KR102536973B1 - Preparation method for sealed electronic device, and Sealed electronic device prepared therefrom - Google Patents

Abstract

providing a base substrate on one side of which electronic devices are disposed, within a vacuum enclosure; disposing a first coating layer on the electronic device by supplying at least one of a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, and an aromatic cyclic compound having an unsaturated functional group and a polar functional group; Sealing the electronic device by disposing a second coating layer containing a parylene-based polymer on the first coating layer by supplying parylene-based radicals derived from a parylene-based precursor to the first coating layer; manufacturing a sealed electronic device including A method and a sealed electronic device produced thereby are presented.

Description

Method for manufacturing a sealed electronic device, and a sealed electronic device manufactured thereby {Preparation method for sealed electronic device, and Sealed electronic device prepared therefrom}

A method for manufacturing a sealed electronic device, and a sealed electronic device manufactured thereby.

Electronic devices such as OLEDs and LCDs contain organic materials, but organic materials are vulnerable to moisture and oxygen in the air. In order to protect the electronic device from them, the electronic device is sealed with a barrier thin film.

With the advent of flexible OLEDs, organic barrier thin films that are flexible, have moisture barrier properties, can be formed at low temperatures, and have transparency are required.

In order to introduce a polymer coating layer on the surface of a substrate, a wet method such as spin coating is generally used.

Spin coating involves a solvent. It is difficult to introduce a uniform coating layer on the surface of a substrate having a three-dimensional structure due to a difference in volatilization rate of a solvent on the surface of a substrate having a three-dimensional structure.

A dry method such as iCVD is used to introduce a coating layer on the surface of the substrate. In iCVD, an initiator is pyrolyzed into radicals by a hot filament, and then the radicals proceed with a polymerization reaction of monomers to introduce a polymer coating layer on a substrate.

In iCVD, radicals are generated only in adjacent regions of hot filaments arranged in a straight line. Therefore, it is difficult to introduce a uniform coating layer on the surface of the electronic device having a three-dimensional structure that does not have a constant distance from the hot filament.

The organic barrier thin film has low adhesion to the surface of an electronic device and can be easily peeled off from the substrate.

There is a need for a method of introducing a uniform and robust barrier thin film on the surface of an electronic device having a three-dimensional structure.

One aspect of the present invention is to provide a new method for manufacturing a sealed electronic device in which an organic barrier thin film is introduced onto a base substrate on which an electronic device is disposed.

Another aspect of the present invention is to provide a sealed electronic device manufactured by the manufacturing method.

according to one side

providing a base substrate on one side of which electronic devices are disposed, within a vacuum enclosure;

disposing a first coating layer on the electronic device by supplying at least one of a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, and an aromatic cyclic compound having an unsaturated functional group and a polar functional group;

Sealing the electronic device by disposing a second coating layer containing a parylene-based polymer on the first coating layer by supplying parylene-based radicals derived from a parylene-based precursor to the first coating layer; manufacturing a sealed electronic device including A method is provided.

According to another aspect,

a base substrate on one surface of which an electronic device is disposed;

Including; sealing layer for sealing the electronic device,

The sealing layer is a first coating layer; And a second coating layer disposed on the first coating layer; includes,

The first coating layer includes at least one selected from a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, an aromatic cyclic compound having an unsaturated functional group and a polar functional group, and derivatives thereof,

A sealed electronic device is provided in which the second coating layer includes a parylene-based polymer.

According to one aspect, the adhesion of the barrier thin film to the electronic device is improved by disposing an intermediate layer derived from an aromatic heterocyclic compound between the electronic device and the coating layer including the parylene-based polymer.

As a result, electronic elements are more effectively sealed.

1 is a schematic diagram of a method of disposing a first coating layer and a second coating layer according to an exemplary embodiment.
Fig. 2 is a cross-sectional schematic view of a base substrate on which sealed electronic devices are disposed according to an exemplary embodiment.
Fig. 3 is a partial cross-sectional schematic diagram of a sealed electronic device according to an exemplary embodiment.
Fig. 4 is a partial cross-sectional schematic diagram of a sealed electronic device according to an exemplary embodiment.
Fig. 5 is a partial cross-sectional schematic diagram of a sealed electronic device according to an exemplary embodiment.
Fig. 6 is a partial cross-sectional schematic diagram of a sealed electronic device according to an exemplary embodiment.
Fig. 7 is a schematic cross-sectional view of a coating apparatus according to an exemplary embodiment.
8a is an XPS analysis result of the first coating layer of Example 1-1.
8B is an XPS analysis result of the first coating layer of Examples 1-4.
8C is a contact angle measurement result for the first coating layer of Example 1-1.
8d is a contact angle measurement result for the first coating layer of Examples 1-4.
8e is a contact angle measurement result for the first coating layer of Comparative Example 1-1.
8F is an adhesion test result for the coating layer of Example 1-1.
8g is an adhesion test result for the coating layer of Examples 1-6.
8H is an adhesion test result for the coating layer of Examples 1-11.
8i is an adhesion test result for the coating layer of Comparative Example 1-1.
8j is an ATR-FTIR measurement result for the first coating layer of Example 1-1.
8k is an ATR-FTIR measurement result for the first coating layer of Examples 1-4.
8l is an ATR-FTIR measurement result for the second coating layer of Example 1-1.
8m is an ATR-FTIR measurement result for the second coating layer of Examples 1-3.
<Description of symbols for main parts of drawings>
5: base substrate 10: electronic element
15: sealing layer
20: second coating layer 30: third coating layer
100: first vaporizer 110: first transfer pipe
120: first heat source 200: first flow controller
250: first valve 300: pyrolysis machine
310: second transfer pipe 320; 2nd heat source
400: deposition chamber 500: cold trap
600: vacuum pump 700: second vaporizer
710: third transfer pipe 800: second flow controller
850: second valve 1000: coating device

Since the present inventive concept described below may be applied with various transformations and may have various embodiments, specific embodiments are illustrated in the drawings and described in detail. However, this is not intended to limit the present creative idea to a specific embodiment, and should be understood to include all transformations, equivalents, or substitutes included in the technical scope of the present creative idea.

Terms used below are only used to describe specific embodiments, and are not intended to limit the present inventive idea. Singular expressions include plural expressions unless the context clearly dictates otherwise. Hereinafter, terms such as “comprise” or “have” are intended to indicate that there is a feature, number, step, operation, component, part, component, material, or combination thereof described in the specification, but one or the other It should be understood that the presence or addition of the above other features, numbers, steps, operations, components, parts, components, materials, or combinations thereof is not precluded. "/" used below may be interpreted as "and" or "or" depending on the situation.

In the drawings, the thickness is enlarged or reduced to clearly express various layers and regions. Like reference numerals have been assigned to like parts throughout the specification. Throughout the specification, when a part such as a layer, film, region, plate, etc. is said to be "on" or "above" another part, this includes not only the case directly on top of the other part, but also the case where there is another part in the middle thereof. . Throughout the specification, terms such as first and second may be used to describe various components, but the components should not be limited by the terms. Terms are used only to distinguish one component from another. Components having substantially the same functional configuration in the present specification and drawings refer to the same reference numerals, and redundant description is omitted.

In the present specification, "two-dimensional structure" is a structure in which the size of one dimension (eg x dimension) is 1/100 or less compared to the size of the other two dimensions (eg y and z dimensions) means For example, metal thin films, polymer sheets, etc. have a two-dimensional structure.

In this specification, a "three-dimensional structure" means a structure in which the sizes of three dimensions (eg, x, y, and z dimensions) are similar to each other. For example, a sphere, a cube, a regular tetrahedron, and the like have a three-dimensional structure. It is also possible to have a three-dimensional structure introduced into a part of the surface of the two-dimensional structure. For example, a printed circuit board on which a three-dimensional circuit including a concave-convex structure is printed on a two-dimensional substrate also has a three-dimensional structure.

In this specification, “conformal coating layer” means a coating layer disposed on the surface of a substrate to conform to the topology of the substrate.

Hereinafter, a coating method and an article according to exemplary embodiments will be described in more detail.

A method of manufacturing a sealed electronic device according to an embodiment includes providing a base substrate on which an electronic device is disposed on one surface in a vacuum enclosure; Disposing a first coating layer on an electronic device by supplying at least one of a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, and an aromatic cyclic compound having an unsaturated functional group and a polar functional group; and supplying parylene-based radicals derived from a parylene-based precursor onto the first coating layer to place a second coating layer including a parylene-based polymer on the first coating layer to seal the electronic device.

