KR20190062270A - Barrier film - Google Patents

Abstract

The present application relates to a barrier film. In the present application, provided is a barrier film having excellent barrier properties to an external environment and excellent optical properties. The barrier film produced by the present application can be used for electronic products sensitive to moisture or the like. The barrier film includes a substrate layer and a barrier layer.

Description

Barrier film {BARRIER FILM}

The present application is directed to a barrier film.

So-called barrier films having barrier properties against gas and / or moisture have various uses. For example, in addition to the use of packaging materials such as foods and medicines, the film may be used for a display including an organic light emitting device (OLED), a substrate for an OLED (Organic Light Emitting Diode), a member for a solar cell, And may be used as a sealing film included in these. In particular, the barrier film may be applied to a light emitting device or a device associated with the lighting device, for example, an OLED (organic light emitting device) related device, a Liquid Crystal Display (LCD), a TV, a computer, a mobile phone, PDA), a gaming device, an electronic reading device, or a digital camera, transparency (translucency) is required for securing a higher level of moisture barrier and visibility.

On the other hand, a test for verifying the performance of the film can be made before applying the barrier film to such use. For example, the test may be a performance test to measure moisture barrier properties, transparency, and color coordinates of the barrier film, measured at harsh conditions of high temperature and high humidity, such as a temperature of 85 캜 and a relative humidity of 85%. However, as the film characteristics are changed by the severe condition test for the performance verification before shipment of the product, the quality uniformity of the film may not be ensured. On the contrary, the above test may hinder the custiming .

One object of the present application is to provide a barrier film.

Another object of the present invention is to provide a barrier film which is advantageous for custiming and ensures uniformity of quality since the characteristics of the film do not change greatly even after the severe condition test for verifying the barrier property of the film before shipment of the product .

The above and other objects of the present application can be all solved by the present application, which is described in detail below.

In one example of this application, the present application relates to a barrier film. The barrier film comprises a base layer (A) and a barrier layer (B) located on at least one side of the base layer. The barrier layer comprises at least one cured layer of a polysilazane layer containing particles.

The inventor of the present application has found that the film characteristics are changed by the severe condition test for the performance verification before shipment of the product, and the test can deteriorate the uniformity of the quality of the film and hinder the customization according to the use or the customer . Accordingly, the present application provides a barrier film having a small degree of property change such as moisture barrier property and color coordinate even after a severe condition test for verifying the performance of a film. In the present application, the severe condition test means that the moisture permeability and the color coordinate are measured for a barrier film stored for 150 hours at a temperature of 85 ° C and a relative humidity of 85%.

Specifically, the barrier film of the present application may be a film satisfying a change amount (b *) of the b * value calculated according to the following formula (1) is 0.5 or less.

[Equation 1]

_{△ b * = b 2 * -} b 1 *

B ₁ * and b ₂ * are the b * values of the barrier film in the L * a * b * color space of the International Commission on Illumination (CIE) and b ₁ * And b ₂ * is the b * value of the barrier film stored at 85 ° C and 85% relative humidity for 150 hours. Regarding the b ₁ * value, the normal temperature may be a temperature in a particularly warmed or non-warmed state, for example, a temperature in the range of 20 to 35 ° C, a temperature in the range of 23 to 32 ° C, or a temperature in the range of 25 to 30 ° C . Further, regarding the b ₁ * value, the time for storing the barrier film at room temperature is not particularly limited as long as it is 12 hours or less. For example, the storage time may be 12 hours or less, 10 hours or less, 8 hours or less, 6 hours or less, 4 hours or less, or 2 hours or less. Or the retention time may be 12 hours, 10 hours, 8 hours, 6 hours, 4 hours, or 2 hours.

A high b * value in the L * a * b * color space of the International Commission on Illumination (CIE) means that it is yellowish. In general, in the case of a barrier film used for an electronic device such as a display, it is known that a small b * value is advantageous for securing transparency. However, the b * value required for the film may vary depending on the application in which the product is actually used, or depending on the nature or configuration of the adjacent member in contact with the film in certain applications. Taking this into consideration, it is important that the increase in the b * value of the barrier film stored for a long time under severe conditions is not large.

Particularly, the polysilazane layer (i.e., hardened layer) cured through plasma treatment or the like includes a SiO x N y component, and when stored at high temperature / high humidity conditions such as 85 캜 and 85% relative humidity conditions, While changing, the b * value can be increased. Therefore, in the case of a barrier film having components derived from polysilazane, it becomes more important that the b * value rise of the film stored for a long time under severe conditions is controlled so as not to become large.

