KR101953732B1 - layered film for gas barrier having organic film layer containing nanoporous materials, and preparation method and use thereof - Google Patents

Abstract

The present invention relates to a process for producing an article-tailored gas barrier laminate film to be applied, which is capable of adsorbing the gas to be intercepted and adsorbed at a temperature and / or pressure when the gas barrier laminate film is applied to an article A first step of selecting a nanoporous material capable of removing 70% or more of the adsorbed material; And an inorganic film layer of dense structure blocking the permeation of the gas from the first surface side to the gas barrier film laminated film having the first surface exposed to the gas to be cut and the second surface adjacent to the article, And an organic film layer containing a nano-porous body selected in the first step and a binder resin capable of adsorbing the permeated gas without being blocked in the inorganic film layer, And a second step of producing the substrate without the dense inorganic film layer blocking the permeation of the gas.

Description

[0001] 1. Field of the Invention [0002] The present invention relates to a multilayer film for gas barrier film having a nano-porous body containing organic film layer, a method for producing the same,

The present invention relates to a gas barrier film laminated film having a nano-porous body containing organic film layer which can remove at least 70% of an adsorbate adsorbed at a temperature and / or a pressure when applying a gas barrier laminate film to an article, And a method for producing the same.

Plastic films are widely used as packaging materials. Recently, there is a demand to extend the shelf life in terms of distribution and cost as much as possible, and in order to preserve the taste and safety of packaged foods, high quality of the film packaging material is required.

A gas barrier film, that is, a functional film such as a gas barrier film has many uses as a food packaging material, but its use as an industrial material is also increasing. As industrial functional films, transparent conductive films coated with a conductive inorganic material on a PET film have been widely applied to transparent touch panels and the like. Demand for water vapor barrier films for solar cells and organic EL backsheets is also rising.

In recent years, organic EL, solar cell, and LCD have been demanding a higher level of high barrier performance and light transmittance along with the full-scale development of flexible devices using a plastic film as a substrate instead of a plate glass. Therefore, various techniques have been developed to improve both transparency and gas barrier properties.

Among them, a method of alternately laminating oil and inorganic thin films on a base film is most widely used. An inorganic thin film of dense structure such as aluminum oxide, silicon oxide, or silicon nitride is mainly used as an important material for shielding the gas. On the other hand, an organic layer is formed on one side or both sides of the inorganic thin film to protect the inorganic thin film, and the pinhole is blocked or the gas barrier performance is improved as a whole.

However, due to the structural problems of the organic materials, the existing organic layer has a sufficient size to allow the gas to pass therethrough microscopically. Therefore, there is a limit to greatly improve the gas shutoff capability. Further, even when an organic hybrid system is introduced to form a dense film structure, defects such as cracks after drying and curing are likely to occur when an inorganic layer is excessively introduced, thus obstructing the realization of a stable gas barrier film .

An object of the present invention is to provide an object-oriented product-tailored gas barrier laminate film excellent in gas barrier performance and excellent in transparency, a method for producing the same, and its use.

According to a first aspect of the present invention, there is provided a process for producing an article-tailored gas barrier film laminate film to be applied, comprising the steps of: adsorbing a gas to be intercepted and adsorbing the gas barrier laminate film at a temperature and a pressure A first step of selecting a nanoporous material capable of removing 70% or more of the adsorbed material; And an inorganic film layer of dense structure blocking the permeation of the gas from the first surface side to the gas barrier film laminated film having the first surface exposed to the gas to be cut and the second surface adjacent to the article, And an organic film layer containing a nano-porous body selected in the first step and a binder resin capable of adsorbing the permeated gas without being blocked in the inorganic film layer, And a second step of producing the gas-barrier laminate film without the dense inorganic film layer blocking the permeation of the gas.

The second aspect of the present invention is a laminated film for gas-shielding an object-to-be-applied product having a first surface exposed to a gas to be shielded and a second surface adjacent to the article, wherein the gas- A dense structure of an inorganic film layer for intercepting; And a nano-pore structure capable of adsorbing the permeated gas without being blocked by the inorganic film layer and capable of removing 70% or more of the adsorbed adsorbed at a temperature and a pressure at the time of applying the gas- And an organic film layer containing a binder resin, wherein the organic film layer has no dense inorganic film layer blocking the permeation of the gas on the second surface thereof. Thereby providing a laminated film.

In a third aspect of the present invention, there is provided a gas-barrier laminate film for gas-shielding according to the second aspect of the present invention, wherein the second surface of the laminate film is gas- And a step of applying the gas barrier film laminate film to the article.

Hereinafter, the present invention will be described in detail.

As used herein, the term " adsorption " is a concept that includes both adsorption as well as adsorption and sorption.

The conventional gas barrier film has a multilayer thin film structure in which oil and inorganic film layers are alternately laminated. The organic film layer can protect the inorganic film layer while blocking the pinhole, or can function as a gas barrier layer as such. The organic film layer is made of a resin substrate, which has a structural pore size sufficient to allow gas to pass through the substrate, and thus has a limitation in gas barrier ability.

On the other hand, there is a gas barrier film in which an adsorption layer and a gas barrier layer are sequentially laminated on at least one surface of a gas barrier film having an inorganic thin film layer, but the thickness of the gas barrier film becomes thick due to a separate gas barrier layer, There is a problem that flexibility is lowered. In this case, when the thickness of the gas barrier film is reduced in order to improve transparency and / or flexibility, there is a problem that the degree of gas barrier is lowered.