A method of manufacturing a sealed electronic device is to supply at least one of a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, and an aromatic cyclic compound containing an unsaturated functional group and a polar functional group on an electronic device to arrange a first coating layer. By including the step, adhesion between the second coating layer disposed on the first coating layer and the electronic device is improved. Therefore, adhesion between the electronic device and the second coating layer is improved, and the second coating layer provides corrosion resistance, oxidation resistance, water resistance, chemical resistance, and the like to the electronic device. The parylene-based polymer included in the second coating layer has excellent barrier properties against moisture and/or oxygen. Since the first coating layer improves adhesion between the second coating layer and the electronic device, barrier properties, corrosion resistance, oxidation resistance, water resistance, and chemical resistance of the sealing layer including the first coating layer and the second coating layer are improved. Since the second coating layer coated on the electronic device is not easily separated from the electronic device, the electronic device is stably sealed and protected from the environment for a long time. The above-described first coating layer may be called various names such as a modification layer, an intermediate layer, and an adhesive layer. The above-described second coating layer may be otherwise called various names such as a protective layer, a sealing layer, a blocking layer, and an insulating layer.

In the step of providing a base substrate on one side of which electronic devices are disposed, within a vacuum enclosure, the vacuum enclosure is, for example, a vacuum chamber. The first coating layer and the second coating layer may be simultaneously coated on the base substrate and the electronic device. Accordingly, the sealing layer, which is a barrier thin film including the first coating layer and the second coating layer, can effectively seal the electronic device.

Conventionally, a silane-based compound, for example, an alkoxysilane compound represented by the following chemical formula, has been used to improve the binding force between a substrate such as metal, metal oxide, glass, ceramic, and the like and a polymer coating layer. In the formula below, R ₄ is a common organic functional group.

However, in order to bind such a silane-based compound onto the substrate, pretreatment of the substrate is required. For example, through a Piranha solution (H ₂ SO ₄ +H ₂ O ₂ ) solution treatment or oxygen plasma treatment on a substrate such as metal, glass, ceramic, etc., a hydroxyl group (-OH group) is formed on the substrate It is required to introduce The hydroxyl group (-OH group) generated on the surface of the substrate reacts with the silane-based compound, and the silane-based compound is bonded to the surface through a covalent bond. In addition, additional curing by heat treatment is required to provide sufficient binding force between the silane-based compound and the substrate. If there is no additional curing process such as heat treatment, the binding force may be insufficient.

Compared to the conventional method of wet coating a composition containing a silane-based compound to form a first coating layer, the sealing method of the present invention does not require an additional curing process such as plasma treatment and/or heat treatment of the electronic device and the base substrate. is simpler and more efficient. In addition, additional facilities for plasma treatment and/or heat treatment are not required. In addition, since it is a dry method that does not apply a coating solution on an electronic device, additional steps such as removal of a solvent after coating are unnecessary, so the time required for the entire process is shortened and the process is simplified. In addition, there is no problem of environmental contamination by volatilized solvents. Since the first coating layer and the second coating layer can be successively deposited in the same chamber in the same dry method, manufacturing efficiency is improved.

In the step of disposing the first coating layer by supplying at least one of a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, and an aromatic ring compound having a polar functional group on the electronic device and the base substrate, the non-fluorine-based acrylic compound The terminal substituent connected to the oxygen atom of contains 5 or less carbon atoms, and an aromatic heterocyclic compound containing an unsaturated functional group and an aromatic ring compound containing an unsaturated functional group and a polar functional group are, for example, a 5 membered ring Or a 6-membered ring, the aromatic heterocyclic compound includes at least one hetero atom selected from nitrogen, oxygen, and sulfur, and the aromatic heterocyclic compound includes 1 to 4 hetero atoms, and the aromatic ring compound It does not contain a hetero atom, the unsaturated functional group may be a functional group containing a double bond or a triple bond, and the polar functional group may be a functional group containing an oxygen or sulfur atom.

The non-fluorine-based acrylic compound does not contain a fluorine atom in its molecule, and may contain 5 or less carbon atoms in a substituent bonded to the terminal oxygen of the ester bond (-C(=O)O-). If the fluorine atom is included in the molecule, adhesion between the electronic device and the base substrate may be deteriorated. If the number of carbon atoms bonded to the terminal oxygen atom is excessively increased to 6 or more, adhesion between the electronic device and the base substrate may deteriorate.

The heterocyclic compound containing an unsaturated functional group may be, for example, a compound represented by Formulas 1 to 9 below, and an aromatic compound containing an unsaturated functional group and a polar functional group may be a compound represented by Formulas 10 to 11 below:

<Formula 1> <Formula 2> <Formula 3>

<Formula 4> <Formula 5> <Formula 7>

<Formula 7> <Formula 8> <Formula 9>

<Formula 10> <Formula 11>

In the above formulas, R ₁ to R ₁₄ are each independently selected from unshared electrons, hydrogen, an alkyl group having 1 to 5 carbon atoms, a vinyl group, an allyl group, or a propargyl group, and R ₁ to R ₄ is a vinyl group, an allyl group, or a propalyl group, at least one of R ₆ , R ₇ and R ₉ is a vinyl group, an allyl group, or a propalyl group, and at least one of R ₁₀ to R ₁₄ is One is a vinyl group, an allyl group, or a propalyl group, R ₁₅ to R ₂₅ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a thiol group, a vinyl group (vinyl), an allyl group (allyl) , Or is selected from a propargyl group, at least one of R ₁₅ to R ₂₀ is a vinyl group, an allyl group, or a propargyl group, and at least the other is a hydroxy group or a thiol group, and R ₂₁ to R ₂₆ At least one of them is a vinyl group, an allyl group, or a propalyl group, and at least the other is a hydroxyl group or a thiol group. Compounds represented by Formulas 1 to 11 may include, for example, a vinyl group. Compounds represented by Chemical Formulas 10 to 11 may further include a hydroxy group or a thiol group in addition to a vinyl group. The number of hydroxyl groups included in the compounds represented by Chemical Formulas 10 and 11 may be, for example, one or two. Compounds represented by Chemical Formulas 10 to 11 may be more firmly bound to the substrate by including two hydroxy groups or thiol groups.

The aromatic heterocyclic compound including an unsaturated functional group may be, for example, an azole-based compound having a vinyl group, a pyridine-based compound having a vinyl group, and the like. Aromatic heterocyclic compounds containing an unsaturated functional group are, for example, 4-vinylpyridine, 2-vinylpyridine, 3-allypyridine, and 1-vinylimide. sol (1-vinylimidazole) or 2-methyl-1-vinylimidazole (2-methyl-1-vinylimidazole).

The aromatic ring compound containing an unsaturated functional group and a polar functional group is, for example, a phenyl-based compound having a vinyl group and a hydroxyl group, a cyclopentadienyl-based compound having a vinyl group and a hydroxyl group, a phenyl-based compound having a vinyl group and a thiol group, and vinyl and a cyclopentadienyl-based compound having a thiol group. An aromatic ring compound containing an unsaturated functional group and a polar functional group is, for example, 1,2-dihydroxy-4-vinylbenzene, 1,2-dithiol-4-vinylbenzene, 1,2-dihydroxy-4- vinyl cyclopentadiene, 1,2-dithiol-4-vinylcyclopentadiene.

The non-fluorine-based acrylic compound may be, for example, a compound represented by Formula 20 below:

<Formula 20>

In the formula, R ₂₇ is hydrogen, methyl, ethyl, propyl, butyl, hydroxymethyl, or 2-hydroxyethyl, and R ₂₈ is hydrogen or methyl.

The non-fluorine-based acrylic compound may be, for example, (2-hydroxyethyl) methacrylate or (2-hydroxyethyl) acrylate.