Considering the results of the following experimental examples, it is considered that the property that the amount of change (b *) of the b * value satisfies 0.5 or less is suppressed through the use of particles for the polysilazane layer. In particular, when the particles used comprise silica particles, since the content of silicon oxide (SiO 2) in the polysilazane layer is already high prior to curing and before the harsh conditions test, It is thought that it can do. In other words, the use of particles seems to suppress the large change in b * value that appears after a severe condition test. The specific types of particles, particle characteristics (e.g., diameter), and usage content are described below.

In one example, the change amount (b *) of the b * value of the barrier film is 0.45 or less, 0.4 or less, 0.35 or less, 0.30 or less, 0.25 or less, 0.20 or less, 0.15 or less, 0.05 or less. The change amount (b *) of the b * value of the barrier film may preferably be about zero.

The barrier film of the present application satisfying the variation according to the above-mentioned formula (1) can ensure the uniform quality of the film because the change of the film properties is small even after the performance test under severe conditions, and the barrier film of the present invention satisfying the custiming ). Further, the fact that the barrier film satisfies the b * value change amount means that the increase in the b * value under the severe condition is not large, so that even when the barrier film is subjected to a severe condition similar to the test, / It can be seen that it exhibits high humidity durability.

The barrier film of the present application satisfying the change characteristics after the above severe condition can have the following lamination structure.

In one example, the barrier layer (B) may be formed on only one side of the base layer (A) or on both sides of the base layer (A) facing each other.

Unless otherwise specifically defined, the terms " on " or " on " used in connection with interlayer deposition locations in the present application are intended to encompass not only the case where a configuration lies directly on another, And may be used in the meaning including the case where the constitution is intervened.

The kind of the base layer (A) is not particularly limited. For example, the substrate layer may comprise a glass substrate or a plastic substrate.

In one example, the base layer may be formed of a polyester film such as a polyethylene terephthalate (PET) film, a polycarbonate film, a polyethylene naphthalate film or a polyarylate film, a polyether film film such as a polyethersulfone film, A polyolefin film such as a film, a polyethylene film or a polypropylene film, a cellulose resin film such as a diacetylcellulose film, a triacetylcellulose film or an acetylcellulose butyrate film, a polyimide film, an acrylic film or an epoxy resin film and the like .

The substrate layer may comprise one or more of the films listed. That is, the substrate layer may be a single layer or a multi-layer structure.

The thickness of the base layer is not particularly limited. For example, in the range of 2 to 200 mu m, in the range of 5 to 190 mu m, in the range of 10 to 180 mu m, in the range of 20 to 180 mu m, or in the range of 20 to 150 mu m.

In the present application, the barrier layer (B) comprises at least one cured layer of the polysilazane described below. For example, the barrier layer (B) may be a cured layer (b1) of a polysilazane containing particles. In another example, the barrier layer (B) may include a cured layer (b2) of a polysilazane that does not contain particles in addition to the cured layer (b1) of the polysilazane containing the particles. At this time, one or more of the cured layer (b1) of the polysilazane containing particles and / or the cured layer (b2) of the polysilazane containing no particles may be contained in the barrier layer.

In the present application, the polysilazane layer may be a layer formed by coating the base layer with a polysilazane-containing composition (coating composition) described below, for example, before curing. The cured layer is a layer formed by curing the polysilazane layer and has blocking properties against an external environment (e.g., moisture or gas).

In the present application, the polysilazane layer means a layer containing polysilazane as a main component (a coating layer formed on the base layer before curing). The main component is, for example, a polysilazane-containing layer or polysilazane-containing composition in which the proportion of polysilazane is 55% or more, 60% or more, 65% or more, 70% or more, 75% 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 term " polysilazane " in the present application means a polymer in which silicon atoms (Si) and nitrogen atoms (N) are repeated to form a basic backbone. Such a polysilazane can be modified through a predetermined treatment (for example, a plasma treatment described below) to form silicon oxide and / or silicon oxynitride having barrier properties. Accordingly, the cured product of the polysilazane layer, that is, the cured layer contains Si, N and / or O, and has a barrier property to the external environment.

In one example, the polysilazane used in the present application may comprise a unit represented by the following formula (1).

[Chemical Formula 1]

In formula (1), R ¹ , R ² and R ³ may each independently be a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylsilyl group, an alkylamido group or an alkoxy group.

The term "alkyl group" in the present application 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.

The term "alkenyl group" as used herein 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 optionally be substituted with one or more substituents.

The term "alkynyl group" as used herein may mean 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 optionally be substituted with one or more substituents.

The term " aryl group " as used herein, unless otherwise specified, includes a benzene ring or a compound having a structure in which two or more benzene rings are connected or condensed or bonded while sharing one or two or more carbon atoms Or a monovalent residue derived therefrom. The range of the aryl group in the present specification may include not only a functional group commonly referred to as an aryl group but also an 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 a phenyl group, dichlorophenyl, chlorophenyl, phenylethyl, phenylpropyl, benzyl, tolyl, xylyl group or naphthyl group.

