀₆₀ / [Si-N] ₈₄₀ is 2 or less. film. The method of claim 1,
The gas barrier film may include a polysilazane layer from a gas permeation direction; organic film layer; and a base film; a gas barrier film that is sequentially stacked. The method of claim 1,
The gas barrier film may include a polysilazane layer from a gas permeation direction; base film; and an organic film layer; a gas barrier film that is sequentially stacked. delete The method of claim 1,
The bonding enhancing coating layer is a gas barrier film formed by applying a curable resin composition. The method of claim 1,
The gas barrier film further comprising a protective coating layer on top of the polysilazane layer. 7. The method of claim 6,
The protective coating layer is a gas barrier film formed by applying a curable resin composition. The method of claim 1,
The polysilazane layer is a gas barrier film that satisfies Equation 1 below.
[Equation 1]
0.2 < [Si-O] ₁₀₆₀ /[Si-N] ₈₄₀ < 2
In the formula 1, [Si-O] ₁₀₆₀ is an absorbance (AU) of Si-O peak in the wavelength range of ^{1060cm -1, [Si-N]} 840 is a Si-N peak at a wavelength range of 840 cm ^-1 Absorbance (AU). delete The method of claim 1,
The polysilazane layer is a gas barrier film that is converted by irradiating a low pressure mercury lamp of 184 nm for 10 minutes to 2 hours under nitrogen and ozone atmosphere. The method of claim 1,
The base film is a gas barrier film that is a polymer film. The method of claim 1,
The nanoporous body is a gas barrier film selected from micropores having a pore size of 2 nm or less, mesopores having a level of 2 to 50 nm, and an ultraporous hybrid nanoporous body having both pore size regions. 13. The method of claim 12,
The nanoporous body is a gas barrier film which is a zeolite or an organic-inorganic hybrid nanoporous body. The method of claim 1,
The polysilazane layer has a thickness of 10 to 1000 nm,
The organic film layer has a thickness of 1 to 300 μm,
The base film is a gas barrier film having a thickness of 30 to 500 μm. 3. The method of claim 1 or 2,
A gas barrier film having a difference in water permeability (WVTR) of the gas barrier film and water permeability (WVTR) of 1 × 10 ¹ g/m 2 ·day or less compared to a gas barrier film having a polysilazane layer without UV ozone treatment. The method of claim 1,
The gas to be blocked is a gas barrier film that is moisture. The method of claim 1,
The gas barrier film has a transmittance of 90% or more at 550 nm and a surface roughness of 0.1 μm or less. a) forming an organic film layer containing nanopores and a binder resin on a base film;
b) forming a bonding enhancing coating layer on the organic film layer or on the other surface of the base film;
c) Forming a layer containing a polysilazane compound on the bond-promoting coating layer, and performing ultraviolet ozone treatment at room temperature and atmospheric pressure to analyze the spectrum by infrared spectroscopy (FT-IR), Si-O in a wavelength region of ^{1060 cm -1} Converting the polysilazane layer having the absorbance (AU) of the peak and the absorbance (AU) of the Si-N peak in the wavelength region of 840 cm ^{-1 ;} A method for producing a gas barrier film comprising:
The gas barrier film has a gas barrier in which the difference between [Si-O] ₁₀₆₀ / [Si-N] ₈₄₀ measured 7 days after manufacture and the initially measured [Si-O] ₁₀₆₀ / [Si-N] ₈₄₀ is 2 or less. A method for producing a film. 19. The method of claim 18,
In step c), the conversion treatment was performed by irradiating a low-pressure mercury lamp of 184 nm for 10 minutes to 2 hours under a nitrogen and ozone atmosphere.