KR101631331B1 - Inorganic complex and barrier film comprising the same - Google Patents

Abstract

The present invention relates to aluminum oxide or nitride; And an ionic metal oxide, wherein the ionic metal oxide has a binding energy (O1s) of 529.6 to 530.4 eV by X-ray photoelectron spectroscopy, and a barrier film using the composite inorganic material. The barrier film according to the present invention is excellent in water and gas barrier properties without lowering the light transmittance.

Description

TECHNICAL FIELD [0001] The present invention relates to a composite inorganic material and a barrier film containing the same,

The present invention relates to a composite inorganic material and a barrier film comprising the same.

Display devices using liquid crystal devices, electronic ink devices, organic light emitting devices (OLED), and the like are widely used or appearing in the market, and photovoltaic devices using organic or inorganic materials are also used for producing pollution-free energy. Electronic devices and metal wires constituting such devices are vulnerable to chemical substances widely present in living environments such as moisture, oxygen, etc., and are denatured or oxidized. Therefore, it is very difficult to block such substances from approaching electronic devices existing in the device It is important.

Conventionally, a method of using a glass plate as a substrate or a cover plate to protect an internal electric device vulnerable to a chemical substance is used. These glass plates have satisfactory characteristics in terms of light transmittance, thermal expansion coefficient, and chemical resistance, but they are heavy, fragile, and hard, requiring careful handling, and are a limiting factor in product design.

As a result of the above problems, attempts have been made to replace a glass plate used as a substrate material for an electronic device with a plastic film having lightweight properties, excellent impact resistance, and flexibility. The plastic film is excellent in flexibility and is strong against impact and thinner than a glass plate. However, the plastic film has a problem of deteriorating the effect of preventing deterioration of the display device due to penetration of water or oxygen because of insufficient gas barrier property.

An object of the present invention is to provide a composite inorganic material having a novel composition and to provide a film excellent in gas barrier property and light transmittance using the composite inorganic material.

The present invention relates to aluminum oxide or nitride; And an ionic metal oxide, wherein the ionic metal oxide has a binding energy (O1s) by X-ray photoelectron spectroscopy of 529.6 to 530.4 eV.

Further, a barrier film using the composite inorganic material is provided.

The barrier film according to the present invention is excellent in water and gas barrier properties without lowering the light transmittance.

1 to 7 each show a side view of a gas barrier film according to one embodiment of the present invention.

In order to achieve the above object, the present invention provides a nitride semiconductor device comprising: an aluminum oxide or nitride; And an ionic metal oxide, wherein the ionic metal oxide has a binding energy (O1s) by X-ray photoelectron spectroscopy of 529.6 to 530.4 eV. Further, a barrier film and an electronic device including the complex inorganic material are provided.

Hereinafter, the present invention will be described in detail.

The composite inorganic material according to the present invention includes aluminum oxide or nitride; And an ionic metal oxide, and the film produced using the film is excellent in gas barrier property and moisture barrier property. Specifically, the aluminum oxide or nitride may impart moisture barrier properties to the plastic film, and the ionic inorganic material may increase gas barrier properties.

In one example of the present invention, the aluminum oxide may satisfy the following formula (1).

[Chemical Formula 1]

Al _x O _y

In this formula,

x and y are independently an integer of 1 or more.

For example, Al ₂ O ₃ or the like may be used as the aluminum oxide.

As another example of the present invention, the aluminum nitride may satisfy the following general formula (2).

(2)

Al _w N _z

In this formula,

w and z are independently an integer of 1 or more.

For example, AlN or the like may be used as the aluminum nitride.

In the case of manufacturing a gas barrier layer using an inorganic material such as SiO 2 or AlOa (a is an integer of 1 or more) known in the art, the gas barrier properties do not increase or decrease more than a certain thickness. This is because defects grow together as the thickness of the used inorganic material increases, and cracks are generated due to an increase in stress.