On the other hand, if the gas barrier layer is not present on at least one side of the adsorption layer, the adsorption layer is exposed to the surrounding environment before application of the gas barrier film to the article or before application to the article, There is a problem that it can not be inactivated.

Therefore, the present invention solves the above-mentioned problem that the gas barrier layer which does not adversely affect transparency and / or flexibility on one side of the adsorbent layer is not applied to reduce the manufacturing cost due to simplification of the structure, The adsorbed adsorbed material can be removed in an amount of 70% or more, preferably 80% or more, more preferably 90% to 99.9%, in the temperature / pressure condition when the gas barrier film is applied to articles. The nanoporous materials are selectively applied to the adsorption organic layer and the adsorbed material adsorbed on the nanoporous material can be removed under heating and / or reduced pressure conditions to form the laminated inorganic thin film layer and the adsorption organic layer Characterized in that the gas barrier layer film is applied to the article such that the inorganic thin film layer is directed to the exposed surface and the adsorption organic layer is directed to the article. Further, by applying the nano-scale adsorbing porous body to the adsorption organic layer, the gas barrier performance can be improved to 2 to 1000 times without significantly decreasing the transparency of the gas barrier laminate film.

Further, when the inner side (or the second side) of the gas barrier film laminate film and the opposite side face thereof are referred to as the outer side (or the first side) of the gas barrier laminating film, An inorganic film layer of dense structure blocking the gas permeation from the outside (or the first side) of the barrier laminate film; And an organic film layer containing a nano-porous body and a binder resin capable of adsorbing permeated gas not blocked in the inorganic film layer are stacked in this order, the inorganic film layer is exposed to a gas which is intended to be blocked earlier than the organic film layer The blocking performance of the inorganic film layer can be increased by 2 to 1,000 times by the nano-pores-containing organic film layer which has not been inactivated, so that the thickness of the inorganic film layer can be reduced by 1.1 to 3 times As well as the transparency of the gas barrier laminate film can be maintained. In addition, it is possible to drastically reduce the risk of occurrence of pinholes and cracks, which are likely to occur as the inorganic film layer becomes thick.

Particularly, in the present invention, when organic-inorganic hybrid nanoporous materials are contained as the nanoporous material, it is found that the organic hybrid nanoparticles are well dispersed in the resin in the primary particle state without aggregation Respectively. Due to the high dispersibility of the organic / inorganic hybrid nanoporous material, the transparency of the entire film can be increased by increasing the light transmittance, and the gas adsorption characteristics of the organic hybrid nanoporous material can be easily exhibited to substantially disperse the organic / inorganic hybrid nanoporous material It is confirmed that the gas barrier ability is increased 5 times or more as compared with the conventional gas barrier film in which the organic film layer and the inorganic film layer are laminated.

Therefore, according to the present invention, an object-gas-barrier laminate film for application to an object to be applied having a first surface exposed to a gas to be shielded and a second surface adjacent to the article,

An inorganic film layer of dense structure for blocking permeation of the gas; And

The adsorbent adsorbed at the temperature or pressure when the gas barrier film laminate film is applied to the article is not less than 70%, preferably not less than 80%, more preferably not less than 80% More preferably 90% to 99.9%, and an organic film layer containing a binder resin,

And the second surface of the organic film layer does not have a dense inorganic film layer blocking the permeation of the gas.

Conventionally, inorganic porous materials such as zeolite, mesoporous and clay have been reported as adsorbents for moisture.

The moisture adsorption characteristics of the porous material can be divided into four types depending on the amount of adsorption depending on the relative humidity at the isotherm of water (H ₂ O). First, in the case of an adsorbent strongly adsorbing water, the adsorption amount of water increases sharply at a relative humidity (p / p ₀ ) of 0.1 or lower (representative pores are zeolites having fine pores) In the case of the adsorbent, the amount of moisture adsorption increases rapidly at a relative humidity (p / p ₀ ) of about 0.1 to 0.3. On the other hand, an adsorbent having a moisture adsorption characteristic slightly lower than the middle exhibits an abrupt increase in moisture adsorption amount in the range of relative humidity (p / p ₀ ) 0.3 to 0.6, and finally, At a humidity (p / p ₀ ) of 0.7 or more, the amount of moisture adsorption increases sharply.

On the other hand, the desorption characteristics of water tend to be opposite to the adsorption characteristics to moisture. Specifically, when the adsorbing force against moisture is strong, such as zeolite, desorption occurs at a high temperature of 200 ° C or higher, and when the adsorption force is somewhat lower than that of the hybrid nanoporous organic material, it may be desorbed at 150 ° C or lower. In addition, the degree of desorption can be varied depending on the adsorption characteristics depending on the type of the organic hybrid nanoporous material.

The nanoporous material used in the present invention may be a zeolite or an organic hybrid nanoporous material.

