KR102089409B1 - Barrier film - Google Patents

Abstract

This application relates to a barrier film and its manufacturing method. In the present application, a barrier film having excellent barrier properties and optical performance may be provided. Barrier film of the present application, as well as packaging materials such as food and pharmaceuticals, FPD (Flat Panel Display) such as LCD (Liquid Crystal Display) or member for solar cells, electronic paper or OLED (Organic Light Emitting Diode) substrate or It can be effectively used in various applications such as sealing films.

Description

 Barrier film

The present invention relates to a barrier film and a method for manufacturing the same.

Barrier films are used for packaging materials such as food and pharmaceuticals, as well as for FPD (Flat Panel Display) such as LCD (Liquid Crystal Display) or for solar cells, substrates for electronic paper or OLED (Organic Light Emitting Diode) or sealing film It has been used for various purposes.

Conventional barrier films generally employ metal oxides or metal oxynitrides such as SiOx, AlOy, SiOaNb, AlOcNd, or Indium Tin Oxide (ITO) as a gas barrier inorganic thin film (Patent Document 1).

However, the above barrier film is vulnerable to moisture and exhibits a tendency to increase gas permeability with humidity.

KR 2014-007081 A

This application provides a barrier film.

This application relates to a barrier film. In the present application, the term barrier film may mean a film having a water vapor transmission rate (WVTR) in an intended range. For example, the barrier film has a moisture permeability of 10 g / m ² / day or less g / m ² / day or less, 8 g / m ² / day or less, 6 g or less at a temperature of 40 ° C. and a relative humidity of 90%. / m ² / day or less, 4 g / m ² / day or less, 2 g / m ² / day or less, 1 g / m ² / day or less, 0.5 g / m ² / day or less, 0.3 g / m ² / day Hereinafter, it may mean a layer of 0.1 g / m ² / day or less, or 0.05 g / m ² / day or less. The lower the moisture permeability means that the layer exhibits excellent barrier properties, the lower limit of the moisture permeability is not particularly limited. In one example, the lower limit of the moisture permeability is 0.00005 g / m ² / day or more, 0.0005 g / m ² / day or more, 0.001 g / m ² / day or more, 0.003 g / m ² / day or more, 0.005 g / m ² / day or more, 0.01 g / m ² / day or more, 0.015 g / m ² / day or more, or 0.02 g / m ² / day or more. The moisture permeability can be measured, for example, at a relative humidity of about 100% and a temperature of about 38 ° C.

The barrier film of the present application may include a barrier layer comprising a multi-component metal oxynitride containing silicon atom, tin atom, oxygen atom and nitrogen atom. The present inventors have confirmed that the barrier layer containing the above components at the same time exhibits excellent barrier properties, and that such barrier properties can be stably maintained without being influenced by an external environment such as humidity. In one example, the blocking layer may include the multi-component metal oxynitride as a main component. In the above, the blocking layer includes the multi-component metal oxynitride as a main component. The proportion of the multi-component metal oxynitride in the blocking layer is 55% or more, 60% or more, 65% or more, 70% or more based on weight, It may mean a case of 75% or more, 80% or more, 85% or more, or 90% or more. The weight ratio may be, for example, 100% or less, 99% or less, 98% or less, 97% or less, 96% or less, or 95% or less.

The multi-component metal oxynitride may include 5 to 30 atomic% silicon atom, 5 to 30 atomic% tin atom, 30 to 60 atomic% oxygen atom, and 0.2 to 15 atomic% nitrogen atom. More preferably, the multi-component metal oxynitride may include 10 to 30 atomic%, 15 to 30 atomic%, or 20 to 30 atomic% of the silicon atom. In addition, the multi-component metal oxynitride may suitably contain the tin atom in 10 to 30 atomic%, 15 to 30 atomic%, or 20 to 30 atomic%. In another suitable example, the multi-component metal oxynitride may include oxygen atoms at 35 to 60 atomic%, 40 to 60 atomic% or 40 to 55 atomic%. On the other hand, in another suitable example, the multi-component metal oxynitride may include 1 to 15 atomic%, 1.5 to 15 atomic%, 1.5 to 10 atomic%, or 1.5 to 6 atomic% nitrogen atoms.

The present inventors have confirmed that the performance of the barrier film is improved as the multi-component metal oxynitride contains the silicon atom, tin atom, oxygen atom, and nitrogen atom in the more appropriate ratio.