The composite inorganic material according to the present invention further comprises an ionic inorganic substance. By adding an ionic inorganic substance, the above problems can be solved. Specifically, when an ionic inorganic substance is added to aluminum oxide or nitride, excellent gas barrier property can be secured even with a thin thickness. Therefore, it is not necessary to increase the thickness of the gas barrier single layer in order to secure a certain level of gas barrier property, and it is possible to prevent the occurrence of defects or cracks caused by the increase in thickness in advance.

Wherein the ionic inorganic material is formed of at least one material selected from metal oxides having a binding energy (O1s) by photoelectron spectroscopy ranging from 529.6 eV to 530.4 eV, and mixtures thereof. The ionic inorganic material may be at least one selected from the group consisting of calcium (Ca), titanium (Ti), nickel (Ni), zinc (Zn), zirconium (Zr), indium (In), tin Nitrides or nitrides of at least one metal selected from the group consisting of oxides, nitrides and oxides of metals. For example, the ionic inorganic material may include at least one of CaO, TiO ₂ , NiO, ZnO, ZrO ₂ , In ₂ O ₃ , SnO _2, and CeO ₂ .

On the other hand, the energy band gap of the inorganic material is an important factor in light transmittance. The energy bandgaps of the ionic inorganic substances CaO, TiO ₂ , NiO, ZnO, ZrO ₂ , In ₂ O ₃ , SnO ₂ and CeO ₂ of the present invention are 7.1 eV, 3.2 eV, 3.6 eV, 3.4 eV and 5.0 eV, 3.7 eV and 3.6 eV, respectively. The ionic inorganic material has an energy band gap of 3 eV or more and is excellent in light transmittance in the visible light region. In one embodiment, the ionic inorganic material may have an energy band gap of 3 eV or greater. For example, the ionic inorganic material may have an energy band gap ranging from 3 eV to 10 eV, specifically from 3 eV to 7.5 eV. In the present invention, the " energy band gap " means a difference in energy value when the material is in the HOMO state and in the LUMO state.

The ionic inorganic substance mentioned in the present invention will be described in more detail as follows.

The physical and chemical properties of the oxide depend on properties such as ion polarizability, cation polarizability, optical basicity, or interaction parameter, which are characteristic of oxides . The oxides have been classified in various ways on the basis of the above-mentioned various characteristics. It has been known that the above properties have a certain relationship with the binding energy (T.L. Barr, " Modern ESCA, The Principles and Practice of X-Ray Phtoelectron Spectroscopy ", CRC Press, Boca Raton, FL, 1994; V. Dimitrov & Komatsu, J. Solid State Chem. 163 (2002) 100). On the other hand, it is known that the iconicity of an inorganic compound depends on the electronegativity difference of the constituent atoms and the bonding structure of the substance and has a close correlation with binding energy. According to this, according to the magnitude of binding energy (O1s) that can be easily determined by X-ray photoelectron spectroscopy, it can be classified into three kinds such as anticommunication, ionic and strong ionic. For example, from 530.5 eV to 533.5 eV based on the binding energy (O1s) obtained in the X-ray photoelectron spectroscopy technique; 529.6 eV to 530.4 eV; And 528.0 eV to 529.5 eV, respectively, semicovalent; Ionic; And very ionic oxides.

The aluminum oxide or nitride; And the ionic metal oxide may be in the range of 95: 5 to 10:90, or in the range of 90:10 to 20:80 in terms of molar ratio, so far as they can realize excellent gas barrier properties without lowering the light transmittance. have.

The present invention provides a barrier film comprising the composite inorganic material described above.

As an example of the present invention, the barrier film comprises a substrate layer; And a composite inorganic layer provided on one or both surfaces of the substrate layer.

The substrate layer is not particularly limited, but may be a plastic film material. Accordingly, the present invention provides a plastic barrier film having excellent gas barrier properties including a base layer. When a plastic film having excellent flexibility is used as a base layer to form a barrier film, gas barrier properties and flexibility of the film can be simultaneously realized. In order to increase the mechanical and thermal properties of the plastic film, one or more selected from the group consisting of simple fillers or fillers in the form of fibers, and mixtures thereof may be further added. Examples of the simple filler include metal, glass powder, diamond powder, silicon oxide, clay, calcium phosphate, magnesium phosphate, barium sulfate, aluminum fluoride, calcium silicate, magnesium silicate, barium silicate, barium carbonate, barium hydroxide Side and aluminum silicate may be used. As the filler of fiber type, glass fiber or woven glass fiber may be used.