Zeolites are generically referred to as crystalline aluminosilicates. Various zeotype molecular sieves have been known in which silicon or aluminum is replaced with various other elements in place of silicon (Si) and aluminum (Al), which constitute the skeletal structure of zeolite. For example, there have been proposed alumina (AlPO ₄ ) -based zeolite analogues in which aluminum is completely removed from porous silicalite and silicon is replaced by phosphorus, and Ti, Mn, Co, Fe And zeolite analogs obtained by partially substituting various metal elements such as Zn are known. Examples of the MFI-structured zeolite or analogue thereof include ZSM-5, silicalite-1, TS-1, AZ-1, Bor-C, Boralite C, Nucilite, FZ-1, LZ- H-ZSM-5, mucinite, NU-4, NU-5, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH and ZKQ-1B. 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 only silica (SiO ₂ ) structure. TS- Zeolite of the MFI structure. As described above, although the adsorption and desorption properties are opposite to each other and zeolite has a good adsorption property, it is difficult to desorb easily in the process of applying the gas barrier laminate film to the article, and the property of easy desorption at high temperature The zeolite can not be utilized in the case where the high-temperature heat treatment is difficult due to the characteristics of the article.

Organic hybrid nanoporous materials are generally referred to as " porous coordination polymers " (Angew. Chem. Intl. Ed., 43, 2334. 2004], or "metal-organic frameworks" (MOF).

The organic / inorganic hybrid nanoporous material is a porous organic / inorganic polymer compound formed by bonding a central metal ion to an organic ligand through molecular coordination and contains both organic and inorganic materials in the skeleton structure and has a molecular size or nano-sized pore structure Crystalline compound. The organic / inorganic hybrid nanoporous material containing a polar metal ion and a carboxylic acid oxygen anion in the crystalline skeleton and coexisting with a non-polar aromatic compound group may have both hydrophilicity and hydrophobicity.

Since the organic / inorganic hybrid nanoporous material has high surface area and molecular size 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 molecules using pores. At this time, the pore size of the organic / inorganic hybrid nanoporous material can be controlled by controlling the length and / or the type of the ligand.

The organic or inorganic hybrid nanoporous material 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, furan dicarboxylic acid anion, pyridine dicarboxylic acid anion, benzenetricarboxylic acid, thiopendicarboxylic acid anion and pyrazole dicarboxylic acid anion It can be one or more selected.

In addition, the organic / inorganic hybrid nanoporous material may be an organic or inorganic hybrid nanoporous material having a skeleton, a surface or an unsaturated metal coordination site in the pores. Wherein the organic or inorganic hybrid nanoporous material has at least one selected from the group consisting of chromium ion, iron ion, nickel ion, cobalt ion, molybdenum ion, manganese ion, copper ion, magnesium and zinc ion and zirconium ion Metal ions.

The unsaturated metal coordination site may be formed in the skeleton or may be formed in a metal ion or an organic metal compound existing in the surface or pores of the organic hybrid nanoporous material. The unsaturated metal coordination site is a ligand coordinated to the metal ion of the organic or inorganic hybrid nanoporous material, typically, a coordination site of a metal from which water or an organic solvent has been removed, and means a position where another ligand can form a coordination bond again do. The unsaturated metal coordination site may be formed by removing water or a solvent molecule or ligand other than water contained in the organic hybrid nanoporous material. In order to secure an unsaturated metal coordination site of the organic / inorganic hybrid nanoporous material, it may be preferable to proceed with a pretreatment step of removing water or solvent components bound to the unsaturated metal coordination site.

The pretreatment can be carried out by any method as long as it can remove water or a solvent component without causing deformation of the organic hybrid nanoporous material. For example, the pretreatment can be achieved by heating at a temperature of 100 ° C or higher under reduced pressure, But it is not limited thereto. Or a method of removing a solvent known in the art, such as vacuum treatment, solvent exchange, ultrasonic treatment and the like. MIL-100, MIL-101, MOF-74, Cu-BTC, MIL-127, CPO-27 and the like are typical examples of the organic hybrid nanoporous material which can secure an unsaturated metal site through heat treatment as described above .

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

The organic / inorganic hybrid nanoporous material containing a hydrophilic OH group ligand, which is weaker than the unsaturated coordination metal ion site in the skeleton, exhibits a very weak interaction with polar molecules such as water, so that it is effective as a moisture adsorbent, So that water can be desorbed and regenerated.

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

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

On the other hand, not only is the desired degree of gas blocking depending on the use, part and material of the article, but also the permissible temperature and / or pressure range varies depending on the material and / or the manufacturing method of the article.

In the gas barrier laminate film according to the present invention, the nanoporous material is selected and used in a product-customized manner. That is, depending on the article, when the gas barrier laminate film is applied to an article, the permissible temperature and / or pressure which does not adversely affect the original performance of the article are different. In addition, the temperature and / or pressure at which more than 70% of the adsorbed material adsorbed per nano-pore-forming material type can be removed are different. Accordingly, the present invention selects nanoporous materials capable of removing 70% or more of the adsorbed adsorbed material when the temperature and pressure are determined when the gas barrier laminate film is applied to an article. For example, when a gas barrier laminate film is applied on an organic layer of an article, the gas barrier laminate film must be applied on the article at a temperature lower than the glass transition temperature or decomposition temperature of the organic layer, Select nanoporous materials that can remove 70% or more of adsorbate.

In the case where the nanoporous material is an organic hybrid nanopore, depending on the central metal ion, depending on the organic ligand, the temperature and / or pressure at which more than 70% of the adsorbed material adsorbed depending on the concentration of the unsaturated metal coordination site can be removed can do. The zeolite can also be different depending on the constituent elements, pore size and type thereof.

The gas barrier film laminated film according to the present invention may further comprise a plastic substrate on the first surface side of the inorganic film layer.

Preferably, the gas barrier laminate film according to the present invention may further comprise an undercoat layer between the plastic substrate and the inorganic film layer.