The term "alkoxy group" in the present application 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.

The specific type of polysilazane is not particularly limited as long as it includes the unit represented by the above formula (1).

In one example, considering the denseness of the denatured polysilazane layer, the polysilazane of the present application includes a polysilazane containing a unit of the formula (1) in which all of R ¹ to R ³ are hydrogen atoms, for example, , Perhydro polysilazane can be used.

In one example, the polysilazane layer may be formed, for example, by coating a substrate layer (substrate film) with a composition (a coating liquid containing polysilazane as a main component) prepared by dissolving polysilazane in an appropriate organic solvent . The type of the solvent contained in the coating liquid is not particularly limited as far as it is a solvent that is not reactive with the polysilazane and can dissolve the polysilazane. Examples of the solvent include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers. Specific examples thereof include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and tallow, halogen hydrocarbons such as methylene chloride and tricholoroethane, ethers such as dibutyl ether, dioxane and tetra- And the like can be used as a solvent.

In one example, a commercial polysilazane or a composition comprising it may be used. For example, when AZ Electronic Materials is manufactured by Aquamica (registered trademark) NN120-10, NN120-20, NAX120-10, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, or SP140 may be used, but the present invention is not limited thereto.

When the thickness of the polysilazane layer coated on the base layer is too thin, the coating process is not smooth and the barrier property can not be sufficiently secured. If the thickness is too large, cracks (damage) may occur due to shrinkage of the polysilazane layer during the curing process. The thickness of the coated polysilazane layer may be, for example, not less than about 20 nm, not less than 30 nm, not less than 40 nm, not less than 50 nm, not less than 60 nm, not less than 70 nm, nm or more, 80 nm or more, 90 nm or more, or 100 nm or more. And the upper limit thereof may be, for example, 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 400 nm or less, 300 nm or less or 200 nm or less. The thickness in the above range is the thickness of the polysilazane layer formed on one side of the substrate layer, for example, the thickness of the polysilazane layer which is a single layer formed by applying the composition once.

The thickness of the cured layer obtained by curing the polysilazane layer having the above thickness can be determined, for example, according to the thickness of the polysilazane layer described above. In addition, the thickness of the barrier layer including at least one hardened layer can be appropriately adjusted in accordance with the number of the hardened layer or the polysilazane layer within a range of 1,500 nm or less.

The polysilazane layer contains a particulate component in addition to the polysilazane.

As the particle component, organic particles and / or inorganic particles may be used. The shape of the particles is not particularly limited. For example, the particles may be spherical, ellipsoidal, pyramidal, or amorphous.

In one example, the particles may be particles that have undergone surface treatment. For example, the surface of the inorganic particles may be coated with an acrylic compound. Particles that have undergone appropriate surface treatment can have good miscibility with adjacent cured polysilazane cures.

In one example, the refractive index of the particles can be in the range of 1 to 2, 1 to 1.9, 1 to 1.8, 1 to 1.7, 1 to 1.6, or 1 to 1.55. When the above range is satisfied, appropriate transparency can be ensured.

The diameter (particle diameter) of the particles used is not particularly limited. The diameter of the particles in the present application may mean the length of the longest dimension among the shapes of the particles and can be measured using a known scanning electron microscope (SEM).

In one example, the particles may have a diameter of at least 15 nm. If the diameter of the particles is smaller than the above range, an increase in the water permeability through the interface of the particles may occur. Specifically, the particles may be at least 20 nm, at least 25 nm, at least 30 nm, at least 35 nm, at least 40 nm, at least 45 nm, at least 50 nm, at least 55 nm, at least 60 nm, at least 65 nm, And may have a diameter of 75 nm or more or 80 nm or more. The upper limit of the particle size can be, for example, 500 nm. Specifically, the upper limit of the particle size of the particles may be 400 nm or less and 300 nm or less, and more specifically, 200 nm or less, 190 nm or less, 180 nm or less, 170 nm or less, 160 nm or less, . The diameters of the particles used need not be all the same, and it is sufficient to satisfy the particle diameters within the above range. More specifically, in order to satisfy the aforementioned degree of b * value change, it is preferable that the particle size of the particles is in the range of 40 to 120 nm, in the range of 45 to 110 nm, or in the range of 50 to 100 nm.

With respect to the cured layer or the polysilazane layer thickness, the diameter of the particles may be lower than the thickness of the layer, although it is not particularly limited. For example, it can have a size of about 3/4, 1/2 or 1/4 or less of the thickness of the polysilazane layer or cured layer. Further, in order to prevent light scattering, the particle size may be 100 nm or less.

In one example, an inorganic particle may be used as the particle component. For example, inorganic particles selected from clay, talc, alumina, calcium carbonate, zirconia and silica particles can be used. Compared with the organic particle component, since the inorganic particle component has better barrier properties against moisture and the like, use of the inorganic particle may be advantageous for improving the barrier property (barrier property) to the external environment of the film.