The first coating layer is a self-assembled layer of a non-fluorine-based acrylic compound chemically adsorbed on the electronic device and the base substrate, an aromatic heterocyclic compound including an unsaturated functional group, and/or an aromatic cyclic compound including an unsaturated functional group and a polar functional group. layer). A non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, and/or an aromatic cyclic compound having an unsaturated functional group and a polar functional group are adsorbed and/or condensed on the electronic device and the base substrate to chemically bond with the electronic device and the base substrate. It can be chemisorbed by forming. For example, as shown in FIG. 1 , nitrogen atoms of 1-vinylimidazole may be chemically adsorbed by forming chemical bonds on the surface of the electronic device and the base substrate. In addition, a non-fluorine-based acrylic compound, an aromatic heterocyclic compound including an unsaturated functional group, and/or an aromatic cyclic compound including an unsaturated functional group and a polar functional group may be self-assembled on the electronic device and the base substrate to form a monolayer. It is also possible to form a plurality of layers of a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, and/or an aromatic cyclic compound containing an unsaturated functional group and a polar functional group. The first coating layer may be formed of, for example, a monomolecular compound without including a polymer. The first coating layer may be obtained by, for example, chemical vapor deposition (CVD).

In the step of disposing a second coating layer containing a parylene-based polymer on the first coating layer by supplying parylene-based radicals derived from a parylene-based precursor onto the first coating layer, the second coating layer comprises an unsaturated functional group included in the first coating layer. It may contain a parylene-based polymer grafted on (grafted). For example, referring to FIG. 1, a parylene-based polymer is formed on an unsaturated functional group included in the first coating layer by reacting a radical derived from a parylene-based precursor with an unsaturated functional group included in an aromatic heterocyclic compound forming the first coating layer. It may be grafted to form a second coating layer. Since the unsaturated functional group included in the first coating layer reacts with radicals derived from the parylene-based precursor to form a parylene-based polymer, a separate catalyst or initiator for the graft reaction may not be used. Accordingly, the formation of the second coating layer can proceed more simply. Since the chemically adsorbed first coating layer is disposed on the electronic device and the base substrate, the second coating layer and the first coating layer may be bonded more easily and strongly. As a result, the second coating layer is more strongly bound on the electronic element and the base substrate, and as a result, the electronic element can be more firmly sealed. The second coating layer can be obtained by, for example, chemical vapor deposition (CVD). The first coating layer and the second coating layer may be, for example, conformal coating layers. Accordingly, the first coating layer and the second coating layer may form a uniform coating layer on the electronic device and the base substrate having a three-dimensional structure.

In order to help the understanding of this creative idea, the mechanism by which the parylene-based polymer forms the second coating layer and the effect obtained by the second coating layer are explained in more detail, but this is to help the understanding of this creative idea, and this creative idea in any form does not limit the scope of

The second coating layer containing the parylene-based polymer is obtained by forming a polymer-type thin film by chemical vapor deposition (CVD) from parylene-based dimer powder represented by the following Chemical Formulas 12 to 19, for example. lose In the second coating layer containing the parylene-based polymer, the parylene-based dimer in powder form is evaporated by heat, and the evaporated parylene-based dimer is thermally decomposed while passing through the thermal decomposition unit of the coating device to be converted into parylene-based monomers, and the parylene-based monomer is cooled before being diffused into the vacuum chamber, and the cooled monomer is polymerized in the vacuum chamber to form a polymer layer in the form of a film on the surface of the electronic device and the base substrate. Since the polymerization reaction of the parylene-based monomer proceeds at a very low pressure and room temperature of 30° C. or less, thermal stress is not generated on the surface of the electronic device and the base substrate. In addition, since the coating using the parylene-based monomer is a dry coating, unlike the wet coating, the coating is uniformly applied even in the minute gaps on the electronic element and base substrate, and the electronic element and base such as sharp needles, holes, corners, corners, and minute holes Regardless of the shape of the substrate, it is possible to form a uniform conformal coating film on the substrate. In addition, since pinholes and/or pores do not occur in the second coating layer including the parylene-based polymer, excellent protective film properties can be provided on the inorganic compound electronic device and the base substrate as well as the organic compound electronic device and the base substrate. In addition, the second coating layer comprising a parylene-based polymer can completely seal the electronic device and the base substrate and has excellent water resistance because it absorbs little moisture and/or oxygen. Accordingly, the water resistance of the electronic device and the base substrate coated with the second coating layer containing the parylene-based polymer is improved. In addition, the second coating layer including the parylene-based polymer has excellent chemical resistance because it is hardly affected by most chemicals such as acids, alkalis, or solvents. In addition, the second coating layer including the parylene-based polymer has excellent light transmittance before coating. After that, there is no change in the appearance of the surface of the electronic device and the base substrate, and the decrease in light transmittance is suppressed. In addition, surface lubricity of the electronic device and the base substrate coated with the second coating layer containing the parylene-based polymer is improved. Therefore, there is little adsorption of fine dust or viscous oil components on the coated electronic device and base substrate. As a result, the contamination resistance of the coated electronic device and the base substrate is improved.

The parylene precursor may include, for example, at least one selected from dimers represented by Chemical Formulas 12 to 19:

<Formula 12> <Formula 13> <Formula 14> <Formula 15>

<Formula 16> <Formula 17> <Formula 18> <Formula 19>

Parylene-based polymers included in the second coating layer include Parylene N, Parylene C, Parylene D, Parylene AF-4, Parylene HT, Parylene VT-4, Parylene CF, Parylene A, Parylene AM, It may include at least one selected from Parylene H, Parylene SR, Parylene HR, and Parylene NR. Water resistance may be improved by including the parylene-based compound in the parylene-based polymer. Parylene-based polymers may include, for example, Parylene N.

In order to supply a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, and/or an aromatic cyclic compound containing an unsaturated functional group and a polar functional group on the surface of an electronic device and a base substrate, a heterocyclic compound containing an unsaturated functional group And / or the vaporization temperature of the aromatic ring compound containing an unsaturated functional group and a polar functional group is, for example, 25 ~ 150 ℃, 30 ~ 140 ℃, 40 ~ 130 ℃, 50 ~ 120 ℃, 60 ~ 110 ℃, or 70 ~ 100 ℃ It may be ℃, but it is not necessarily limited to this range and may be adjusted according to the boiling point (boiling point) of the compound to be vaporized.

In order to supply parylene-based radicals derived from the parylene-based precursor on the first coating layer, the vaporization temperature of the parylene-based precursor is, for example, 100 to 200 ° C, 110 to 190 ° C, 120 to 180 ° C, or 130 to 170 ° C, and , The thermal decomposition temperature of the parylene precursor may be, for example, 500 to 750 ° C, 550 to 750 ° C, 550 to 700 ° C, 600 to 700 ° C, 650 to 700 ° C, 660 to 700 ° C, or 670 to 690 ° C. While the first coating layer and the second coating layer are introduced, the temperature of the electronic device and the base substrate may be 20 to 40°C, 20 to 35°C, or 20 to 30°C. By having the vaporization temperature, the thermal decomposition temperature, and/or the temperature of the electronic device and the base substrate within these ranges, water resistance and adhesion of the coating layer may be improved, and a more uniform and robust coating layer may be introduced.

The thickness of the first coating layer may be, for example, 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 40 nm or less, 30 nm or less, 20 nm or less, or 10 nm or less. The thickness of the first coating layer is, for example, 0.1 nm to 100 nm, 0.5 nm to 90 nm, 1 nm to 80 nm, 1 nm to 70 nm, 1 nm to 60 nm, 1 nm to 50 nm, 1 nm to 40 nm, 1 nm to 30 nm, 1 nm to 20 nm, or 1 nm to 1 nm. It may be 10 nm. When the first coating layer has a thickness within this range, binding force of the second coating layer may be further improved.

The thickness of the second coating layer is 10 nm to 500 μm, 10 nm to 200 μm, 10 nm to 100 μm, 10 nm to 50 μm, 10 nm to 20 μm, 10 nm to 15 μm, 10 nm to 10 μm, 10 nm to 5 μm, and 10 nm to 1 μm. , 10 nm to 500 nm, 10 nm to 300 nm, 10 nm to 200 nm, or 10 nm to 100 nm. When the second coating layer has a thickness within this range, water resistance and adhesiveness of the second coating layer may be improved, and a more uniform coating layer may be introduced. If the thickness of the second coating layer is too thin, the coating effect may be insignificant. If the thickness of the coating layer is too thick, a uniform coating layer may not be obtained.