1, the gas barrier laminate film according to the present invention is characterized in that a flow of the gas to be intercepted is formed on the outer side (or the first side) of the gas barrier laminating film to the inner side of the gas barrier laminating film Second surface), from the outside (or the first surface)

Plastic substrates; An undercoat layer; An inorganic film layer of a dense structure blocking the gas permeation; And an organic film layer containing a nano-porous body and a binder resin capable of adsorbing the permeated gas not blocked in the inorganic film layer,

The inorganic film layer may be exposed to the gas to be blocked earlier than the organic film layer.

As an embodiment, the gas barrier film laminated film according to the present invention may have an outer side (or a first side)

Plastic substrates; An inorganic film layer of a dense structure blocking the gas permeation; And an organic film layer containing a nano-porous body and a binder resin capable of adsorbing the permeated gas not blocked in the inorganic film layer,

The inorganic film layer may be exposed to the gas to be blocked earlier than the organic film layer.

As a preferred embodiment, the gas barrier film laminate film according to the present invention may be one in which two sets or more of one set including the inorganic film layer and the organic film layer are sequentially laminated.

In a preferred embodiment, in the gas barrier film laminate film according to the present invention, the inorganic film layer includes an organic film layer not containing the nano-porous body between two inorganic film layers of dense structure blocking gas permeation .

In the case of nanoporous materials, the capability of absorbing gases including moisture is limited to a certain level. Therefore, when the nanoporous material is exposed to an excessive amount of gas to be initially absorbed, the amount of adsorbed nanoporous material I can not help but lose performance. In the present invention, when the flow of the gas to be intercepted is from the first surface to the second surface, from the first surface side, due to the order in which the inorganic film layers are laminated first and then the organic film layers are laminated, It is possible to maintain the gas blocking performance of the film for a long time and to improve the gas blocking performance of the film by itself by preventing most of the gas in the inorganic film layer and then adsorbing the remaining residual gas without blocking in the organic film layer (Fig. 3).

The " organic film layer " in the present invention may mean a thin film-like structure containing an organic substance. The organic film layer may be a concept including not only a film layer containing an organic substance as a main component but also a film layer containing a small amount of organic matter. The organic material of the organic film layer may be derived from a binder resin or may be derived from an organic ligand contained in an organic hybrid nanoporous material (MOF) structure. The organic film layer may be formed by a wet coating method.

In the present invention, the organic film layer may contain a nano-porous body and a binder resin capable of adsorbing the permeated gas without being blocked in the inorganic film layer. In one embodiment, the organic film layer may contain an organic binder resin and an organic or inorganic hybrid nanoporous material dispersed in the resin.

The binder resin may be an organic binder resin, an inorganic binder resin, or an organic binder resin.

The organic binder resin may be a resin serving as a binder, a gas barrier resin, or a gas (e.g., moisture) adsorbing resin. Examples of the gas barrier resin include polyolefin 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 resins (PAR); Polytetrafluoroethylene resins (PTFE); Vinylidene fluoride resin (PVDF); Vinyl fluoride resin (PVF); Polyvinyl chloride resin (PVC); Polyvinylidene chloride resin (PVDC) or the like. The water-absorbent resin may be selected from the group consisting of polyacrylic acids (polyacrylic acid and polymethacrylic acid), polyalkylene oxides (polyethylene oxide, polypropylene glycol and polypropylene oxide), celluloses (methylcellulose, ethylcellulose, hydroxyethyl Cellulose starch, starch, starch, soluble starch such as dextrin), polyacrylic acid amides (such as polyacrylamide, polymethacrylic acid, Amide), gelatin (gelatin, phthalated gelatin, etc.), alginic acid (alginic acid, sodium alginate, etc.), vinyl alcohols (polyvinyl alcohol, ethylene-vinyl alcohol copolymer), poly 2- , Polyvinyl pyrrolidone, polyvinylimidazole, polyoxazoline, isobutylene maleic anhydride copolymer, One member selected from light, silica gel, Kara past, agarose, kaolin, polystyrene sulfonic acid, agar, xanthan gum or the like can be greater. 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.

As the organic binder resin, 0.1 to 150 parts by weight of an organic binder resin may be mixed with 100 parts by weight of colloidal inorganic particles. 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 gas barrier film laminate film according to the present invention may contain a binder resin and a nanoporous material dispersed in the resin, wherein the nanoporous material is dispersed in the primary particle state without aggregation in the binder resin to provide a transparent organic film layer.

The binder resin used for the organic film layer in the gas barrier film laminate film according to the present invention is characterized in that there is a space that allows gas to pass through when forming the film, A porous body may be selected and dispersed in the binder resin so that an organic film layer having a dense film structure is formed.

In the present invention, the nanoporous material is a microporous material having a pore size of 2 nm or less (e.g., zeolite), a mesoporous material having a size of 2 to 50 nm (e.g., mesoporous carbon and nanosilica) And may be a hybrid nanoporous material having a super porous property.

The average particle size of the primary particles of the nanoporous material may be 10 nm to 1,000 nm, and may be varied depending on the type of the nanoporous material.

In the present invention, the organic film layer may have a film thickness of 1 탆 to 300 탆, preferably 2 탆 to 30 탆. The organic film layer serves as a gas barrier and a protective film for the inorganic film layer while serving as a matrix in which the nanoporous material can be dispersed in the thickness range.