The gas barrier film may comprise a buffer layer formed between the substrate layer and the composite inorganic layer. The buffer layer between the substrate layer and the composite inorganic layer can be used to planarize the surface of the substrate layer or to increase the interlaminar adhesion strength comprising the substrate layer or to alleviate the stress experienced by the barrier film when mechanical deformation occurs, May be provided to prevent damage to the film during handling. In addition, the buffer layer can prevent growth of defects or interlayer flaws generated in the inorganic layer from being connected and enhance the moisture blocking effect.

The gas barrier film may further comprise a protective layer formed on the opposite side of the surface of the composite inorganic layer facing the base layer. The protective layer serves to protect the outer surface of the barrier film. The protective layer may be provided to mitigate stresses experienced by the barrier film when mechanical deformation occurs, or to prevent damage to the film during handling of the barrier film.

Further, the barrier film may include a composite inorganic material layer, And a laminated structure including at least one of a buffer layer and a protective layer. The specific laminated structure is not particularly limited, and includes a structure including a buffer layer, a composite inorganic material layer, and a protective layer on one or both sides of the substrate layer.

The thickness of the complex inorganic material layer is not particularly limited but may be 5 nm to 800 nm, specifically 10 nm to 400 nm, and more specifically, 15 nm to 200 nm. If the thickness of the composite inorganic material layer is thinner than the above range, continuity of the composite inorganic material layer becomes difficult to obtain, and thus it may not be easy to achieve a desired level of gas barrier performance. On the contrary, if the thickness of the composite inorganic layer exceeds the above range, the internal stress may increase or the flexibility of the composite inorganic layer may be deteriorated and cracks may easily occur.

The composite inorganic material layer may be formed by chemical vapor deposition (CVD), sputtering, evaporation, atomic layer deposition, or ion plating, but is not limited thereto . Hereinafter, the components constituting each layer will be described in more detail.

As the base layer, a plastic film having flexibility and having transparency of 60% or more, more specifically 90% or more can be used. The plastic film that can be formed of the base layer includes, for example, polyethylene terephthalate (PET), polyethersulfone (PES), polycarbonate (PC), polyethylenenaphthalate (PEN), polyimide , PI), polyarylate, and epoxy resin.

The buffer layer and the protective layer may be formed of at least one selected from the group consisting of an acrylic coating liquid composition, an epoxy coating liquid composition, a metal alkoxide composition, and a urethane coating liquid composition as independent organic-inorganic mixed layers. Alternatively, the buffer layer and the protective layer can be formed independently of each other using a sol-gel coating liquid composition, and the sol-gel coating liquid composition includes, for example, an organic silane and a metal alkoxide, , A solvent or a reaction catalyst.

The organosilane may be at least one compound represented by the following general formula (3). When one type of organosilane compound is used, crosslinking is possible.

 (3)

(R ¹ ) _m -Si-X _(4-m)

In this formula,

X may be the same or different from each other, hydrogen, halogen, alkoxy of 1 to 12 carbon atoms, acyloxy, alkylcarbonyl, alkoxycarbonyl, or -N (R ^{₂₎ 2} (where R ² is from 1 to 12 carbon atoms or hydrogen Lt; / RTI > alkyl)

R ¹ may be the same or different from each other and is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl, alkynylaryl, A substituted or unsubstituted amino, an amide, an aldehyde, a keto, an alkylcarbonyl, a carboxy, a mercapto, a cyano, hydroxy, alkoxy of 1 to 12 carbon atoms, alkoxycarbonyl of 1 to 12 carbon atoms, sulfonic acid, Oxy, epoxy or vinyl group,