The material of the base substrate may be, for example, metal, metalloid, metal oxide, metal nitride, glass, organic/inorganic composite, polymer, fiber, paper, or wood. The base substrate may be a silicon (Si) substrate, a silica (SiO ₂ ) substrate, a carbon substrate, a graphite substrate, a metal substrate, or a polymer substrate. The base substrate may be, for example, an article or article having a two-dimensional structure. The base substrate may be, for example, a polycarbonate substrate, a polyethylene terephthalate substrate, a glass substrate, an ITO substrate (a glass substrate coated with indium tin oxide), and the like. The metal may include, for example, a metal element belonging to Groups 1 to 16 of the Periodic Table of Elements. Metals include, for example, copper (Cu), aluminum (Al), stainless steel, nickel (Ni), zinc (Zn), iron (Ti), titanium (Ti), lead (Pb), cobalt (Co), chromium (Cr), tungsten (W), magnesium (Mg), gold (Au), silver (Ag), platinum (Pt), or alloys thereof.

The base substrate may be a flexible base substrate or a non-flexible base substrate. The flexible base substrate refers to a base substrate that can be bent or bent. The material of the flexible base substrate is not limited as long as it has flexibility. The non-flexible base substrate refers to a base substrate that is substantially not bent or bent. If the thickness of the flexible base substrate increases, it may become a non-flexible base substrate, and if the thickness of the non-flexible base substrate decreases, it may become a flexible base substrate. Metals, metalloids, polymers, paper, fibers, etc. are flexible base substrates. A glass substrate is a flexible substrate if it is thin.

A surface material of the electronic device may be the same as that of the base substrate. For example, the surface material of the electronic device may be a metal electrode such as silver (Ag). Alternatively, the surface of the electronic device may be pre-coated with a protective layer before the first coating layer and the second coating layer are applied. The material of this protective layer may be the same as that of the above-described base substrate. The protective layer material may be, for example, a metal thin film, an organic-inorganic composite thin film, or a polymer thin film.

The surface material of the electronic device may be, for example, polycarbonate, polyethylene terephthalate, glass, or indium tin oxide (ITO).

Electronic devices may have flexibility. Thus, electronic elements can be bent or bent. For example, an organic light emitting device including an organic layer disposed between flexible electrodes may be bendable.

Referring to Figure 7 will be described in more detail with respect to the coating method according to one embodiment.

First, a coating device is prepared.

The coating device 1000 includes a first vaporizer 100 that accommodates and vaporizes the parylene precursor powder, a first flow controller 200 connected to the first vaporizer 100, and a first flow controller 200. A thermal decomposition device 300 connected thereto, a deposition chamber 400 in which parylene glass radicals passing through the thermal decomposition device 300 are deposited on a substrate, a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group and/or an unsaturated functional group, and A second vaporizer 700 for accommodating and vaporizing an aromatic ring compound containing a polar functional group therein, a second flow rate controller 800 communicating with the second vaporizer 700, cooling for cooling by discharging gas generated during deposition, etc. A trap 500 and a vacuum pump 600 for maintaining a vacuum inside the deposition chamber 400 are included. A first valve 250 capable of opening and closing is disposed between the first flow controller 200 and the thermal decomposer 300, and a second valve 850 capable of opening and closing between the second flow controller 800 and the deposition chamber 300 is placed

The second vaporizer 700 heats the non-fluorine-based acrylic compound supplied to the inside, an aromatic heterocyclic compound having an unsaturated functional group, and/or an aromatic ring compound including an unsaturated functional group and a polar functional group, and vaporizes the non-fluorine-based acrylic compound and the unsaturated functional group. Produces an aromatic heterocyclic compound having and/or an aromatic cyclic compound containing an unsaturated functional group and a polar functional group. For example, in a predetermined space connected to the second vaporizer 700, a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, and/or an aromatic ring including an unsaturated functional group and a polar functional group are introduced into the second vaporizer 700. It is possible to introduce compounds. The second vaporizer 700 is provided with a third transfer pipe 710 formed with a long cylindrical inner space on the left and right to move along the inner space. A non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, and/or an aromatic cyclic compound including an unsaturated functional group and a polar functional group are heated and vaporized at a temperature of about 25 to 150° C. in the second vaporizer 700. The compound, an aromatic heterocyclic compound having an unsaturated functional group, and/or an aromatic cyclic compound having an unsaturated functional group and a polar functional group is supplied to the deposition chamber 400 along the third transfer pipe 710 in the form of a single molecule.

The first vaporizer 100 generates a vaporized parylene precursor by heating the parylene precursor powder supplied therein. A container (not shown) containing parylene powder may be disposed in the first vaporizer 100 . Alternatively, it is possible to introduce parylene precursor powder into the first vaporizer 100 in a predetermined space connected to the first vaporizer 100 . The first vaporizer 100 is provided with a first transfer pipe 110 formed with a long cylindrical inner space on the left and right, and a first heat source 120 is disposed on the outer surface of the space to vaporize parylene powder accommodated therein. It allows you to move along the inner space. A heat wire coil or the like may be used as the heat source 120 on the outer surface of the first vaporizer 100 . The parylene precursor powder is heated to a temperature of about 100 to 200° C. in the first vaporizer 100 and moved toward the thermal decomposer 300 along the first transfer pipe 110 in the form of a vaporized parylene precursor.

The thermal cracker 300 communicates with the first vaporizer 100, includes a second transfer pipe 310 through which the vaporized parylene precursor generated in the first vaporizer 100 moves, and includes a vaporized non-fluorine-based acrylic compound. , and a second heat source 320 generating parylene free radicals by heating and thermally decomposing the parylene precursor. In the thermal decomposer 300, the vaporized parylene precursor supplied from the first vaporizer 100 is thermally decomposed to generate parylene free radicals, that is, parylene monomer. The internal temperature of the thermal decomposer 300 is about 500 to 750 °C. The form of the pyrolysis machine 300 is, for example, a form of a furnace through which a second transfer pipe 310 made of quartz passes therein. In order to minimize heat loss of the first vaporizer 100 and the thermal cracker 300, a heat insulating layer may be disposed outside them.

The deposition chamber 400 communicates with the thermal decomposer 300 and includes a space formed therein. A base substrate on which electronic devices are disposed on one surface is disposed in an inner space of the deposition chamber 400 . A base substrate on which electronic devices are disposed on one surface has a three-dimensional structure.

Next, the vaporized non-fluorine-based acrylic compound generated from the second vaporizer 700, an aromatic heterocyclic compound having an unsaturated functional group, and/or an unsaturated functional group and a polar functional group are grouped on the surface of the base substrate on which the electronic device is disposed on one surface. An aromatic ring compound containing is supplied. A non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, and/or an aromatic cyclic compound having an unsaturated functional group and a polar functional group are chemically adsorbed on the surface of an electronic device and a base substrate to form a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group A first coating layer in which a compound and/or an aromatic ring compound including an unsaturated functional group and a polar functional group is self-assembled is deposited. The inside of the deposition chamber 400 is a low-temperature environment of about 20 to 40° C. adjacent to room temperature. The supply time of the vaporized non-fluorine-based acrylic compound, the aromatic heterocyclic compound having an unsaturated functional group, and/or the aromatic cyclic compound including an unsaturated functional group and a polar functional group into the deposition chamber 400 is 10 to 50 minutes, 15 to 30 minutes, It may be 20 to 40 minutes. If the supply time of the vaporized non-fluorine-based acrylic compound, the aromatic heterocyclic compound having an unsaturated functional group, and/or the aromatic cyclic compound having an unsaturated functional group and a polar functional group is too short, the first coating layer may not be formed properly, and the first coating layer may not be formed properly. If the formation time is excessively long, a substantial change in the first coating layer may be insignificant. The pressure inside the deposition chamber 400 is 2 to 20 times greater than before supplying the vaporized non-fluorine-based acrylic compound, the aromatic heterocyclic compound having an unsaturated functional group, and/or the aromatic cyclic compound having an unsaturated functional group and a polar functional group. can be maintained In this pressure range, the first coating layer may be deposited more efficiently. The rate at which the vaporized non-fluorine-based acrylic compound, the aromatic heterocyclic compound having an unsaturated functional group, and/or the aromatic cyclic compound including an unsaturated functional group and a polar functional group are supplied to the inside of the deposition chamber 400 is It can be adjusted within the range where the pressure is maintained.