The thickness of the organic film layer can be adjusted so that 70% or more of the adsorbed matter adsorbed in the nano-porous body in the organic film layer can be removed at the temperature and pressure when the gas barrier laminate film is applied to the article, As the thickness of the layer becomes thicker, it is preferable that the adsorbent removal ability is high in the nanoporous material.

In the present invention, the inorganic film layer may mean a thin film-like structure in which an inorganic material is a main component. The inorganic film layer may include an organic film layer that does not contain the nanoporous material between two inorganic film layers of a dense structure blocking permeation of gas.

The inorganic film layer may be formed by a dry coating method, but is not limited thereto. For example, the inorganic film layer may be formed by physical vapor deposition (vacuum deposition, ionization deposition, sputtering, ion beam deposition, etc.) or chemical vapor deposition (plasma CVD, thermal CVD, CVD method (gas source CVD) or the like).

Examples of the vacuum deposition method include a resistance heating method, a high frequency induction heating method, an electron beam heating method, an arc discharge method, a laser ablation method, and a molecular beam epitaxy method. Examples of the ionization deposition method include a DC ion plating method, an RF ion plating method (plasma polymerization method), an activation reactive deposition method, and a cluster ion beam method. Examples of the sputtering method include a DC magnetron method, an AC magnetron method, a dual magnetron method, an ion beam sputtering method, and an ECR sputtering method. Examples of the ion beam method include an ion beam deposition method, an ion beam assist method, and an ion beam sputtering method.

The inorganic film layer is not particularly limited as long as it is transparent and has gas barrier properties. Examples of the inorganic film include inorganic oxides (MOx), inorganic nitrides (MNy), inorganic oxynitride (MOxNy), inorganic oxide carbides (MOxCz) Carbide (MNyCz), and inorganic oxide nitrified carbide (MOxNyCz). Wherein O represents an oxygen atom, N represents a nitrogen atom, C represents a carbon atom, and M represents a metal element. Specific examples of the metal element M include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B) , Lead (Pb), zirconium (Zr), and yttrium (Y). In the present invention, the inorganic oxides, inorganic nitrides, inorganic oxides nitrides, inorganic oxides carbides, inorganic nitrides carbides and inorganic oxides nitrides include those having x, y and z values less than a predetermined chemical equivalent. From the viewpoints of transparency and gas barrier properties, the inorganic film layer is preferably an inorganic oxide (MOx), an inorganic nitride (MNy) or an inorganic oxynitride (MOxNy) composed of silicon (Si) and a metallic element M of aluminum (Al) ). Of these, silicon oxide and aluminum oxide are particularly preferable.

In the present invention, the inorganic film layer may have a film thickness of 30 nm to 1,000 nm. By having the inorganic film layer have a relatively thin thickness in the above range, it is possible to provide a transparent inorganic film layer.

In the present invention, the plastic substrate may be a plastic substrate which is transparent and can be formed into a film. Specifically, the plastic substrate may be an ester-based polymer such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN); Cellulosic polymers such as diacetylcellulose or triacetylcellulose; Carbonate-based polymers such as polycarbonate (PC); Acrylic polymers such as poly (methyl) methacrylate; An acrylic resin such as an acrylic resin having an aromatic ring or a lactone modified acrylic resin; Styrenic polymers such as polystyrene or acrylonitrile-styrene copolymer; Olefin-based polymers such as polyethylene, polypropylene, cyclo-olefin polymer (COP) or ethylene-propylene copolymer; Vinyl chloride type polymers; Amide-based polymers such as nylon or aromatic polyamide; Imide polymers; Sulfonic polymers; Polyether sulfone type polymers; Polyether ether ketone type polymers; Polyphenylene sulfide type polymers; Vinyl alcohol type polymers; Vinylidene chloride polymers; Vinyl butyl aldehyde type polymers; An arylate-based polymer; Polyoxymethylene polymers; Epoxy-based polymers; Or blend polymers obtained by blending them. Preferably, polyethylene terephthalate, which is advantageous as a transparent film at a price, or a film formed from poly (methyl) methacrylate or triacetyl cellulose, which is advantageous in light resistance and weather resistance, as a raw material can be used.

In the present invention, the undercoat layer can improve the bonding force between the plastic substrate and the inorganic film layer, flatten the substrate surface, improve the overall strength of the film, and improve the light transmittance. Specifically, the undercoat layer may be formed of a resin such as a polyester resin, a polyamide resin, a polyurethane resin, an epoxy resin, a phenol resin, a (meth) acrylic resin, a polyvinyl acetate resin, a polyolefin resin such as polyethylene or polypropylene , Or a resin composition containing the copolymer as a main component of a vehicle, a modified resin, a cellulose-based resin, or the like.

As a preferred embodiment, the gas barrier laminate film according to the present invention may be moisture, oxygen, nitrogen, carbon dioxide, HF, or the like.

In a preferred embodiment, the gas barrier laminate film according to the present invention may be flexible.

As a preferred embodiment, the gas barrier laminate film according to the present invention may be used for packaging, packaging or sealing. As a preferred embodiment, the gas barrier laminate film according to the present invention may be for packaging, packaging or sealing food packaging, drug packaging, organic devices, and electric / electronic devices.