In one example, the particles used in the polysilazane layer may be silica particles. As described above, when silica particles are used, it may be more advantageous to suppress the increase in the b * value change after the abrupt test to within a predetermined range.

In another example, the polysilazane layer may comprise silica particles.

In another example, the polysilazane layer may comprise silica particles, and other types of particles. Other kinds of particles can be selected from among the inorganic particles described above.

In one example, the use amount of the particles may be 5 parts by weight or more based on 100 parts by weight of polysilazane. When the content is less than the above-mentioned content, the effect of suppressing the increase in b * value change after the severe test may not be sufficient. Specifically, the content is 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more, 45 parts by weight or more, . The upper limit of the particle content is not particularly limited as long as the change in physical properties after the severe test is satisfied, but the upper limit of the particle content is, for example, not more than 150 parts by weight, not more than 140 parts by weight, not more than 130 parts by weight, , 110 parts by weight or less, or 100 parts by weight or less.

Considering that in some cases the interface of the particles may act as a defect in which moisture penetration may occur, it may not be desirable to use an excess of particles. Considering this point, the content of the particles may be 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or 50 parts by weight or less based on 100 parts by weight of polysilazane.

In one example, the polysilazane layer may further include organic particles in addition to inorganic particles. The organic particles may be polymer particles having the above-mentioned diameter, for example, acrylic particles. The content of the organic particles is not particularly limited, but when used, for example, with inorganic particles, the total content of organic and inorganic particles can be adjusted to satisfy the particle content range described above.

In one example, the barrier layer (B) and the base layer (A) can be in contact with each other. For example, the cured layer constituting the barrier layer (B) may be directly located on one side or both sides of the base layer (A). At this time, the barrier layer may include one or more cured layers derived from polysilazane.

In another example, the film may further include an intermediate layer (C) between the base layer (A) and the barrier layer (B). For example, the barrier film may be a film formed by coating a polysilazane composition on a coating material comprising a substrate layer (A) and an intermediate layer (C) formed on one side or both sides of the substrate layer, followed by curing . In some cases, the base layer may have irregularities (for example, several tens of nm, several hundred nm or several thousands nm or several um thick irregularities) on the surface on which the barrier layer is formed, Therefore, it may become an obstacle to stably form a cured layer. In view of this point, the barrier film may further include an intermediate layer (C) as a planarizing layer which provides a flat surface on which a cured layer can be formed.

The intermediate layer may contain at least one selected from the group consisting of, for example, acrylic resin, urethane resin, melamine resin, alkyd resin, epoxy resin, siloxane polymer and / or condensation product of organosilane compound represented by the following formula .

(2)

In formula (2), X is a hydrogen, a halogen, an alkoxy group, an acyloxy group, an alkylcarbonyl group, an alkoxycarbonyl group or -N (R ₂ ) ₂ , R ₂ is hydrogen or an alkyl group, R 1 is an alkyl group, An aryl group, an aryl group, an arylalkyl group, an alkylaryl group, an arylalkenyl group, an alkenylaryl group, an arylalkynyl group, an alkynylaryl group, a halogen, an amino group, an amide group, an aldehyde group, an alkylcarbonyl group, a carboxy group, An alkoxy group, an alkoxycarbonyl group, a sulfonyl group, a phosphoryl group, an acryloyloxy group, a methacryloyloxy group or an epoxy group, Q is a single bond, an oxygen atom or -N (R2 ) -, wherein R 2 is a hydrogen atom or an alkyl group, and m may be a number within a range of 1 to 3.

As the organosilane, at least one kind selected from the group consisting of the compounds represented by the above-mentioned general formula (2) can be used. In this case, when one type of organosilane compound is used, crosslinking may be possible.

Examples of the organosilane include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane , Phenyldimethoxysilane, phenyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, tri Phenyl ethoxysilane, phenylethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, dimethylethoxysilane, dimethylethoxysilane, diphenylmethoxysilane, diphenyl Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-aminophenylsilane, allyltrimethoxysilane, n- (2-aminoethyl) Ethoxy silane, 3-amine pro 3-aminopropyltrimethoxysilane, 3-glycidoxypropyldiisopropylethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltri Methoxysilane, n-phenylaminopropyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and mixtures thereof.