Subsequently, parylene-based radicals derived from the parylene precursor generated in the thermal decomposition unit 300 are supplied onto the first coating layer. Parylene free radicals generated in the thermal decomposition unit 300 proceed with a graft polymerization reaction on the surface of the first coating layer to the unsaturated functional group of the non-fluorine-based acrylic compound, aromatic heterocyclic compound, and/or aromatic ring compound, and A second coating layer containing a parylene-based polymer is formed. The inside of the deposition chamber 400 is a low-temperature environment of about 20 to 40° C. adjacent to room temperature. The second coating layer containing the parylene-based polymer is formed by graft polymerization of vaporized parylene free radicals and unsaturated functional groups of non-fluorine-based acrylic compounds/aromatic heterocyclic compounds/aromatic ring compounds. This polymerization reaction is carried out at about room temperature. It is carried out at a low temperature of 20 to 40 ° C. Accordingly, the electronic device and the base substrate may be made of materials having low heat resistance at high temperatures, such as thermoplastic polymer films and thermoplastics, in addition to heat-resistant materials such as metals, metalloids, semiconductors, and glass. Since the deposition is substantially performed at room temperature, thermal deterioration and deterioration by heat of an electronic device having a complex three-dimensional structure can be prevented. Therefore, it is applicable to practically all types of electronic devices. A base substrate on which electronic devices are disposed on one surface may have a complex three-dimensional structure. Electronic devices include, for example, organic light emitting devices (OLEDs), liquid crystal displays (LCDs), charge-coupled devices (CCDs), and micro-electro-mechanical sensors. -mechanical sensors (MEMS), and organic or inorganic photoelectric conversion devices based on thin-film solar cells. For example, referring to FIG. 6 , a conformal coating layer having a constant thickness is formed on the electronic device and the base substrate to conform to their surface contours. The pressure inside the deposition chamber 400 may be maintained at 1.5 to 10 times the pressure before parylene glass radicals are supplied. In this pressure range, the second coating layer may be deposited more efficiently. A rate at which parylene glass radicals are supplied into the deposition chamber 400 may be controlled within a range in which the above-described internal pressure of the deposition chamber 400 is maintained.

The first vaporizer 100, the second vaporizer 700, the thermal decomposer 300, and the deposition chamber 400 all maintain an internal vacuum state during the coating process. To this end, a cooling trap 500 and a vacuum pump 600 are connected to the deposition chamber 400 . The cooling trap 500 is a device for collecting and cooling gases generated during coating, and the vacuum pump 600 communicating with the cooling trap 500 is a first vaporizer 100 and a second vaporizer 700 during the coating process. ), the thermal decomposer 300 and the deposition chamber 400, and serves to make a vacuum inside and maintain their vacuum state.

A first flow rate controller 200 is disposed between the first vaporizer 100 and the thermal decomposer 300 . The first flow rate controller 200 controls the rate at which the vaporized parylene precursor passes through the thermal decomposer 300 and is supplied into the deposition chamber 400 . The first flow rate controller 200 constantly controls the amount of the vaporized parylene precursor supplied to the deposition chamber 400 after passing through the thermal decomposer 300 .

A first valve 250 capable of opening and closing is disposed between the first flow controller 200 and the thermal decomposer 300 . The first valve 250 may be closed when preparing for the next step after the coating layer forming step is completed or when charging of the parylene precursor powder is required during the coating layer forming step. The first valve 250 is, for example, a vacuum ball valve.

A second flow controller 800 is disposed between the second vaporizer 700 and the deposition chamber 400 . The second flow controller 800 controls the rate at which the vaporized non-fluorine-based acrylic compound and the aromatic heterocyclic compound having an unsaturated functional group are supplied into the deposition chamber 300 . The content of the vaporized non-fluorine-based acrylic compound, the aromatic heterocyclic compound having an unsaturated functional group, and/or the aromatic cyclic compound having an unsaturated functional group and a polar functional group being supplied to the deposition chamber 400 by the second flow controller 800 is kept constant. Adjust.

A second valve 850 capable of opening and closing is disposed between the second flow controller 700 and the deposition chamber 400 . The second valve 850 prepares for the next step after the coating layer forming step is completed, or, during the coating layer forming step, a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, and/or an aromatic cyclic compound including an unsaturated functional group and a polar functional group. can be locked if recharging is required. The second valve 850 is, for example, a vacuum ball valve.

The amount of the vaporized parylene precursor supplied into the deposition chamber 400 is constantly controlled by the first flow controller 200 . Accordingly, as the pressure inside the deposition chamber 400 is maintained within a certain range, it is easy to control the process of forming a coating layer on the surface of the substrate. In addition, it is possible to prevent a decrease in the deposition rate of the coating layer due to pressure variations inside the deposition chamber 400 . Thus, the coating layer deposition rate is improved, and consequently, the productivity of coating layer manufacturing is improved.

Referring to FIGS. 2 to 6 , a sealed electronic device according to another embodiment includes a base substrate 5 on which an electronic device 10 is disposed on one surface; and a sealing layer 15 for sealing the electronic device 10, wherein the sealing layer 15 includes a first coating layer (not shown); and a second coating layer 20 disposed on the first coating layer (not shown), wherein the first coating layer (not shown) includes a non-fluorine-based acrylic compound, an aromatic heterocyclic compound including an unsaturated functional group, an unsaturated functional group, and a polar It includes at least one selected from an aromatic ring compound containing a functional group and a derivative thereof, and the second coating layer 20 includes a parylene-based polymer.

The electronic device 10 is, for example, an organic light emitting device (OLED), a liquid crystal display (LCD), a charge-coupled device (CCD), microelectromechanical sensors ( micro-electro-mechanical sensors (MEMS), and organic or inorganic photoelectric conversion devices based on thin-film solar cells.

Referring to FIG. 3 , the sealed electronic device includes, for example, a first coating layer (not shown) disposed on the surface of the electronic device 10, and the first coating layer includes a non-fluorine-based acrylic compound and an unsaturated functional group. A second coating layer 20 comprising at least one selected from aromatic heterocyclic compounds and derivatives thereof and disposed on the surface of the first coating layer (not shown), wherein the second coating layer 20 is formed from a parylene precursor. and parylene-based polymers derived from The sealed electronic device 10 includes a first coating layer (not shown) and a second coating layer 20, which are conformal coating layers introduced on the surface of the electronic device 10 and the base substrate 5, so that the electronic device 10 ) can improve durability, water resistance, chemical resistance, etc.

Referring to FIG. 4 , the sealed electronic device may include, for example, an electronic device 10; A first coating layer (not shown) comprising at least one selected from a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, and a derivative thereof; a second coating layer 20 comprising a parylene-based polymer derived from a parylene precursor; and a third coating layer 30 including a copolymer of a parylene-based radical derived from a parylene precursor and another organic monomer. Adhesion, water resistance, and chemical resistance of the coating layer may be further improved by including the three-layer structure of the coating layer. Other organic monomers may be, for example, acrylic monomers, siloxane-based monomers, silazane-based monomers, and the like. The third coating layer 30 may be an organic-inorganic composite layer.

Referring to FIG. 5 , the sealed electronic device may include, for example, an electronic device 10; A first coating layer (not shown) comprising at least one selected from a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, and a derivative thereof; a second coating layer 20 comprising a parylene-based polymer derived from a parylene precursor; a third coating layer 30 comprising a copolymer of a parylene-based radical derived from a parylene precursor and another organic monomer; and a fourth coating layer 20 including a parylene-based polymer derived from a parylene precursor. Adhesion, water resistance, and chemical resistance of the coating layer may be further improved by including the four-layer structure of the coating layer. Other organic monomers may be, for example, acrylic monomers, siloxane-based monomers, silazane-based monomers, and the like. The third coating layer 30 may be an organic-inorganic composite layer.

Referring to FIG. 6 , the sealed electronic device may include, for example, an electronic device 10; A first coating layer (not shown) comprising at least one selected from a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, and a derivative thereof; a second coating layer 20 comprising a parylene-based polymer derived from a parylene precursor; a third coating layer 30 comprising a copolymer of a parylene-based radical derived from a parylene precursor and another organic monomer; a fourth coating layer 20 comprising a parylene-based polymer derived from a parylene precursor; and a fifth coating layer 30 including a copolymer of a parylene-based radical derived from a parylene precursor and another organic monomer. Adhesion, water resistance, and chemical resistance of the coating layer may be further improved by including the five-layer structure of the coating layer. Other organic monomers may be, for example, acrylic monomers, siloxane-based monomers, silazane-based monomers, and the like. The third coating layer 30 may be an organic-inorganic composite layer.