The thickness of the barrier layer including the multi-component metal oxynitride as described above is not particularly limited, and may be selected in consideration of desired performance or use. In one example, the thickness of the blocking layer may be selected within a range of about 10 nm to 1,000 nm.

The barrier film of the present application may further include a base film. In this case, the blocking layer may be formed on one side or both sides of the base film.

In the above, the type of the base film is not particularly limited. For example, polyethylene terephthalate (PET) films, polycarbonate films, polyester naphthalate films or polyester films such as polyarylate films, polyether film films such as polyether sulfone films, cycloolefin polymer films, polyethylene films, or Polyolefin films, such as a polypropylene film, a diacetyl cellulose film, a triacetyl cellulose film, or a cellulose resin film, such as an acetyl cellulose butylate film, a polyimide film, an acrylic film, an epoxy resin film, etc. can be illustrated. In the present application, the base film may be a single layer or a multilayer structure. The thickness of the base film may also be appropriately selected depending on the application, for example, within the range of 2 μm to 200 μm, within the range of 5 μm to 190 μm, within the range of 10 μm to 180 μm, between 20 μm to 180 μm It can be selected within the range of 20 μm or within the range of 20 μm to 150 μm.

The barrier film of the present application may further include an intermediate layer present between the base film and the barrier layer when the barrier layer is formed on one side or both sides of the base film. Such an intermediate layer can act, for example, as a so-called dielectric layer or planarization layer.

The intermediate layer includes, for example, at least one selected from the group consisting of acrylic resins, urethane resins, melamine resins, alkyd resins, epoxy resins, siloxane polymers, and / or condensates of organosilane compounds represented by the following formula (2) can do.

[Formula 2]

In Chemical Formula 1, X is hydrogen, halogen, alkoxy group, acyloxy group, alkylcarbonyl group, alkoxycarbonyl group or -N (R ₂ ) ₂ , wherein R ₂ is hydrogen or alkyl group, R ₁ is alkyl group, Alkenyl group, alkynyl group, aryl group, arylalkyl group, alkylaryl group, arylalkenyl group, alkenylaryl group, arylalkynyl group, alkynylaryl group, halogen, amino group, amide group, aldehyde group, alkylcarbonyl group, carboxy group, mercap Earthenware, cyano group, hydroxy group, alkoxy group, alkoxycarbonyl group, sulfonyl group, phosphoryl group, acryloyloxy group, methacryloyloxy group or epoxy group, Q is single bond, oxygen atom or- N (R ₂ )-, wherein R ₂ is a hydrogen atom or an alkyl group, and m may be a number in the range of 1 to 3.

As the organic silane, one or more types may be selected from the group consisting of compounds represented by Chemical Formula 2, and at this time, crosslinking may be possible when one type of organosilane compound is used.

Examples of the organic silane are methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane , Phenyldimethoxysilane, phenyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, tri Phenylethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, dimethylethoxysilane, dimethylethoxysilane, diphenylmethoxysilane, diphenyl Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-aminophenylsilane, allyltrimethoxysilane, n- (2-aminoethyl) -3-aminopropyltrimethoxy Thoxysilane, 3-amine pro Triethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyldiisopropylethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltri It can be selected from the group consisting of methoxysilane, n-phenylaminopropyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane and mixtures thereof.

In another example, the intermediate layer, pentaerythritol triacrylate (pentaerythritol triacrylate), hydroxyethyl acrylate (hydroxyethylacrylate), hydroxypropyl acrylate (hydroxyethylacrylate), polyethylene glycol monoacrylate (polyethyleneglycol monoacrylate), ethylene glycol mono Acrylate (ethyleneglycol monoacrylate), hydroxybutylacrylate, glycidoxymethacrylate, propyleneglycol monoacrylate, trimethoxysilylethyl epoxycyclohexane, trimethoxysilylethyl epoxycyclohexane, acrylic acid It may be formed by polymerizing at least one selected from the group consisting of (acrylic acid) and methacrylic acid.

