KR102071915B1 - Method for preparing barrier film - Google Patents

Abstract

The present application relates to a method for producing a barrier film and a barrier film produced by the method, and to improve the processability and convenience in mass production of the barrier film, a method for producing a barrier film having excellent barrier properties at low cost To provide.

Description

Production Method of Barrier Film {METHOD FOR PREPARING BARRIER FILM}

The present application relates to a method for producing a barrier film and a barrier film produced by the method.

Various displays such as solar cells, liquid crystals, organic or inorganic electroluminescence (hereinafter sometimes referred to as "EL"), and electronic devices such as electronic papers protect their internal structure and provide oxygen or water vapor from the outside. Although a glass substrate is generally used as a sealing material for blocking, the use of the transparent barrier film based on a plastic film is examined for the purpose of thinning, lightening, or providing a flexible product (for example, patent document 1 and 2).

Japanese Laid-Open Patent Publication 2005-77553 Japanese Laid-Open Patent Publication No. 2010-253861

The present application relates to a method for producing a barrier film having excellent barrier properties at a low cost and a barrier film produced by the manufacturing method by improving the processability and convenience in mass production of the barrier film.

The present application relates to a method for producing a barrier film. The barrier film of the present application can be applied to various applications. For example, the barrier film may be applied to an illumination device or a display device. In addition, the barrier film can be applied to applications requiring high wear resistance of the glass film.

The exemplary barrier film may include forming a moisture providing layer 100 on one surface of the barrier layer 200 including polysilazane, as shown in FIG. 1. In the present application, the barrier layer includes polysilazane, wherein polysilazane is a compound having a silicon-nitrogen bond in its structure, and is a compound that becomes a precursor of silicon oxynitride or silicon oxide, and such polysilazane is silicon -A step of substituting a nitrogen bond with a silicon-oxygen bond is necessary. This step has conventionally required a polysilazane compound coated on a silicon wafer, metal surface, etc., to undergo a curing process for as little as 30 minutes or one hour in an oxygen atmosphere of less than 1000 ° C. This technique is limited in its application range because the material serving as the base layer can be applied only to a material capable of withstanding the curing temperature, such as glass. In recent years, the temperature can be lowered by using a catalyst such as palladium or amine, but the range of application thereof is limited because the temperature must be maintained for at least 1 hour at a temperature of 150 ° C or higher. In addition, nitrogen may be replaced with oxygen using vacuum ultraviolet (VUV), vacuum plasma, or the like, but this method has a disadvantage in that the manufacturing cost is quite high because expensive processing equipment and the like must be used.

However, the present application is a method of using water, by forming a moisture providing layer on one surface of the barrier layer, the moisture supply layer provides oxygen to the barrier layer during the storage of the barrier film to replace the nitrogen of the polysilazane with oxygen The barrier film can be manufactured at a low cost while simplifying the manufacturing process.

In one example, the manufacturing method of the present application may further include the step of storing for 20 minutes to 5 hours in the temperature range of 30 ℃ to 130 ℃ after forming the moisture providing layer. In an embodiment of the present application, the storing step is at a temperature of 30 ℃ to 120 ℃ 30 ℃ 110 ℃ 40 ℃ to 100 ℃ 50 ℃ to 90 ℃ or 50 ℃ to 80 ℃, 20 minutes to 5 hours, 30 minutes to 4 hours, 40 minutes to 200 minutes or 50 minutes to 150 minutes. The present application, by forming a barrier layer on the moisture providing layer, it is possible to simplify the manufacturing process of the barrier film to increase the process efficiency, and the moisture and oxygen barrier properties can be stably maintained for a long time even in harsh conditions such as high temperature and high humidity conditions. A barrier film that can be provided.

In one example, after the storing step, the barrier layer may include a polymer having a polymer unit represented by Formula 1 below. Thus, the polymer may be a compound of polysilazane precursor, and may mean a compound derived from polysilazane, which is a precursor. For example, the polymer may be a compound in which nitrogen of polysilazane, which is a precursor, is replaced with oxygen.

[Formula 1]

In Formula 1, n is a number in the range of 2 to 50, X is -O- or -NW-, R ₁ and R ₂ are each independently hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl And W is hydrogen or an alkyl group. In addition, in one example, all of R ₁ and R ₂ and W may be hydrogen, but is not limited thereto. On the other hand, n may be a number within the range of 5 to 45, 10 to 40, 15 to 35 or 20 to 30.