In the present specification, "aromatic heterocyclic compound" refers to a monocyclic compound in which an aromatic ring contains one or more heteroatoms selected from N, O, P, or S, and the remaining ring atoms are carbon. ) or a bicyclic organic compound. The aromatic heterocycle may include, for example, 1-5 heteroatoms and 5-10 ring members. The O, S or N may be oxidized and have various oxidation states.

Aromatic monocyclic heterocyclic compounds include, for example, thiophene, pyrrole, imidazole, pyrazole, thiazole isothiazole 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2 ,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3 ,4-thiadiazole, isothiazole, oxazole, isoxazole, 1,2,4-triazole, 1,2,3-triazole, tetrazole pyridine, 2-pyrazine, pyrazine, pyrimidine, etc. can be heard

The aromatic heterocyclic compound includes a case in which an aromatic heterocyclic ring is fused to one or more aromatic rings (cylco aromatic), alicyclic rings (cyclo aliphatic), or heteroaromatic rings (cyclo heteroaromatic).

Aromatic bicyclic heterocyclic compounds include, for example, indole, isoindole, indazole, purine, quinoline, isoquinoline, and the like.

In the present specification, "cyclic aromatic compound" refers to a compound in which a hetero atom constituting a ring member included in the "heterocyclic aromatic compound" is substituted with a carbon atom. In other words, “cyclic aromatic compound” means a monocyclic or bicyclic organic compound in which all ring atoms in the aromatic ring are carbon. That is, aromatic It is a carbon ring compound.

In the present specification, "unsaturated functional group" means a functional group having one or more carbon-carbon double bonds or carbon-carbon triple bonds. The unsaturated functional group is, for example, a vinyl group, an allyl group, and the like. In the present specification, "aromatic heterocyclic compound containing an unsaturated functional group" refers to a compound in which the above-mentioned unsaturated functional group is substituted in the aromatic heterocyclic ring of the above-mentioned aromatic heterocyclic compound. it means. For example, imidazole substituted with a vinyl group, pyridine substituted with a vinyl group, and the like.

In the present specification, "polar functional group" means a functional group having polarity including an atom having high electronegativity such as an oxygen or sulfur atom. Polar functional groups are, for example, hydroxy groups, thiol groups and the like.

In the present specification, "aromatic ring compound containing an unsaturated functional group and a polar functional group" means a compound in which the above-described unsaturated functional group and the polar functional group are respectively substituted on the aromatic carbon ring of the above-mentioned aromatic ring compound. For example, benzene in which a vinyl group and 1 to 2 hydroxy groups are substituted, cyclopentadiene in which a vinyl group and 1 to 2 hydroxy groups are substituted, and the like.

As used herein, "alkyl group" refers to a group of fully saturated branched or unbranched (or straight-chain or linear) hydrocarbons.

Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, iso-amyl, n-hexyl , 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl and the like.

Hereinafter, the coating layer forming method related to the embodiment will be described in detail with reference to Examples and Comparative Examples. Incidentally, the examples shown below are only provided for illustrative purposes, and the present invention is not limited to the following examples.

(Manufacture of sealing layer)

Example 1: First coating layer (1-vinylimidazole) and second coating layer (parylene N) coating

A chamber in which the first vaporizer, the second vaporizer, and the pyrolysis unit were connected was prepared.

One sheet of aluminum foil (thickness: 100 μm) with a size of 300 mm x 300 mm was installed in a vertical direction inside a vacuum chamber having a diameter of 700 mm and a height of 800 mm.

The temperature of the second vaporizer was adjusted to 80° C., and the pressure inside the vacuum chamber was adjusted to 10 mTorr or less. The temperature of the vacuum chamber was 25°C.

1-vinylimidazole was introduced into the second vaporizer. 1-vinylimidazole was supplied at a constant flow rate to the vacuum chamber via the second vaporizer. The rate at which vaporized 1-vinylimidazole was supplied to the vacuum chamber was maintained at 100 mTorr by using a second MFC (Mass Flow Controller, MKS 1152C, MKS Instruments, USA). After 20 minutes have elapsed from the point at which 1-vinylimidazole is supplied into the chamber (the point at which 1-vinylimidazole is adsorbed and/or condensed on the surface of the aluminum foil), the needle valve of the second vaporizer is closed and The supply of imidazole (1-vinylimidazole) was stopped and deposition was terminated.

The temperature of the first vaporizer was adjusted to 140°C, the temperature of the thermal decomposer to 670°C, and the pressure inside the vacuum chamber was adjusted to 10 mTorr or less. The temperature of the vacuum chamber was 25°C.

Parylene N dimer powder was introduced into the first vaporizer. Parylene N dimer powder was supplied to the vacuum chamber via the first vaporizer and the pyrolysis unit. Parylene N dimer was vaporized in a vaporizer and then pyrolyzed into free radicals in a thermal decomposer and supplied into the vacuum chamber at a constant flow rate. The rate at which parylene dimer vaporized in the first vaporizer is supplied to the thermal decomposer was maintained at a pressure of 20 mTorr in the reaction chamber using a first MFC (mass flow controller, MKS 1153A, MKS Instruments, USA). The temperature of the MFC was maintained at 185°C. After 90 minutes had elapsed from the point at which parylene radicals were supplied into the chamber (the point at which deposition of the second coating layer started), the supply of parylene N dimer powder was stopped. After confirming that the monomer was completely deposited by reducing the pressure in the vacuum chamber to 10 mTorr or less, the deposition was terminated. After adjusting the pressure of the vacuum chamber to atmospheric pressure, the coated aluminum foil was taken out.

X-ray photoelectron spectroscopy (XPS), Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) spectroscopy, and water (H ₂ O) contact angle measurement of 1-vinylimidazole chemisorption on the surface of aluminum foil - It was confirmed that the first coating layer, which is a self-assembly layer of vinylamidazole monomers, was deposited. Through SEM (Scanning Electron Microscope) cross-sectional analysis, it was found that a second coating layer, a parylene polymer, was deposited on the first coating layer by a graft reaction between the 1-vinylamidazole monomer chemically adsorbed on the surface of the aluminum foil and the parylene radical. Confirmed. The thickness of the second coating layer was about 2 μm.

Example 2: First coating layer (4-vinylpyrine) and second coating layer (parylene N) coating

A coating layer was deposited in the same manner as in Example 1, except that 4-vinylpyridine was used instead of 1-vinylimidazole.

Example 3: First coating layer (1-vinylimidazole) and second coating layer (Parylene C) coating

A coating layer was deposited in the same manner as in Example 1, except that Parylene C dimer was used instead of Parylene N dimer.

Example 1-4

A coating layer was deposited in the same manner as in Example 1-1, except that (hydroxyethyl)methacrylate was used instead of 1-vinylimidazole.

Example 1-5

A coating layer was deposited in the same manner as in Example 1-3, except that (hydroxyethyl)methacrylate was used instead of 1-vinylimidazole.

Examples 1-6 to 1-10

Coating layers were deposited in the same manner as in Examples 1-1 to 1-5, respectively, except that the time for supplying the compound for forming the first coating layer into the chamber was changed from 20 minutes to 40 minutes.

Examples 1-11 to 1-15

Coating layers were deposited in the same manner as in Examples 1-1 to 1-5, except that the supply time of the compound for forming the first coating layer into the chamber was changed from 20 minutes to 60 minutes.

Comparative Example 1-1: Parylene N alone coating

A coating layer was deposited in the same manner as in Example 1-1, except that the step of depositing the first coating layer containing 1-vinylimidazole was omitted and only the second coating layer containing parylene N was deposited.

Comparative Example 1-2: Parylene C single coating

A coating layer was deposited in the same manner as in Examples 1-3, except that the step of depositing the first coating layer containing 1-vinylimidazole was omitted and only the second coating layer containing Parylene C was deposited.

Comparative Example 1-3: First coating layer (siloxane compound) and second coating layer (parylene N) coating

Instead of 1-vinylimidazole monomer, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (1,3,5,7-tetravinyl-1 A coating layer was deposited in the same manner as in Example 1-1, except that ,3,5,7-tetramethyltetrasiloxane, pV4D4) was used.