Oxygen or -NR ² (wherein, R ² is hydrogen or alkyl of 1 to 12 carbon atoms) is inserted between the radicals R ¹ and _{^{Si (R 1) m -O-}} Si-X (4-m) or (R ¹ ) _m -NR ² -Si-X _(4-m)

m is an integer of 1 to 3;

Examples of the organosilane compound include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldimethoxysilane, diphenyldimethoxysilane, But are not limited to, diethoxysilane, phenyldimethoxysilane, phenyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxy Silane, triphenylethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, dimethylethoxysilane, dimethylethoxysilane, diphenylmethoxysilane, diphenylmethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-aminophenylsilane, allyltrimethoxysilane, n- (2-aminoethyl) -3-amino Propyl trimethoxy silane , 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyldiisopropylethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3- 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- Methacryloxypropyltrimethoxysilane, n-phenylaminopropyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and the like.

The metal alkoxide may be at least one compound represented by the following general formula (4).

[Chemical Formula 4]

M- (R ³⁾ _z

In this formula,

M is at least one metal selected from the group consisting of aluminum, zirconium, titanium, tin and silicon; R ³ is halo, alkyl having 1 to 12 carbon atoms, acyloxy or acyloxy; Lt; / RTI >

Examples of the filler include metal, glass powder, diamond powder, silicon oxide (SiOx where x is an integer of 2 to 4), clay (bentonite, smectite, kaolin etc.), calcium phosphate, magnesium phosphate, barium sulfate, aluminum fluoride, Calcium silicate, magnesium silicate, barium silicate, aluminum silicate, and the like.

As the solvent, a solvent used for a conventional hydrolysis reaction may be used. For example, an alcohol-based, a ketone-based, or distilled water may be used. The catalyst is not particularly limited, and aluminum butoxide and / or zirconium propoxide may be used. The amount of the filler, solvent and catalyst to be used is not particularly limited and may be added as needed.

The coating liquid composition may be formed as a buffer layer or a protective layer by using a thermosetting or photocuring technique alone or in combination. The buffer layer or the protective layer may be formed by treating the surface of the substrate with an ultraviolet ray, a corona, a flame, a plasma, a sputtering, an ion beam, a chemical or the like or an undercoat layer in order to improve the adhesion with the substrate layer.

Further, the barrier film according to the present invention can be utilized variously as a material of an electronic device. For example, the electronic device may include an electronic device packaged with a barrier film according to the present invention. The barrier film may be included in the electronic device in the form of a substrate material, a protective cover or a packaging material. The barrier film may include a separate base layer or, in some cases, a barrier film having no base layer may be applied to the electronic device and used as a protective layer of the electronic device. The electronic device is not particularly limited, but may be an organic or inorganic light emitting device, a display device, a film-type battery, a detector, or a solar power plant.

Hereinafter, the barrier film according to the present invention will be described in detail with reference to FIGS. 1 to 7. FIG.

1 to 4 are side views of a barrier film according to an embodiment of the present invention, respectively. Referring to FIG. 1, a composite inorganic material layer 20 is formed on a plastic substrate layer 10. The structure disclosed in FIG. 1 may be variously modified. For example, FIG. 2 shows a structure in which a protective layer 30 is formed on a laminated structure of a base layer 10 and a composite inorganic layer 20. 3 shows a structure in which a separate buffer layer 40 is formed between the base layer 10 and the composite inorganic layer 20. 4 shows a barrier film having a structure in which a base layer 10, a buffer layer 40, a composite inorganic material layer 20, and a protective layer 30 are sequentially laminated.

5 to 7 are side views of a barrier film according to another embodiment of the present invention, respectively. Referring to FIG. 5, the composite polymer layers 21 and 22 are formed on both sides of the plastic substrate layer 10 as a reference. The structure disclosed in FIG. 5 may be variously modified. For example, in Fig. 6, a buffer layer 41, a composite inorganic material layer 21 and a protective layer 31 are sequentially laminated on the upper surface of the base material layer 10, and a composite inorganic material layer 22 ). 7 shows a structure in which the buffer layers 41 and 42, the composite inorganic layers 21 and 22 and the protective layers 31 and 32 are symmetrically stacked on the basis of the base layer 10.