In one example, the polysilazane may be a molecular structure in which a linear structure and a ring structure centered on a 6-membered ring or an 8-membered ring exist. The number average molecular weight (Mn) of the polysilazane may be 200 to 2000 (polystyrene conversion by gel permeation chromatography), and may be a liquid or a solid.

In the present application, the term "alkoxy group" may mean an alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. The alkoxy group may be linear, branched or cyclic. In addition, the alkoxy group may be optionally substituted with one or more substituents.

In the present application, the term "alkyl group" may mean an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. The alkyl group may be linear, branched or cyclic. In addition, the alkyl group may be optionally substituted with one or more substituents.

In the present application, the term "alkenyl group" may mean an alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, unless otherwise specified. The alkenyl group may be linear, branched, or cyclic, and may be optionally substituted with one or more substituents.

In the present application, the term "alkynyl group" may refer to an alkynyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, unless otherwise specified. The alkynyl group may be linear, branched or cyclic, and may be optionally substituted with one or more substituents.

In the present application, the term "aryl group" may refer to a monovalent moiety derived from a compound or a derivative thereof including a structure in which a benzene ring or a structure in which two or more benzene rings are condensed or bonded, unless otherwise specified. The range of the aryl group may include a functional group commonly referred to as an aryl group as well as a so-called aralkyl group or an arylalkyl group. The aryl group may be, for example, an aryl group having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. Examples of the aryl group include phenyl group, phenoxy group, phenoxyphenyl group, phenoxybenzyl group, dichlorophenyl, chlorophenyl, phenylethyl group, phenylpropyl group, benzyl group, tolyl group, xylyl group or naphthyl group. Can be.

As the substituent which may be optionally substituted in the alkoxy group, alkylene group or epoxy group in the present application, epoxy groups such as halogen, glycidyl group, epoxyalkyl group, glycidoxyalkyl group or alicyclic epoxy group such as chlorine or fluorine, Acryloyl group, methacryloyl group, isocyanate group, thiol group or monovalent hydrocarbon group and the like can be exemplified, but is not limited thereto.

In an embodiment of the present application, the barrier layer may include a coating layer including a substrate layer and polysilazane, and a moisture providing layer may be formed to contact the moisture providing layer. In addition, the moisture providing layer may be formed such that the coating layer is in contact with the moisture providing layer.

In one example, the content of the polysilazane in the coating layer may be adjusted according to the layer thickness of the barrier film, for example, it may be in the range of 0.2 to 55 wt% or 0.2 to 35 wt%. In the present application range, in the storage step, the nitrogen of the polysilazane of the barrier layer may be efficiently replaced with oxygen, thereby maintaining excellent moisture barrier properties of the barrier film.

In addition, the thickness of a coating layer may be suitably set according to the objective. For example, the thickness of the coating layer may be in the range of 1 nm to 2 μm, 10 nm to 1.5 μm, or 50 nm to 1 μm as the thickness after drying. The coating layer may have a single layer or a multilayer structure of two or more layers. In the case of a multilayer structure, the total thickness of the coating layer may range from 50 nm to 10 μm. The present application by controlling the thickness of the coating layer in the above range, or by forming a layer structure as described above, by efficiently replacing the nitrogen of the polysilazane with oxygen to increase the convenience of the process, excellent barrier properties of the barrier film I can keep it.

In an embodiment of the present application, the material constituting the base layer is not limited, and may be a material having transparency and flexibility in the nature of the barrier film. In one example, the substrate layer has a transmittance of at least one of the wavelengths in the visible region, for example, a wavelength in the range of 420 nm to 680 nm, or at least 90%, at least 91%, of all the light within the range, At least 92%, at least 93%, at least 94% or at least 95%. The transmittance means a point having excellent transparency and the like as the range is higher, and the upper limit thereof is not particularly limited.

In one example, the base layer is a polyester resin such as polyethylene terephthalate, polycarbonate, polyethylene naphthalate, polyarylate, polyether resin such as polyether sulfone, cycloolefin polymer, polyethylene resin, polypropylene resin It may contain one or more selected from the group consisting of cellulose resins such as polyolefin resins, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, polyimide resins and epoxy resins. In one example, the thickness of the substrate layer is not particularly limited, but may be 2 μm to 200 μm, and may be 5 μm to 190 μm, 10 μm to 180 μm, 20 μm to 180 μm, or 20 μm to 150 μm. .