Evaluation Example 1-1: XPS analysis of Al substrate with first coating layer introduced

In the process of manufacturing the substrates coated in Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-3, XPS (X-ray Photoelectron Spectroscopy) analysis was performed on the surface of the substrate after the first coating layer was introduced. It was confirmed whether or not the first coating layer was introduced.

Some of the analysis results are shown in Figs. 8a to 8b. 8A is for Example 1-1, and FIG. 8B is for Example 1-4.

As shown in FIG. 8A, after 1-vinylimidazole was coated on the Al substrate, peaks for oxygen atoms, nitrogen atoms, and carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that 1-vinylimidazole was coated. The peak for the oxygen atom was determined to be due to a hydrophilic functional group such as a hydroxyl group present on the Al substrate.

As shown in FIG. 8B, after (hydroxyethyl)methacrylate was coated on the Al substrate, peaks for oxygen atoms and peaks for carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that (hydroxyethyl) methacrylate was coated.

It was determined that zinc (Zn) and lead (Pb) peaks were detected as impurities contained in aluminum metal.

Evaluation Example 1-2: Water (H ₂ O) Measurement of contact angle

In the process of manufacturing the coated substrates prepared in Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-3, a contact angle measuring instrument was used for the surface of the substrate after the first coating layer was formed at 25° C. of atmospheric pressure. The contact angle for water was measured.

Some of the measurement results are shown in FIGS. 8C to 8E and Table 1 below. The contact angle is the angle between the interface between water and the substrate and the interface between water and air.

FIG. 8C is for Example 1-1, FIG. 8D is for Example 1-4, and FIG. 8E is for Comparative Example 1-1.

contact angle [°] Example 1-1 63.3 Example 1-4 53.8 Comparative Example 1-1 43.0

As shown in Table 1, the contact angle increased by introducing the first coating layer on the Al substrate. Therefore, it was confirmed that the first coating layer was introduced on the Al substrate.

Evaluation Example 1-3: Adhesion test

Adhesion tests were performed on the coated substrates prepared in Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-3. The adhesion test was evaluated by a Scotch Tape Test based on ASTM D3002 and D3359.

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at intervals of 1 mm to form a grid, and then Scotch tape was attached and peeled off on the grid-shaped coating layer to evaluate the area of the coating layer removed. .

The evaluation criteria are as follows.

5B: 0% of the removed area, 4B: less than 5% of the removed area, 3B: 5-15% of the removed area, 2B: 15-35% of the removed area, 1B: 35-65% of the removed area, 0B: removal 65% or more of the area covered

5B to 3B are excellent, and 2B to 0B are poor.

Some of the measurement results are shown in Table 2 and FIGS. 8F to 8I below.

Adhesion evaluation Example 1-1 5B Example 1-2 5B Example 1-3 5B Example 1-4 0B Example 1-5 2B Example 1-6 5B Examples 1-8 5B Examples 1-9 2B Examples 1-10 4B Example 1-11 5B Examples 1-13 5B Examples 1-14 2B Examples 1-15 4B Comparative Example 1-1 0B Comparative Example 1-2 0B Comparative Example 1-3 0B

As shown in Table 2 and FIGS. 8f to 8i, the adhesion of the coating layers of Examples was excellent as most of 4B or more, and the adhesion of the coating layers of Comparative Examples 1-1 to 1-3 were all 0B and poor.

FIG. 8f is the coating layer of Example 1-1, FIG. 8g is the coating layer of Example 1-6, FIG. 8h is the coating layer of Example 1-11, and FIG. 8i is the adhesion test result of the coating layer of Comparative Example 1-1. The coating layer was transparent. Therefore, the surface of the substrate was seen as it was.

8f to 8h, the coating layer was hardly detached.

On the other hand, in FIG. 8i, most of the coating layer was desorbed, and the coating layer was partially desorbed, and the coating layer appeared opaque due to the empty space generated between the substrate and the coating layer.

That is, in FIG. 8i , most of the coating layer was desorbed and only a portion of the coating layer remained and appeared opaque.

Therefore, it was confirmed that the adhesion between the substrate and the second coating layer was remarkably improved by the introduction of the first coating layer.

Evaluation Example 1-4: ATR-FTIR analysis of Al substrate with first coating layer and second coating layer introduced

In the manufacturing process of the substrates coated in Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-3, ATR on the surface of the substrate after the introduction of the first coating layer and the surface of the substrate after the introduction of the second coating layer -FTIR (Attenuated Total Reflection Fourier Transform Infrared) spectroscopy was performed to confirm whether the first coating layer and the second coating layer were formed. Some of the analysis results are shown in FIGS. 8j to 8m.

FIG. 8j is for the surface of the substrate on which the first coating layer is formed in Example 1-1, and FIG. 8k is for the surface of the substrate on which the first coating layer is formed in Example 1-4.

FIG. 8l is for the surface of the substrate on which the second coating layer is formed in Example 1-1, and FIG. 8m is for the surface of the substrate on which the second coating layer is formed in Example 1-3.

As shown in FIG. 8j, after 1-vinylimidazole is coated on the Al substrate, 1557 cm ^-1 (C = C strethcing), 1604 (C = N stretching), 1490 cm ^-1 (imidazole ring stretching) ), 1204 cm ^-1 (CN streching), 1048 (imidazole ring bending and stretching), 761 cm ^-1 (imidazole ring bending), and 668 cm ^-1 (imidazole ring torsion) due to 1-vinylimidazole peaks were identified. Therefore, it was confirmed that 1-vinylimidazole was coated.

As shown in Figure 8k, after (hydroxyethyl) methacrylate is coated on an Al substrate, 3100-3500 cm ^-1 (OH Stretching), 1716 cm ^-1 (C = O stretching), 1607 cm ^{- 1} (C=C stretching) and 1161 cm ^-1 (ester OC-OC stretching), characteristic peaks attributed to (hydroxyethyl) methacrylate were confirmed. Therefore, it was confirmed that (hydroxyethyl) methacrylate was coated. OH stretching vibration (hydrogen bonding) of ATR-FTIR of pure (hydroxyethyl) methacrylate in solution phase is confirmed as a broad peak in the 3100-3600 cm ^-1 region, but on an Al substrate (hydroxyethyl) When coated with methacrylate, it was confirmed that four peaks were split in the 3100-3500 cm ^-1 region.

As shown in FIG. 8L, after parylene N was additionally coated on the first coating layer of 1-vinylimidazole, 3084 cm ^-1 (aromatic CH stretching), 3007 cm ^-1 (CH ₂ stretching), 2917 cm ^-1 (CH ₂ stretching), 2852 cm ^-1 (CH ₂ stretching), 1511 cm ^-1 (aromatic CC stretching), 1448 cm ^-1 (CH bending), 817 cm ^-1 (two adjacent aromatic CH bending), A characteristic peak due to parylene N was confirmed at 540 cm ^-1 (out-of-plane ring bending). Thus, it was confirmed that parylene N was coated.

As shown in FIG. 8m, after parylene C was additionally coated on the first coating layer of 1-vinylimidazole, 3023 cm ^-1 (CH ₂ stretching), 2926 cm ^-1 (CH ₂ stretching), 2858 cm ^-1 (CH ₂ stretching), 1604 (aromatic CC stretching), 1557 cm ^-1 (aromatic CC stretching), 1449 cm ^-1 (CH bending), 1048 cm ^-1 (aromatic Ar-Cl bending), 877 cm ^{- 1} (neighboring chlorine and ethyl group CH bending) and 820 cm ^-1 (two adjacent aromatic CH bending), characteristic peaks attributed to parylene C were confirmed. Thus, it was confirmed that parylene C was coated.

(Based on Cu)

Example 2-1

A coating layer was deposited in the same manner as in Example 1-1, except that copper foil was used instead of the aluminum foil.

Examples 2-2 to 2-15 and Comparative Examples 2-1 to 2-3

A coating layer was deposited in the same manner as in Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-3, except that copper foil was used instead of the aluminum foil.

Evaluation Example 2-1: XPS analysis of Cu substrate with first coating layer introduced

In the process of manufacturing the substrates coated in Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2-3, XPS (X-ray Photoelectron Spectroscopy) analysis was performed on the surface of the substrate after the first coating layer was introduced. It was confirmed whether or not the first coating layer was introduced.