In another example, the intermediate layer may be prepared by polymerizing one or more polyfunctional acrylates. Examples of the polyfunctional acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene (Meth) acrylate, neopentylglycol adipate di (meth) acrylate, hydroxyl puivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (Meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (meth) acryloxyethyl isocyanurate, allyl cyclohexyl Di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, dimethylol dicyclopentanedi (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) (Meth) acrylate, neopentyl glycol-modified trimethylpropane di (meth) acrylate, adamantane di (meth) acrylate or 9,9-bis [4- 2-hydroxyethoxy) phenyl] fluorine; and the like; (Meth) acrylates such as trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri Trifunctional acrylates such as modified trimethylolpropane tri (meth) acrylate, trifunctional urethane (meth) acrylate or tris (meth) acryloxyethylisocyanurate; Tetrafunctional acrylates such as diglycerin tetra (meth) acrylate or pentaerythritol tetra (meth) acrylate; Pentafunctional acrylates such as propionic acid-modified dipentaerythritol penta (meth) acrylate; And dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate or urethane (meth) acrylate (e.g., an isocyanate monomer and trimethylolpropane tri A hexafunctional acrylate such as a reaction product, and the like, but the present invention is not limited thereto.

In one example, the intermediate layer may include a fluorine-based compound. For example, a fluorine-based (meth) acrylate or a fluorine-based siloxane compound may be used. A perfluoro compound such as perfluoropolyether acrylate may be used as the fluorine-based (meth) acrylate, and an alkoxysilane compound substituted with a fluorine-containing chain may be used as the fluorine-based siloxane compound.

As the epoxy resin applicable to the formation of the intermediate layer, at least one selected from the group consisting of an alicyclic epoxy resin and an aromatic epoxy resin 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 can be used. 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate and its derivatives such as Celloxide 2021P (Daicel Co.), 3,4-epoxycyclohexyl- Derivatives, which are stable at high temperatures, colorless and transparent, and are excellent in toughness, adhesion and adhesiveness for lamination. Especially when used for coating, surface hardness is excellent.

Examples of the aromatic epoxy resin include, for example, epoxy resins such as 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 Lt; / RTI > aromatic epoxy resin may be used.

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

The intermediate layer may contain a metal alkoxide represented by the following formula (3) or a condensate thereof.

(3)

In Formula (3), M is any metal selected from the group consisting of aluminum, zirconium, and titanium; R3 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 can 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 may be selected from the group consisting of 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 , NiO and Al ₂ O ₃ may be used.

The method of forming the intermediate layer using the above materials is not particularly limited and various dry and / or wet coating methods such as a deposition method and a sol-gel coating method may be used depending on the material used have. After the coating, suitable curing (e.g., thermal curing or photo-curing, etc.) may be made depending on the resin used.

The thickness of the intermediate layer is not particularly limited. For example, it may be 50 [mu] m or less. Specifically, the upper limit of the thickness may be 40 占 퐉 or less, 30 占 퐉 or less, 20 占 퐉 or less, 10 占 퐉 or 5 占 퐉 or less, and the lower limit may be 0.5 占 퐉 or more or 1 占 퐉 or more.

In one example, the barrier film of the above configuration may be a film that satisfies the intended light transmittance and barrier properties.

With respect to light transmittance, the barrier film may mean a film having a transmittance of 90% or more or 95% or more to visible light within a wavelength range of 380 nm to 780 nm, specifically, light having a wavelength of 550 nm. The upper limit of the transmittance is, for example, about 100%, and the film may have a transmittance of less than 100%.

In one example, the barrier film having the above-described characteristics and configuration can satisfy the change in the moisture permeability calculated according to the following equation (2) to 10 or less.

[Equation 2]

Change in moisture permeability = M ₂ / M ₁

Wherein M ₁ and M ₂ are the moisture permeability of the barrier film measured according to the ISO 15106-3 standard and M ₁ is the moisture permeability of the barrier film measured at 38 ° C and 100% % ≪ / RTI > relative humidity after storage of the barrier film for 150 hours.

The barrier film of the present application satisfying the variation according to the above-mentioned formula (2) can ensure the uniform quality of the film since the degree of decrease in the moisture permeability of the film is small even after the performance test under severe conditions, custimzing. In addition, the fact that the barrier film satisfies the above-described moisture permeability variation means that the increase in moisture permeability (degree of deterioration of the barrier property) is not large even under severe conditions, so that even when the barrier film is subjected to a severe condition similar to the test, It can be seen that it exhibits excellent high temperature / high humidity durability.

Specifically, the barrier film preferably has a moisture permeability variation of 9.5 or less, 9.0 or less, 8.5 or less, 8.0 or less, 7.5 or less, 7.0 or less, 6.5 or less, 6.0 or less, 5.5 or less, 5.0 or less, Or less, 3.5 or less, 3.0 or less, 2.5 or less, or 2.0 or less.