As the epoxy resin that can be applied to the formation of the intermediate layer, one or more selected from the group consisting of alicyclic epoxy resins and aromatic epoxy resins can be used. As the alicyclic epoxy resin, for example, at least one selected from the group consisting of an alicyclic glycidyl ether type epoxy resin and an alicyclic glycidyl ester type epoxy resin may be used. Further, for example, Celloxide 2021P (Daicel) 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate (3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate) and its Derivatives can be used, they are stable, colorless, transparent, tough even at high temperatures, and have excellent adhesion and adhesion for lamination. Especially when used for coating, the surface hardness is excellent.

Examples of the aromatic epoxy resin include bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, fluorene-containing epoxy resin, and triglycidyl isocyanurate. One or more aromatic epoxy resins selected from the group may be used.

The intermediate layer may be, for example, a coating layer formed by a sol-gel reaction. For example, selected from the group consisting of SiOx (where x is an integer from 1 to 4), SiOxNy (where x and y are integers from 1 to 3, respectively), Al ₂ O ₃ , TiO ₂ , ZrO and ITO. One or more types may be included in the intermediate layer.

Further, the intermediate layer may include a metal alkoxide represented by the following Chemical Formula 3 or a condensate thereof.

[Formula 3]

In Formula 3, M is any metal selected from the group consisting of aluminum, zirconium and titanium, R ₃ is a halogen, an alkyl group, an alkoxy group, an acyloxy group or a hydroxyl group, and z may be 3 or 4.

In one example, the intermediate layer may further include a filler. The filler may be used in consideration of, for example, adjusting the refractive index of the intermediate layer and / or adjusting the mechanical strength. In one example, the filler includes CaO, CaF ₂ , MgO, ZrO ₂ , TiO ₂ , SiO ₂ , In ₂ O ₃ , SnO ₂ , CeO ₂ , BaO, Ga ₂ O ₃ , ZnO, Sb ₂ O ₃ , One or more selected from the group consisting of NiO and Al ₂ O ₃ may be used.

The method of forming the intermediate layer using the above material is not particularly limited, and various dry and / or wet coating methods such as a known method, for example, a deposition method, a sol-gel coating method, may be used depending on the material used. have.

The barrier film of the present application may also further include a surface layer present on the surface of the barrier layer. Such a surface layer can act as a so-called dielectric layer and / or protective layer. The material forming the surface layer is not particularly limited, and, for example, a suitable material may be selected from various materials applied to forming the above-described intermediate layer. In addition, an appropriate method may also be adopted in consideration of the type of material to be selected in the method of forming the surface layer.

The present application also relates to a method for manufacturing a barrier film, for example, a method for manufacturing a barrier film described above.

The method of manufacturing the barrier film in the present application is not particularly limited, and may be performed by a known deposition method, such as a sputtering method. For example, the method may include the multi-component metal oxynitride containing silicon atoms, tin atoms, oxygen atoms and nitrogen atoms through a sputtering process using a metal or metal oxide target containing silicon atoms and tin atoms as targets. It may include forming a blocking layer.

The method of performing the sputtering process as described above in the present application is not particularly limited, and may be performed in a known manner. For example, the sputtering process may be performed while injecting oxygen gas and / or nitrogen gas as a process gas, and in this case, the conditions under which the sputtering process proceeds are appropriate considering the type of target used or process efficiency, etc. Can be adjusted.

The barrier film of the present application as described above has excellent barrier properties, and such barrier properties do not fluctuate depending on the influence of external environmental factors, and can be stably maintained for a long time. Therefore, such a barrier film is a packaging material for food or pharmaceuticals, a flat panel display (FPD) such as a liquid crystal display (LCD), a member for a solar cell, a substrate for electronic paper or an organic light emitting diode (OLED), or a sealing film. It can be effectively used in a variety of applications. In particular, the barrier film has excellent optical performance such as transparency, and thus can be effectively used in optical devices such as various display devices or lighting devices.

In the present application, a barrier film having excellent barrier properties and optical performance and a method of manufacturing the same can be provided. Barrier films produced by the method of the present application, as well as packaging materials such as food and medicine, as well as FPD (Flat Panel Display) such as LCD (Liquid Crystal Display) or members for solar cells, electronic paper or OLED (Organic Light Emitting) Diode) can be effectively used in various applications such as substrates and sealing films.

Hereinafter, the manufacturing method of the present application will be described through examples and comparative examples according to the present application, but the scope of the present application is not limited by the following examples.

Example  One.