The method for producing an article-customized gas barrier laminate film to be applied according to the present invention comprises

A first step of selecting a nano-porous body capable of adsorbing the gas to be intercepted and capable of removing 70% or more of the adsorbed material adsorbed at a temperature and / or a pressure at the time of applying the gas- step; And

An inorganic film layer of dense structure blocking the permeation of the gas from the first surface side to the gas barrier film laminated film having the first surface exposed to the gas to be shielded and the second surface adjacent to the article; And an organic film layer containing a nano-porous body selected in the first step and a binder resin capable of adsorbing the permeated gas without being blocked in the inorganic film layer, A second step of manufacturing without a dense inorganic film layer blocking the permeation of the gas

.

In the second step, the organic film layer may be formed by coating a nano-porous body-containing coating liquid on the second surface of the inorganic film layer.

In order to form a transparent organic film layer, it is preferable to maintain a state in which the nano-impregnated body is dispersed in the primary particle size during the manufacturing process of the gas barrier film laminated film according to the present invention.

The formation of the organic film layer can be performed by applying a coating liquid in which the nano-particles are uniformly dispersed in an organic solvent or a monomer, an oligomer, or a polymer of a binder resin. At this time, the monomer or oligomer of the binder resin may be UV-curable, and may be film-formed after curing by UV irradiation.

In forming the organic film layer, the coating may be performed by a roll coating, a slot die coating, a bar coating, a dip coating, or a spin coating.

The present invention also provides a method of manufacturing a gas barrier film, comprising the steps of: (a) applying a second surface of a gas barrier film laminated film according to the present invention to an article under conditions capable of removing adsorbed matter adsorbed on the nano- And a method of producing an article to which a gas barrier film laminated film is applied.

The present invention also provides a method for producing a gas-barrier laminate film for a gas-shielding laminate, comprising the steps of: applying a gas-barrier laminate film to a substrate, It is possible to provide an article to which a gas barrier laminate film is applied in a manner to be applied.

The article may be one in which the gas barrier laminate film is applied flexibly in correspondence with the shape of the article.

In the present invention, the article may be a food, a medicine, an organic element or an electric and electronic element, but is not limited thereto.

The gas barrier degree and / or the transparency required depending on the use, the site and the material of the article are different.

BACKGROUND ART Flexible plastic films are used for substrates such as organic EL and solar cells, and barrier properties are required. The barrier properties required in the electronics field are more stringent than the barrier properties required in the food packaging sector by several orders of magnitude.

In order to increase the longevity of solar cells, organic EL, etc., improvement of durability of module is a problem, and there is improvement of water vapor and oxygen barrier property of used materials.

Table 1 shows the barrier levels for various solar cells.

[Table 1]

The permissible water vapor permeability of the organic EL is 10 ^-5 to 10 ^-6 g / m 2 / day and the oxygen permeability is reported to be 10 ^-4 to 10 ^-6 cc / m 2 / day / atm.

The barrier film for organic EL can be classified into a substrate side and a sealing side as shown in Fig. A barrier film is not required for the substrate side when glass is used, but it is necessary when a plastic substrate is used. Glass bags and metal bags have been studied for the bag side, but glass and metal bags are bulky, lacking in flexibility and lack of transparency There is a problem that it can not cope with the flexibility. Therefore, the gas barrier laminate film according to the present invention can be applied to the solution even in the encapsulation.

In the case of switching from a glass substrate to a film substrate, since a display defect (black spot) occurs and a driving voltage fluctuates when bubbles enter the liquid crystal layer due to intrusion of moisture and gas into the liquid crystal layer, a gas barrier layer is required . Therefore, it has been reported that the required gas barrier property is in the range of WVTR = 10 ^-2 to 10 ^-1 g / m 2 / day and OTR = 10 ^-2 to 10 ^-1 cc / m 2 / day / atm, Order high gas barrier film is required.

When the TFT is formed, since the electrode layer which is a constituent layer of the TFT is easily deteriorated by water vapor and oxygen, WVTR = 10 ^-3 to 10 ^-2 g / m 2 / day, OTR = 10 ^-3 to 10 ^-2 cc / / day / atm and an additional 1 order higher barrier property than the TFT-free configuration.

Therefore, the present invention can provide a nano-porous organic-inorganic hybrid film which is required to have a dense structure of inorganic film layers blocking the gas permeation by a factor of 2 to 1000, It is possible to reduce the degree of gas blocking and thickness of the inorganic film layer itself in the production of the gas barrier laminate film having various gas barrier properties, thereby providing improved flexibility and transparency to the gas barrier laminate film.

The gas barrier film laminate film according to the present invention is characterized in that a nanoporous material capable of removing 70% or more of adsorbed material at a specific temperature and pressure according to an object to be applied is selected, and an inorganic thin film layer and a nano- The inorganic film layer for gas shielding is exposed to the gas to be blocked earlier than the organic film layer for adsorption by applying the gas barrier laminate film to the article so that the inorganic thin film layer faces the exposed surface and the adsorption organic layer faces the article, The adsorption layer can exhibit its function even if there is no gas barrier layer on one side of the adsorption organic film layer. Therefore, the manufacturing cost due to the simplification of the structure can be reduced and the transparency and / Or flexibility can be improved.

1 is a conceptual view schematically showing a sectional structure of a gas barrier film laminated film according to an embodiment of the present invention.
2 is a conceptual view schematically showing a sectional structure of a gas barrier film laminated film according to another embodiment of the present invention.
3 is a conceptual diagram schematically showing a gas exposure sequence of each film layer according to the introduction direction of the exposure gas to the gas barrier film laminate film of the present invention.
4 shows various barrier films of organic EL.
FIGS. 5 and 6 are the results of examining the gas barrier properties of the gas barrier laminate films produced in Example 1 and Comparative Examples 1 and 2. FIG.
Fig. 7 shows the gas barrier properties of the gas barrier laminate films prepared in Examples 1 and 2. Fig.