With respect to the moisture permeability in harsh conditions, the barrier film can have excellent moisture barrier properties. Specifically, the barrier film may be a film having a measured moisture permeability after storage at 85 ° C and 85% relative humidity for 150 hours, that is, a film having an M ₂ moisture permeability of 20 × 10 ^-3 g / m ² · day or less. Specifically, the M ₂ moisture permeability is, for example, 19 × 10 ^-3 g / m ² · day or less, 18 × 10 ^-3 g / m ² · day or less, 17 × 10 ^-3 g / m ² · day or ^{less, 16 × 10 -3 g / m} 2 · day or ^{less, 15 × 10 -3 g / m} 2 · day or ^{less, 14 × 10 -3 g / m} 2 · day or ^{less, 13 × 10 -3 g / m} 2 · day or ^{less, 12 × 10 -3 g / m} 2 · day or ^{less, 11 × 10 -3 g / m} 2 · day or ^{less, 10 × 10 -3 g / m} 2 · day or less, 9 × 10 ^-3 g / m ² · day or ^{less, 8 × 10 -3 g / m} 2 · day or ^{less, 7 × 10 -3 g / m} 2 · day or ^{less, 6 × 10 -3 g / m} 2 · day or less, 5 × 10 ^-3 g / m ² · day or ^{less, 4 × 10 -3 g / m} 2 · day or ^{less, 3 × 10 -3 g / m} 2 · day or ^{less, 2 × 10 -3 g / m} 2 · day or less, or 1 × 10 Can be less than ^-3 g / m ² · day. Since the lower the moisture permeability is, the lower the lower limit is, for example, 0.1 × 10 ^-3 g / m ² · day.

In another example of the present application, the present application relates to a method for producing a barrier film. The method may comprise curing the polysilazane layer formed on the substrate layer.

In one example, the substrate layer may be the same as that described above. The polysilazane layer may be a layer formed by being directly applied on the substrate layer.

In one example, the polysilazane layer may be a layer formed by applying directly on the substrate layer. The polysilazane layer is formed by applying the above-described polysilazane-containing composition onto a substrate, and may include polysilazane and particles as a main component. In addition, the composition for forming a polysilazane layer may further comprise a solvent. Specific details regarding polysilazane, particles and solvent are the same as those mentioned above.

In one aspect, the polysilazane layer may be a layer formed by applying on the intermediate layer. In this case, the intermediate layer may be a layer previously formed on the base layer. The constitution of the intermediate layer may be formed from the same constitution as described above.

The coating method for forming the polysilazane layer or the intermediate layer on the base layer is not particularly limited, and various known methods can be used. For example, a composition for forming a polysilazane layer or an intermediate layer may be formed using, for example, a roll coating, a spin coating, a dip coating, a flow coating, a spray coating, It can be applied on the base layer or the coated body.

In one example, the formation of a cured layer, i. E. Curing to a polysilazane layer, can be accomplished by plasma treatment.

The plasma treatment is performed by generating a plasma in an atmosphere containing a plasma generation gas such as Ar and injecting positive ions into the plasma to the polysilazane layer. The plasma may be generated, for example, by an external electric field or a negative high voltage pulse have. Such a plasma treatment can be performed using a known apparatus.

The plasma treatment for forming the cured layer may be performed while injecting the discharge gas Ar and oxygen in a predetermined processing space. More specifically, the plasma treatment may be performed under the following conditions.

In one example, the plasma treatment may be performed at a predetermined power density. Specifically, the power density per unit area of the electrode in the plasma treatment may be about 0.05 W / cm ² or 0.10 W / cm ^{2 or} more. The power density in another example about 0.2 W / cm ^2, greater than or equal to about 0.3 W / cm ^2, greater than or equal to about 0.4 W / cm ^2, greater than or equal to about 0.5 W / cm ^2, greater than or equal to about 0.6 W / cm ^2, greater than or equal to about 0.7 W / cm ^{2, at} least about 0.8 W / cm ^2, or at least about 0.9 W / cm ² . Within the range that satisfies the power density, in the case of a positive electrode, the higher the power density, the higher the degree of plasma treatment for a short time, and the degree of denaturation of the polysilazane due to the application of a high voltage can be increased. Considering this point, the upper limit of the power density is about 2 W / cm ² or less, 1.5 W / cm ² or less, or 1.0 W / cm ^{2 in} the case of a negative electrode because an excessively high power density may cause damage of the base layer due to high voltage. / cm < ² >.

In one example, in the case of having the power density, the processing energy in the plasma treatment, which is determined by multiplying the power density by the processing time, may be 50 J / cm ² or less. Specifically, the energy may be 45 J / cm ² or less, 40 J / cm ² or less, 35 J / cm ² or less, 30 J / cm ² or less, 25 J / cm ² or less, or 20 J / cm ² or less, The lower limit may be at least 5 J / cm ^{2, at} least 10 J / cm ^2, or at least 15 J / cm ² .