In an embodiment of the present application, the method for manufacturing a barrier film may include applying a coating solution including polysilazane on a substrate layer to prepare a barrier layer before forming a moisture providing layer. As an organic solvent for preparing a coating solution containing polysilazane, it may be desirable to exclude an alcohol-based or water-containing substance that easily reacts with the polysilazane. For example, as the organic solvent, ethers such as hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers can be used, and specifically, pentane, hexane, cyclohexane And hydrocarbons such as toluene, xylene, sorbet, and taben, halogen hydrocarbons such as methylene chloride and torichloroethane, ethers such as dibutyl ether, dioxane and tetrahydrofuran and the like.

Arbitrary suitable methods may be employ | adopted as a method of apply | coating the coating liquid containing polysilazane. As a specific example, the roll coating method, the flow coating method, the inkjet method, the spray coating method, the printing method, the dip coater method, the cast film forming method, the bar coat method, the gravure printing method, etc. can be illustrated, for example.

In addition, in an embodiment of the present application, the manufacturing method may further comprise the step of drying the applied coating liquid for 30 seconds to 5 minutes in the temperature range of 50 ℃ to 150 ℃. In this step, the organic solvent of the coating solution may be removed.

In addition, in the embodiment of the present application, the manufacturing method may further comprise the step of removing the moisture providing layer. Removal of the moisture providing layer may be performed after the moisture providing layer is formed on one surface of the barrier layer. In addition, in one example, the moisture providing layer may be removed after the storage step described above.

In one example, the moisture providing layer has a moisture content of 1% by weight, 1% by weight to 50% by weight, 3% by weight to a moisture content measured according to Karl-Fischer titration. 40 weight percent, 5 weight percent to 30 weight percent, or 10 weight percent to 20 weight percent. The moisture content rate was measured by using a VA-236S equipment of Mitsubishi Co., Ltd. for about 1 hour after purging nitrogen in the equipment and the container storage chamber, and measuring the moisture content of about 1 g of the moisture providing layer sample (the measurement condition is nitrogen gas). The temperature may be 240 ° C., the flow rate is 250 ml / min, and the measurement time may be measured until the moisture measurement amount is 0.17 μg / s), but is not limited thereto. In the present specification, the moisture content represents the degree of moisture that the moisture providing layer can contain. Therefore, whether the moisture providing layer of the present application actually included moisture in the above range is not limited.

The moisture providing layer may mean a resin layer containing moisture as described above, and the material is not particularly limited as long as the moisture content range is satisfied. For example, the moisture providing layer may include polyvinyl alcohol (PVA) or triacetyl cellulose (TAC).

In one example, the barrier film manufacturing method of the present application may further include forming a moisture providing layer on the other side of the barrier layer. That is, the moisture providing layer can be formed on both sides of the barrier layer.

The present application also relates to a barrier film. The barrier film may be produced by the above-described manufacturing method. The barrier film may include a barrier layer and may not include a moisture providing layer.

In addition, the present application may be related to the lighting device or the use thereof including the barrier film. For example, the present application provides a display device including the lighting device.

The use is, for example, a backlight unit (BLU) of a display device such as a computer, a mobile phone, a smartphone, a personal digital assistant (PDA), a gaming device, an electronic reading device or a digital camera, indoor or outdoor. Lighting, stage lighting, decorative lighting, accent lighting, or museum lighting, and the like, but also used in horticulture, special wavelength lighting required in biology, etc., but the use to which the lighting device can be applied is not limited thereto.

The configuration and structure of the lighting apparatus including a barrier film may include, for example, a light source, the barrier film, and a light emitting film, and the light source and the light emitting film may allow light emitted from the light source to enter the light emitting film. All known configurations and structures may be used without limitation, such as such arrangements may be made.

The present application provides a method for producing a barrier film having excellent barrier properties at a low cost and a barrier film manufactured by the manufacturing method by improving the processability and convenience in mass production of the barrier film.

1 shows a cross-sectional view of an exemplary barrier film.

Hereinafter, the present application will be described in more detail with reference to examples according to the present application and comparative examples according to the present application, but the scope of the present application is not limited to the examples given below.