Hereinafter, the present invention will be described in more detail with reference to Examples. These embodiments are only for describing the present invention more specifically, and the scope of the present invention is not limited by these examples.

Example  1: MOF containing organic The film layer  Production of gas barrier film

As a transparent plastic film used, a polyethylene terephthalate (PET) film (SKC Co., Ltd., Korea) having a thickness of 100 μm was used, and a general-purpose acrylate ultraviolet curable resin was used on one side of the film, To form an undercoat layer. At this time, microgravure method was applied to the head applied to the coating.

On the undercoat layer of the plastic substrate, an SiNx thin film was formed to a thickness of 120 nm as an inorganic film layer as described below.

The ECR PE-CVD method, which combines electron cyclotron resonance (ECC) and plasma chemical vapor deposition (CVD) techniques, was used. A 2.45 GHz microwave wave was generated at a power of 1500 W under an initial vacuum of 10 ^-5 Torr SiH ₄ and NH ₃ gas were mixed as a thin film growth reaction gas, and Ar gas was used as a diluting gas.

MIL-100 (Fe), a kind of MOF, was selected as a nanoporous material which can be removed by 80% or more under 40 ° C vacuum condition.

MIL-100 (Fe) was added in an amount of 3% by weight based on the weight of the total coating solution, and a mixed solution of cycloaliphatic epoxy resin and acrylate as the organic binder resin was prepared by using a mixed solvent of PGME (Propylene Glycol Methyl Ether) and Toluene, The resin was added in an amount of 45% by weight based on the weight of the total coating liquid and uniformly mixed to prepare an organic film layer coating liquid. The organic film layer coating liquid prepared as described above was coated on the inorganic film layer by a Meyer bar coating method and dried at 100 ° C for 10 minutes using a movable dry oven to form an organic film layer.

The thickness of the inorganic film layer was 120 nm and the thickness of the organic film layer was 7 占 퐉 in the gas barrier film laminate film prepared as described above.

Example  2: zeolite-containing organic The film layer  Production of gas barrier film

Except that 4A zeolite having a specific surface area of 300-400 m ² / g was used as the LTA structure instead of MOF in the organic film layer coating liquid and the size of the fine pores was 4 Å. A laminated film for use was produced.

Comparative Example  1: MOF free organic The film layer  Production of gas barrier film

A gas barrier laminate film was prepared in the same manner as in Example 1, except that MOF was not added to the organic film layer coating liquid.

Comparative Example  2: The organic film layer  Production of gas barrier film

Except that only an undercoat layer and an SiNx inorganic film layer were formed on a polyethylene terephthalate (PET) film having a thickness of 100 탆, and an organic film layer was not formed. Respectively.

Comparative Example  3: The organic film layer The inorganic film layer On the opposite side  Production of the formed gas barrier laminate film

A gas barrier laminate film was prepared in the same manner as in Example 1, except that the organic film layer was formed on the transparent substrate film opposite to the inorganic film layer.

Experimental Example  1: Organic Film layer  Dispersion of MOF

As a result of examination of the dispersibility of MOF in the organic film layer in the gas barrier film laminated film of Example 1, it was confirmed that the organic hybrid nanocomposite was well dispersed in the resin in the primary particle state. Further, the better the dispersion degree of MOF, the lower the haze and the better the gas barrier property.

Experimental Example  2: All-light transparency of the gas barrier film laminated film of the present invention

The transparency of the gas barrier laminate film produced in Example 1 and Comparative Example 1 was examined as follows.

The U4100 model of Hitachi High-Technologies in Japan was used, and the transparency was measured at a measurement wavelength range of 240 to 2,600 nanometers using a tungsten filament and deuterium lamp as the light source.

The gas barrier film of Example 1 had a transparency of 88.0%, and the gas barrier film of Comparative Example 1 had a transparency of 88.9%. From the above transparency results, it can be confirmed that when the nanoporous material such as MOF is included in the organic film layer in a well dispersed state, the influence on the luminous transmittance is small and the excellent optical characteristics are maintained. If the total light transmittance is 85%, it can be used for optical applications such as displays. If the transmittance is 50%, it can be used as a transparent material for food packaging.

Experimental Example  3: Gas blocking performance of the gas barrier laminate film of the present invention

(H ₂ O) gas barrier properties of the gas barrier laminate films produced in Examples 1 and 2 and Comparative Examples 1 and 2 were examined.

Using the 'Delta Perm' equipment manufactured by Technolox, UK, to increase the accuracy of the measurement, the measurement sample was placed in the equipment before the measurement, and the film sample was left under the vacuum condition of 40 ° C. for 2 hours, (WVTR: Water Vapor Transmission (WVTR)) was applied to only one side of the laminated film for gas barrier under the condition of temperature 40 ℃ and relative humidity 90% after outgassing process, Rate) was measured. The results are shown in Figs. 5, 6 and 7. Fig.