A barrier layer was formed to a thickness of about 40 nm on a base film COolefin (cycloolefin polymer) film by a sputtering method using a metal target containing about 50 atomic% of silicon atoms and about 50 atomic% of tin atoms. Sputtering was performed while argon gas was injected at a flow rate of about 40 sccm as a process gas, oxygen gas was injected at a flow rate of about 15 sccm, and nitrogen gas was injected at a flow rate of about 40 sccm. Sputtering was performed by reactive sputtering in an atmosphere of 0.4 Pa. The barrier layer formed in this manner contained about 25.4 atomic% of tin, about 46.2 atomic% of oxygen, about 23 atomic% of silicon, and about 4.9 atomic% of nitrogen, and the moisture permeability (WVTR) was measured to be about It was about 2.0 × 10 ^-2 g / m ² day. In the above, the moisture permeability was performed using a known measuring equipment (MOCON Aquatran model 1).

Example  2.

A barrier layer was formed in the same manner as in Example 1, except that the injection flow rate of oxygen gas was about 18 sccm when the barrier layer was formed. In this way, the barrier layer contained about 25.2 atomic% of tin, about 50.2 atomic% of oxygen, about 22 atomic% of silicon, and about 2 atomic% of nitrogen, and the measured moisture permeability (WVTR) was about 4.1 ×. It was about 10 ^-3 g / m ² day. The water vapor transmission rate was performed using a known measuring equipment (MOCON Aquatron 1).

Comparative example  One.

A nitrogen oxide gas was not injected at the time of formation of the blocking layer, and a blocking layer was formed in the same manner as in Example 1 except that the injection flow rate of oxygen gas was about 30 sccm. In this way, the barrier layer contained about 24.6 atomic% of tin, about 53.8 atomic% of oxygen, and about 21.1 atomic% of silicon, and as a result of measuring the moisture permeability (WVTR), about 1.2 × 10 ^-1 g / m ² It was about a day.

Claims (18)

It is a barrier film having a barrier layer comprising a multi-component metal oxynitride containing silicon atom, tin atom, oxygen atom and nitrogen atom,
The multi-component metal oxynitride, a barrier film containing 5 to 30 atomic% silicon atom, 5 to 30 atomic% tin atom, 30 to 60 atomic% oxygen atom and 0.2 to 15 atomic% nitrogen atom. delete The barrier film according to claim 1, wherein the multi-component metal oxynitride contains 10 to 30 atomic% of silicon atoms. The barrier film according to claim 1, wherein the multi-component metal oxynitride contains 15 to 30 atomic% of silicon atoms. The barrier film according to claim 1, wherein the multi-component metal oxynitride contains 20 to 30 atomic% silicon atoms. The barrier film according to claim 1, wherein the multi-component metal oxynitride contains 10 to 30 atomic% of tin atoms. The barrier film according to claim 1, wherein the multi-component metal oxynitride contains 15 to 30 atomic% of tin atoms. The barrier film according to claim 1, wherein the multi-component metal oxynitride contains 20 to 30 atomic% of tin atoms. The barrier film according to claim 1, wherein the multi-component metal oxynitride contains 35 to 60 atomic% oxygen atoms. The barrier film according to claim 1, wherein the multi-component metal oxynitride contains 40 to 60 atomic% oxygen atoms. The barrier film according to claim 1, wherein the multi-component metal oxynitride contains 40 to 55 atomic% oxygen atoms. The barrier film according to claim 1, wherein the multi-component metal oxynitride contains 1 to 15 atomic% of nitrogen atoms. The barrier film according to claim 1, wherein the multi-component metal oxynitride contains 1.5 to 15 atomic% of nitrogen atoms. The barrier film according to claim 1, wherein the multi-component metal oxynitride contains 1.5 to 10 atomic% of nitrogen atoms. The barrier film according to claim 1, wherein the multi-component metal oxynitride contains 1.5 to 6 atomic% of nitrogen atoms. The barrier film according to claim 1, further comprising a base film, and the barrier layer is formed on one side or both sides of the base film. Forming a barrier layer comprising a multi-component metal oxynitride comprising silicon atoms, tin atoms, oxygen atoms and nitrogen atoms through a sputtering process using a metal or metal oxide target containing silicon atoms and tin atoms as targets Method for producing a barrier film according to claim 1. 18. The method of claim 17, wherein the sputtering process is performed while injecting oxygen gas and nitrogen gas as process gas.