Example 1

Polysilazane coating solution was prepared by adding 10 g of polysilazane product (Yupkei Chemical Co., Ltd., Neoceramic AC-119) diluted to 20% by weight of xylene in a container. The prepared coating solution was coated with a meyer bar on a 100 μm thick polyethylene terephthalate film as a base layer and dried at 90 ° C. for 2 minutes to form a coating layer such that the coating solution was 120 nm thick. , A barrier layer was prepared.

A triacetylcellulose film (Fujifilm, NRT60 TAC) having a thickness of 60 μm was laminated on the substrate layer as a moisture providing layer. At this time, the moisture content of the moisture providing layer is 6wt%.

The prepared laminate was stored at 100 ° C. for 30 minutes, and then the moisture providing layer was removed to prepare a barrier film.

1. Measurement of WVTR

The moisture vapor permeability of the ITO-deposited PET and the moisture vapor barrier of the barrier film prepared in the above example were measured according to the standard of ASTM F1249.

Water vapor permeability (mg / m ² · day) PET with ITO deposited 40.16 Example 1 15.50

2. SiO ₂  Confirmation of rise in surface strength by formation

In the examples the surface strength was measured at each time as 0, 6, 12, 18, 24 and 30 minutes in the storage step.

Surface strength was measured by the steel wool method. Specifically, Rhodes American's # 0000 grade was used and a weight of 1 kg was used. The balance was placed on the steel wool to observe whether scratches occurred in the weight of the balance.

Retention time Surface strength 0 min 100g or less 6 minutes 100g or less 12 minutes 300g ~ 500g 18 minutes 300g ~ 500g 24 minutes 500g ~ 800g 30 minutes 800g or more

3. SiO using FT-IR ₂  Formation confirmation

In the Examples, FT-IR analysis was performed at each time as 0, 3, 6, 9, 12, 15 and 18 minutes in the storage step, the results are shown in FIG. As the storage time passes, it can be seen that Si-H and Si-N of the barrier layer decrease and Si-O increases.

100: moisture providing layer
200: barrier layer

Claims (15)

Forming a moisture providing layer on one surface of the barrier layer including polysilazane,
The barrier layer includes a coating layer including a substrate layer and polysilazane, wherein the moisture providing layer is formed such that the substrate layer is in contact with the moisture providing layer. The method of claim 1, further comprising storing the water supply layer for 20 minutes to 5 hours at a temperature ranging from 30 ° C. to 130 ° C. after forming the moisture providing layer. The method of claim 2, wherein after the storing, the barrier layer comprises a polymer having a polymer unit represented by Formula 1 below:
[Formula 1]

In Formula 1, n is a number in the range of 2 to 50, X is -O- or -NW-, R ₁ and R ₂ are each independently hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl And W is hydrogen or an alkyl group. delete The method of claim 1, wherein the coating layer comprises polysilazane in a range of 0.2 to 55 wt%. The method of claim 1, wherein the coating layer is in a thickness range of 1 nm to 2 μm. The method of claim 1, wherein the coating layer has a multilayer structure of two or more. The method of claim 1, wherein the substrate layer is polyethylene terephthalate, polycarbonate, polyethylene naphthalate, polyarylate, polyethersulfone, cycloolefin polymer, polyethylene resin, polypropylene resin, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyl The manufacturing method of the barrier film containing a rate, a polyimide resin, or an epoxy resin. The method of manufacturing a barrier film according to claim 1, wherein a coating liquid containing polysilazane is coated on the substrate layer before the moisture providing layer is formed to produce a barrier layer. 10. The method of claim 9, further comprising the step of drying the applied coating liquid for 30 seconds to 5 minutes in the temperature range of 50 ℃ to 150 ℃. 10. The method of claim 9, wherein the coating liquid is coated with a roll coating method, a flow coating method, an inkjet method, a spray coating method, a printing method, a dip coater method, a flexible film forming method, a bar coating method, or a gravure printing method. Manufacturing method. The method of claim 1, further comprising removing the moisture providing layer. The method of claim 1, wherein the moisture providing layer has a moisture content of 1% by weight or more based on the total mass of the moisture providing layer, measured according to Karl-Fischer titration. The method of claim 1, further comprising forming a moisture providing layer on the other side of the barrier layer. The barrier film manufactured by the manufacturing method of the barrier film in any one of Claims 1-3 and 5-14.

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