5, the gas barrier film laminate film of Example 1 was fabricated in the same manner as in Comparative Example 1, which corresponds to the existing gas barrier film in which the organic film layer and the inorganic film layer in which the organic hybrid nano- It can be seen that the gas barrier ability is increased by 5 times or more as compared with the laminated film for use in the present invention. Also, as shown in FIG. 6, it can be seen that when the organic film layer is first placed in the moisture gas supply portion, the nanoporous material hardly contributes to the improvement of gas barrier capability. This is because if the excessive gas supply does not first penetrate the inorganic film layer having a dense structure but enters the organic film layer having the nanoporous material first, the ability to control the moisture gas in the nanoporous material is saturated in a short time It can be seen that the effect of the organic film layer including the nanoporous material on the gas shutoff disappears.

On the other hand, when MOF (MIL-100) was used (Example 1) as compared with the case where zeolite was used as the gas-adsorbing nano-porous body in the gas barrier layered film (Example 2) It can be seen that water desorption is excellent through the take-out gas, and the gas blocking ability is about 4 times better.

Claims (21)

1. A method for producing a gas-barrier laminate film for an object-to-be-
A first step of selecting a nanoporous material capable of adsorbing the gas to be intercepted and capable of removing 70% or more of adsorbed adsorbed at a temperature and a pressure at the time of applying the gas barrier laminate film to an article; And
An inorganic film layer of dense structure blocking the permeation of the gas from the first surface side to the gas barrier film laminated film having the first surface exposed to the gas to be shielded and the second surface adjacent to the article; And an organic film layer containing a nano-porous body selected in the first step and a binder resin capable of adsorbing the permeated gas without being blocked in the inorganic film layer, A second step of manufacturing without a dense inorganic film layer blocking the permeation of the gas
Wherein the nano-impregnated body is an organic hybrid nanocomposite. delete The method of claim 1, wherein the nanoporous material is maintained in a state of being dispersed in a primary particle size during a manufacturing process for forming a transparent organic film layer. The manufacturing method according to claim 1, wherein in the second step, a coating liquid containing a nano-porous body is coated on a second surface of the inorganic film layer to form an organic film layer. The production method according to claim 4, wherein the nanoporous material is applied to a coating solution uniformly dispersed in an organic solvent or a monomer, oligomer or polymer of the binder resin. 1. A gas-shielding laminated film for gas-shielding an object to be applied, the gas-shielding laminate film having a first side exposed to a gas to be cut and a second side adjacent to the article,
From the first side,
An inorganic film layer of dense structure for blocking permeation of the gas; And
A nano-porous body capable of adsorbing permeated gas without being blocked by the inorganic film layer and capable of removing 70% or more of the adsorbed adsorbed at a temperature and pressure when applying the gas barrier film laminated film to an article, and And an organic film layer containing a binder resin,
Characterized in that the second surface of the organic film layer has no dense inorganic film layer blocking the permeation of the gas, and the nano-porous body is an organic / inorganic hybrid nanocomposite. delete The organic film layer according to claim 6, wherein the organic film layer contains a binder resin and a nanoporous material dispersed in the resin,
Characterized in that the nanoporous material is dispersed in a primary particle state without aggregation in the binder resin to provide a transparent organic film layer. [7] The method of claim 6, wherein the binder resin used in the organic film layer has a size enough to allow gas to pass through when the film is formed, and a nanoporous material having a particle size capable of being accommodated in the space is selected And an organic film layer having a dense film structure is formed by being dispersed in the binder resin. The laminated film for gas-shielding according to claim 6, wherein the inorganic film layer has a film thickness of 30 nm to 1,000 nm. The laminated film for gas-shielding according to claim 6, further comprising a plastic substrate on the first surface side of the inorganic film layer. The laminate film for gas-shielding according to claim 11, further comprising an undercoat layer between the plastic substrate and the inorganic film layer. 13. An object-to-be-applied substrate according to any one of claims 6 and 8 to 12, characterized in that two sets or more of one set including the inorganic film layer and the organic film layer are sequentially laminated Laminated film for blocking. The organic film layer according to any one of claims 6 and 8 to 12, wherein the inorganic film layer is an organic film layer containing no nanoporous material between two inorganic film layers of dense structure for blocking permeation of gas Wherein the gas-barrier laminate film is a laminate film. The laminated film for gas-shielding according to any one of claims 6 to 9, wherein the gas to be cut is moisture, oxygen, nitrogen, carbon dioxide, HF or a combination thereof. The laminated film for gas-shielding according to any one of claims 6 to 9, which is flexible. 13. The gas-shielding laminate film according to any one of claims 6 and 8 to 12, which is packaged, packaged or sealed. 13. The method according to any one of claims 6 and 8 to 12, wherein the blocking performance of the dense inorganic film layer blocking the permeation of gas is measured by the organic hybrid layer containing nanohybrid nano- The thickness of the inorganic film layer is 1.1 to 3 times smaller than that of the conventional gas barrier film in which the porous body is not dispersed and the inorganic film layer is 5 to 1000 times higher than that of the conventional gas barrier film The laminated film for gas-shielding, which is customized for the application subject to the characteristic. The second surface of the laminate film for gas-shielding according to any one of claims 6 and 8 to 12, wherein the second surface of the laminate film for gas-shielding for application is a pressure-reduced or warmed condition capable of removing adsorbed matter adsorbed on the nanoporous material Wherein the gas barrier laminate film is applied to an article. 20. The method of claim 19, wherein the article is a food, a medicine, an organic device, or an electrical or electronic device. 21. The method of manufacturing an article according to claim 20, wherein the gas barrier film laminate film is applied with flexibility in accordance with the shape of the article.

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