In one example, the plasma treatment may be performed at a predetermined process pressure. Specifically, the process pressure during the plasma treatment may be 350 mTorr or less. In the case of the positive electrode, plasma treatment can be performed without loss of energy without energy loss due to collision with gas molecules since the mean free path can be easily secured as the process pressure is lower. For example, the process pressure may be less than 340 mTorr, less than 330 mTorr, less than 320 mTorr, less than 310 mTorr, less than 300 mTorr, less than 290 mTorr, less than 280 mTorr, less than 270 mTorr, less than 260 mTorr, less than 250 mTorr, less than 240 mTorr Less than 230 mTorr, less than 220 mTorr, less than 210 mTorr, or less than 200 mTorr. On the other hand, in the case of a negative electrode, a lower voltage and power may be required to generate a plasma because the lower the process pressure is, the smaller the number of gas molecules. Since the high voltage and high power may cause damage to the substrate layer, The lower limit is at least 50 mTorr, at least 60 mTorr, at least 70 mTorr, at least 80 mTorr, at least 90 mTorr, at least 100 mTorr, at least 110 mTorr, at least 120 mTorr, at least 130 mTorr, at least 140 mTorr, at least 150 mTorr, at least 160 mTorr, 170 mTorr, 180 mTorr, or 190 mTorr. The pressure may be a pressure at the start of the process, and the pressure may be maintained within the range during the process.

When using the discharge gas (Ar) and oxygen (O ₂ ) as the process gas, the vapor pressure of oxygen in the processing space may be in the range of 20 to 80%. The oxygen vapor pressure means a percentage of the injection flow rate of oxygen to be injected relative to the total flow rate of gases injected into the processing space. For example, in the case of performing the plasma treatment while injecting Ar and O ₂ at flow rates of A sccm and B sccm, respectively, the vapor pressure of oxygen can be calculated as 100 x B / (A + B). The flow rate of each gas can be adjusted at a level that satisfies the vapor pressure.

The plasma treatment time can be appropriately adjusted at a level that does not hinder the barrier properties of the film. For example, a plasma treatment may be performed for a time of about 10 seconds to 10 minutes.

In one example, the method may further comprise heating the polysilazane layer prior to performing the plasma treatment. The heating can be carried out, for example, in the range of 40 to 150 DEG C for several minutes to several hours. After the solvent is evaporated through the heating, plasma treatment may be performed.

The film of the present application has excellent barrier properties. Accordingly, it can be used as a barrier film or a sealing film in various applications such as various packaging materials, a display such as a liquid crystal display (LCD), a member for a solar cell, a substrate for an electronic paper or an organic light emitting diode (OLED) have. Particularly, the barrier film formed in the above manner is excellent in optical performance such as transparency and can be effectively used in optical devices such as various display devices or lighting devices. Further, since the barrier film of the present application is required to have a flexible or foldable property, it can be used for a display device or a lighting device in which a polymer substrate is used instead of glass.

When used in this application, the barrier film may be positioned such that the barrier layer (B) is adjacent to a protected object, i.e., a structure susceptible to moisture. For example, when the barrier film is attached to an OLED element, as in FIG. 3, the order of lamination may be a base layer, a barrier layer and an OLED element. A known lamination method may be used for the attachment, or a known adhesive may be used.

According to the example of the present application, since the characteristics of the film do not change greatly even after the severe condition test for verifying the barrier property of the film, a barrier film can be provided which ensures quality uniformity and is advantageous for custimzing .

1 schematically shows a barrier film according to an example of the present application. The barrier film may include a substrate layer 100 and a barrier layer 200 formed on the substrate layer.
2 schematically shows a barrier film according to another example of the present application. The barrier film 1 may include a base layer 100, an intermediate layer 300 formed on the base layer, and a barrier layer 200 formed on the intermediate layer.
3 is a view for explaining the use of the barrier film according to one example of the present application.

Hereinafter, the present application will be described in detail by way of examples. However, the scope of protection of the present application is not limited by the embodiments described below.

Example  One

An about 900 nm thick intermediate layer was formed on the surface of a PET (poly (ethylene terephthalate)) -based film having a thickness of about 50 탆 by using isocyanurate-based acrylate.

Subsequently, a polysilazane solution (produced by adding about 2 parts by weight of dimethylarnolamine (DMEA) as an organic catalyst to 100 parts by weight of polysilazane to CLARIANT's NN 120 solution) and silica particles (Nissan chemical inducstires , 10 parts by weight of MEK-AC-4130Y (relative to 100 parts by weight of polysilazane) was coated to a thickness of about 150 nm (formation of polysilazane layer) and dried at 130 DEG C for 2 minutes. The plasma treatment for the polysilazane layer was then performed at about Ar: O 2 = 1: 1 flow rate (based on sccm), about 138 mTorr pressure, about 0.27 W / cm ² power and about 20 J / cm ² energy .