The present invention will be described more specifically with reference to the following examples. However, these embodiments are merely illustrative and do not limit the technical scope of the present invention.

Example  One

As the plastic substrate layer, a PET film (A4300, manufactured by Toyobo) having a thickness of 50 탆 was used. A silane-based sol-based solution containing 32.5 parts by weight of tetraethoxysilane and 64 parts by weight of glycidyloxypropyltrimethoxysilane as a main component was coated on the upper surface of the plastic substrate layer and thermally cured at 120 ° C for 10 minutes, To form a buffer layer. A mixed inorganic material layer in which Al ₂ O ₃ and CaO were mixed at a molar ratio of 90:10 was deposited to a thickness of 80 nm using a sputtering technique while supplying a mixture gas of argon and oxygen to the deposition equipment. The silane-based sol-like solution was coated on the barrier film by the same process as the upper surface of the base layer and thermally cured to form a barrier layer to produce a barrier film.

The gas permeability of the produced barrier film was evaluated using L80-5000LP manufactured by Lyssy under conditions of relative humidity of 100% and temperature of 38 ° C. The optical properties of the barrier film were evaluated using UV3600 from Shimadzu. The evaluation results are shown in Table 1 below.

Comparative Example  One

Except that a first inorganic material layer made of CaO as a composite inorganic material layer was deposited to a thickness of 20 nm and a second inorganic material layer made of Al ₂ O ₃ was deposited thereon to a thickness of 60 nm , A barrier film was prepared in the same manner as in Example 1. The measured gas permeability and optical characteristics of the barrier film are shown in Table 1 below.

Comparative Example  2

A barrier film was prepared in the same manner as in Example 1, except that an inorganic material layer of Al ₂ O ₃ was deposited as a composite inorganic material layer to a thickness of 80 nm in Example 1. The measured gas permeability and optical characteristics of the barrier film are shown in Table 1 below.

Comparative Example  3

A barrier film was prepared in the same manner as in Example 1, except that an inorganic material layer made of CaO was deposited as a composite inorganic material layer to a thickness of 62 nm in Example 1. The measured gas permeability and optical characteristics of the barrier film are shown in Table 1 below.

Comparative Example  4

A barrier film was prepared in the same manner as in Example 1, except that an inorganic material layer made of SiON was deposited as a composite inorganic material layer to a thickness of 80 nm. The measured gas permeability and optical characteristics of the barrier film are shown in Table 1 below.

Inorganic layer component Thickness (nm) Light transmission characteristics (%) Gas permeability
(g / m ² -day) T (%) Haze Example 1 Al ₂ O ₃ + CaO 80 85.6 0.3 0.004 Comparative Example 1 CaO (1 layer), Al ₂ O _{3 (2} layers) 60/20 85.5 0.3 0.07 Comparative Example 2 Al ₂ O ₃ 80 85.6 0.2 0.008 Comparative Example 3 CaO 62 86.3 0.5 > 0.5 Comparative Example 4 SiON 80 91.3 0.1 0.008

As shown in Table 1, Example 1 using a barrier film of a composite inorganic material showed lower gas permeability than Comparative Examples 1 to 4. Thus, it can be seen that the barrier film according to the present invention has excellent barrier properties.

Example  2

As the plastic substrate layer, a PET film (A4300, manufactured by Toyobo) having a thickness of 50 탆 was used. A silane-based sol-based solution containing 40.0 parts by weight of tetraethoxysilane and 56.5 parts by weight of glycidyloxypropyltrimethoxysilane as a main component was coated on the upper surface of the plastic substrate layer and thermally cured at 120 ° C for 10 minutes to obtain a 0.5 μm Thick buffer layer. An inorganic composite layer of Al ₂ O ₃ and ZnO mixed in a weight ratio of 70:30 was deposited to a thickness of 65 nm using a sputtering technique while supplying a mixture gas of argon and oxygen to the upper surface of the buffer layer, To prepare a barrier film.

The gas permeability of the prepared barrier film was evaluated, and the results are shown in Table 2 below.

Comparative Example  4

Example 2 was carried out in the same manner as in Example 2, except that an inorganic layer made of only SiON was deposited as an inorganic layer to a thickness of 80 nm. The measured gas permeability of the produced barrier film is shown in Table 2 below.

Example  3

As the plastic substrate layer, a PET film (A4300, manufactured by Toyobo) having a thickness of 50 탆 was used. A silane-based sol-based solution containing 40.0 parts by weight of tetraethoxysilane and 56.5 parts by weight of glycidyloxypropyltrimethoxysilane as a main component was coated on the upper surface of the plastic substrate layer and thermally cured at 120 ° C for 10 minutes to obtain a 0.5 μm Thick buffer layer. A composite inorganic material layer, in which AlN and TiO ₂ were mixed in a ratio of 50:50 by weight, was deposited to a thickness of 70 nm using a sputtering technique while supplying a mixture gas of argon and oxygen to the upper surface of the buffer layer.

The gas permeability of the prepared barrier film is shown in Table 2 below.

Inorganic layer component Thickness (nm) Gas permeability (g / m ² -day) Example 2 Al ₂ O ₃ + ZnO 65 0.004 Comparative Example 4 SiON 80 0.008 Example 3 AlN + TiO ₂ 70 0.005

As shown in Table 2, it can be seen that Example 2 and Example 3 according to the present invention exhibit lower gas permeability than Comparative Example 4.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. It is also natural.

10: plastic film base 20, 21, 22: composite inorganic layer
30, 31, 32: protective layer 40, 41, 42: buffer layer

Claims (16)

A base layer; And
An aluminum oxide or nitride provided on one side or both sides of the substrate layer; And a composite inorganic material layer containing an ionic metal oxide containing at least one of CaO, TiO ₂ and ZnO and having a thickness of 65 to 80 nm,
Aluminum oxide or nitride; And the ionic metal oxide is 90:10 to 50:50 parts by weight,
Wherein the ionic metal oxide has a binding energy (O1s) of 529.6 to 530.4 eV by X-ray photoelectron spectroscopy. The method according to claim 1,
Wherein the aluminum oxide satisfies the following formula (1): < EMI ID =
[Chemical Formula 1]
Al _x O _y
In this formula,
x and y are independently an integer of 1 or more. The method according to claim 1,
Wherein the aluminum nitride satisfies the following formula (2): < EMI ID =
(2)
Al _w N _z
In this formula,
w and z are independently an integer of 1 or more. The method according to claim 1,
And a buffer layer formed between the base layer and the composite inorganic layer. The method according to claim 1,
Wherein the composite inorganic layer further comprises a protective layer formed on a surface opposite to a surface facing the substrate layer. The method according to claim 1,
Wherein a laminate structure including a buffer layer, a composite inorganic material layer, and a protective layer is provided on one surface or both surfaces of the substrate layer. The method according to claim 1,
The substrate layer may be selected from the group consisting of polyethyleneterephthalate, polyethersulfone, polycarbonate, polyethylenenaphthalate, polyimide, polyarylate and epoxy resins. Wherein the barrier film comprises at least one of the following materials: 5. The method of claim 4,
Wherein the buffer layer comprises at least one selected from the group consisting of a sol-gel coating liquid composition, an acrylic coating liquid composition, an epoxy coating liquid composition and a urethane coating liquid composition. 9. The method of claim 8,
Wherein the sol-gel-based coating liquid composition comprises an organosilane and a metal alkoxide. 6. The method of claim 5,
Wherein the protective layer comprises at least one selected from the group consisting of a sol-gel coating liquid composition, an acrylic coating liquid composition, an epoxy coating liquid composition and a urethane coating liquid composition. 11. The method of claim 10,
Wherein the sol-gel-based coating liquid composition comprises an organosilane and a metal alkoxide. An electronic device comprising the barrier film for an electronic device according to claim 1. delete delete delete delete

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