Example  2 to 7 and Comparative Example

A barrier film was prepared in the same manner as in Example 1, except that the kind, particle size, and / or content of particles used were different from those of Example 1, as shown in Table 1 below.

The methods of measuring the water permeability, Y and B values shown in Table 1 are as follows.

- Water permeability (Moisture permeability) : MOCON Aquatron 1 was used as measuring equipment and measured according to ISO 15106-3. Specifically, the apparatus and method were used to measure the M ₁ moisture permeability (measured as "before" in Table 1 below) measured at 38 ° C. and 100% relative humidity for 150 hours at 85 ° C. and 85% relative humidity The measured M ₂ moisture permeability (measured as " after " in Table 1 below) was measured after storage of the barrier film.

- b * value : The b * value in the L * a * b * color space of CIE (International Commission on Illumination) of the barrier film was measured according to the manufacturer's manual using a JASCO V-7100 Spectrophotometer. b ₁ * is the b * value of the barrier film stored at room temperature for less than 12 hours (a measurement indicated as "before" in Table 1 below), b ₂ * is stored for 150 hours at 85 ° C. and 85% relative humidity B * value of the barrier film (measured value shown as " before " in Table 1 below).

[Table 1]

As can be seen in Table 1 above, an increase in b ^* value was observed after the harsh condition test in both the example and comparative films using the polysilazane cured layer as the barrier material. However, in the embodiment using the polysilazane cured layer containing particles as described above, it can be seen that the degree of increase of the b ^* value is greatly suppressed as compared with the comparative example.

Claims (10)

A base layer (A); And a barrier layer (B) disposed on one side of the base layer and including at least one cured layer of a polysilazane layer containing particles,
Wherein the change amount (b *) of the b * value calculated according to the following formula (1) satisfies 0.5 or less:
[Equation 1]
^{_{△ b * = b 2 * -}} b 1 *
(Where b ₁ ^* and b ₂ ^* are the b ^* values of the barrier film in the L ^* a ^* b ^* color space of CIE (International Commission on Illumination) and b ₁ ^* B ^* value of the stored barrier film and b ₂ ^* is the b ^* value of the barrier film stored for 150 hours at 85 ° C and 85% relative humidity conditions) The barrier film according to claim 1, wherein the amount of change in the moisture permeability calculated according to the following formula (2) satisfies 10 or less:
[Equation 2]
Change in moisture permeability = M ₂ / M ₁
(In the formula 2, M ₁ and M ₂ is a water vapor permeability of the barrier film, measured according to ISO 15106-3 standard, M ₁ is a water vapor permeability of the barrier film measured at 38 ℃ temperature and 100% relative humidity, and M ₂ is Measured after storage of the barrier film at 85 ° C and 85% relative humidity for 150 hours.) 3. The method of claim 2, 85 ℃ and 85% after storage for 150 hours at a relative humidity is 20 × 10 measured moisture permeability ^-3 g / m ² · day or less insulation film. The barrier film of claim 1, wherein the polysilazane has a unit of the following formula:
[Chemical Formula 1]

In the general formula (1), R1, R2 and R3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylsilyl group, an alkylamido group or an alkoxy group. The barrier film of claim 1, wherein the particles have a diameter of at least 15 nm. The barrier film of claim 1, wherein the particles comprise 5 parts by weight or more of the particles relative to 100 parts by weight of the polysilazane. The barrier film of claim 1, wherein the particles are inorganic particles selected from clay, talc, alumina, calcium carbonate, zirconia, and silica particles. The barrier film of claim 1, comprising silica particles. The method according to claim 1, further comprising an intermediate layer (C) between the base layer (A) and the barrier layer (B)
Wherein the intermediate layer (C) comprises a condensate of an acrylic resin, a urethane resin, a melamine resin, an alkyd resin, an epoxy resin, a siloxane polymer or an organosilane compound represented by the following formula (2)
(2)

In formula (2), X is a hydrogen, a halogen, an alkoxy group, an acyloxy group, an alkylcarbonyl group, an alkoxycarbonyl group or -N (R ₂ ) ₂ , R ₂ is hydrogen or an alkyl group, R 1 is an alkyl group, An aryl group, an aryl group, an arylalkyl group, an alkylaryl group, an arylalkenyl group, an alkenylaryl group, an arylalkynyl group, an alkynylaryl group, a halogen, an amino group, an amide group, an aldehyde group, an alkylcarbonyl group, a carboxy group, An alkoxy group, an alkoxycarbonyl group, a sulfonyl group, a phosphoryl group, an acryloyloxy group, a methacryloyloxy group or an epoxy group, Q is a single bond, an oxygen atom or -N (R2 ) -, wherein R2 is a hydrogen atom or an alkyl group, and m is a number within a range of 1 to 3. An electrical or electronic device comprising a barrier film according to claim 1.

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