In Example 2-1, after 1-vinylimidazole was coated on the Cu substrate, peaks for oxygen atoms, nitrogen atoms, and carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that 1-vinylimidazole was coated. The peak for the oxygen atom was determined to be due to a hydrophilic functional group such as a hydroxyl group present on the Cu substrate.

In Example 2-4, after (hydroxyethyl)methacrylate was coated on the Cu substrate, peaks for oxygen atoms and peaks for carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that (hydroxyethyl) methacrylate was coated.

Evaluation Example 2-2: Water (H ₂ O) Measurement of contact angle

In the manufacturing process of the coated substrates prepared in Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2-3, a contact angle measuring instrument was used for the surface of the substrate after the first coating layer was formed at 25° C. of atmospheric pressure. The contact angle for water was measured.

Some of the measurement results are shown in Table 3 below. The contact angle is the angle between the interface between water and the substrate and the interface between water and air.

contact angle [°] Example 2-1 91.5 Example 2-4 98.8 Comparative Example 2-1 87.4

As shown in Table 3, the contact angle increased by introducing the first coating layer onto the Cu substrate. Therefore, it was confirmed that the first coating layer was introduced on the Cu substrate.

Evaluation Example 2-3: Adhesion test

Adhesion tests were performed on the coated substrates prepared in Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2-3. The adhesion test was evaluated by a Scotch Tape Test based on ASTM D3002 and D3359.

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at intervals of 1 mm to form a grid, and then Scotch tape was attached and peeled off on the grid-shaped coating layer to evaluate the area of the coating layer removed. .

The evaluation criteria are as follows.

5B: 0% of the removed area, 4B: less than 5% of the removed area, 3B: 5-15% of the removed area, 2B: 15-35% of the removed area, 1B: 35-65% of the removed area, 0B: removal 65% or more of the area covered

5B to 3B are excellent, and 2B to 0B are poor.

Some of the measurement results are shown in Table 4 below.

Adhesion evaluation Example 2-1 5B Example 2-3 5B Example 2-4 5B Example 2-5 5B Example 2-6 5B Example 2-8 5B Example 2-9 5B Examples 2-10 5B Examples 2-11 5B Example 2-13 5B Example 2-14 5B Example 2-15 5B Comparative Example 2-1 2B Comparative Example 2-2 0B Comparative Example 2-3 0B

As shown in Table 4, the adhesive strength of the coating layer of Example was excellent as 5B, and the adhesive strength of the coating layers of Comparative Example 2-1 to Comparative Example 2-3 were all poor as 2B or less.

Therefore, it was confirmed that the adhesion between the Cu substrate and the second coating layer was remarkably improved by the introduction of the first coating layer.

Evaluation Example 2-4: ATR-FTIR analysis of Cu substrate with first coating layer and second coating layer introduced

In the process of manufacturing the substrates coated in Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2-3, ATR on the surface of the substrate after the introduction of the first coating layer and the surface of the substrate after the introduction of the second coating layer -FTIR (Attenuated Total Reflection Fourier Transform Infrared) spectroscopy was performed to confirm whether the first coating layer and the second coating layer were formed.

Although not shown in the drawing, a first coating layer is formed in Example 2-1, a first coating layer is formed in Example 2-4, a second coating layer is formed in Example 2-1, and Example 2-3 It was confirmed from the ATR-FTIR spectrum that the second coating layer was formed in

(Fe base)

Example 3-1

A coating layer was deposited in the same manner as in Example 1-1, except that an iron sheet was used instead of the aluminum foil.

Examples 3-2 to 3-15 and Comparative Examples 3-1 to 3-3

A coating layer was deposited in the same manner as in Examples 1-2 to 1-15 and Comparative Examples 1-1 to 1-3, except that an iron sheet was used instead of the aluminum foil.

Evaluation Example 3-1: XPS analysis of Fe substrate with first coating layer introduced

In the process of manufacturing the substrates coated in Examples 3-1 to 3-15 and Comparative Examples 3-1 to 3-3, XPS (X-ray Photoelectron Spectroscopy) analysis was performed on the surface of the substrate after the first coating layer was introduced. It was confirmed whether or not the first coating layer was introduced.

In Example 3-1, after 1-vinylimidazole was coated on the Fe substrate, peaks for oxygen atoms, nitrogen atoms, and carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that 1-vinylimidazole was coated. The peak for the oxygen atom was determined to be due to a hydrophilic functional group such as a hydroxyl group present on the Fe substrate.

In Example 3-4, after (hydroxyethyl)methacrylate was coated on the Fe substrate, peaks for oxygen atoms and peaks for carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that (hydroxyethyl) methacrylate was coated.

Evaluation Example 3-2: Water (H ₂ O) Measurement of contact angle

In the process of manufacturing the coated substrates prepared in Examples 3-1 to 3-15 and Comparative Examples 3-1 to 3-3, a contact angle measuring instrument was used for the surface of the substrate after the first coating layer was formed at 25° C. of atmospheric pressure. The contact angle for water was measured.

Some of the measurement results are shown in Table 5 below. The contact angle is the angle between the interface between water and the substrate and the interface between water and air.

contact angle [°] Example 3-1 83.0 Example 3-4 62.9 Comparative Example 3-1 77.3

As shown in Table 5, the contact angle was changed by introducing the first coating layer on the Fe substrate. Therefore, it was confirmed that the first coating layer was introduced on the Fe substrate.

Evaluation Example 3-3: Adhesion test

Adhesion tests were performed on the coated substrates prepared in Examples 3-1 to 3-15 and Comparative Examples 3-1 to 3-3. The adhesion test was evaluated by a Scotch Tape Test based on ASTM D3002 and D3359.

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at intervals of 1 mm to form a grid, and then Scotch tape was attached and peeled off on the grid-shaped coating layer to evaluate the area of the coating layer removed. .

The evaluation criteria are as follows.

5B: 0% of the removed area, 4B: less than 5% of the removed area, 3B: 5-15% of the removed area, 2B: 15-35% of the removed area, 1B: 35-65% of the removed area, 0B: removal 65% or more of the area covered

5B to 3B are excellent, and 2B to 0B are poor.

Some of the measurement results are shown in Table 6 below.

Adhesion evaluation Example 3-1 5B Example 3-3 5B Example 3-4 5B Example 3-5 5B Example 3-6 5B Example 3-8 5B Examples 3-9 5B Example 3-10 5B Example 3-11 5B Example 3-13 5B Example 3-14 5B Example 3-15 5B Comparative Example 3-1 2B Comparative Example 3-2 0B Comparative Example 3-3 0B

As shown in Table 6, the adhesive strength of the coating layer of Example was excellent as 5B, and the adhesive strength of the coating layers of Comparative Example 3-1 to Comparative Example 3-3 were all poor as 2B or less.

Therefore, it was confirmed that the adhesion between the Fe substrate and the second coating layer was remarkably improved by the introduction of the first coating layer.

Evaluation Example 3-4: ATR-FTIR analysis of Fe substrate with first coating layer and second coating layer introduced

In the manufacturing process of the substrates coated in Examples 3-1 to 3-15 and Comparative Examples 3-1 to 3-3, ATR on the surface of the substrate after the introduction of the first coating layer and the surface of the substrate after the introduction of the second coating layer -FTIR (Attenuated Total Reflection Fourier Transform Infrared) spectroscopy was performed to confirm whether the first coating layer and the second coating layer were formed.

Although not shown in the drawings, a first coating layer is formed in Example 3-1, a first coating layer is formed in Example 3-4, a second coating layer is formed in Example 3-1, and Example 3-3 It was confirmed from the ATR-FTIR spectrum that the second coating layer was formed in

(Ti base)

Example 4-1

A coating layer was deposited in the same manner as in Example 1-1, except that a titanium sheet was used instead of the aluminum foil.

Examples 4-2 to 4-15 and Comparative Examples 4-1 to 4-3

A coating layer was deposited in the same manner as in Examples 1-2 to 1-15 and Comparative Examples 1-1 to 1-3, except that a titanium sheet was used instead of the aluminum foil.

Evaluation Example 4-1: XPS analysis of Ti substrate with first coating layer introduced

In the process of manufacturing the substrates coated in Examples 4-1 to 4-15 and Comparative Examples 4-1 to 4-3, XPS (X-ray Photoelectron Spectroscopy) analysis was performed on the surface of the substrate after the first coating layer was introduced. It was confirmed whether or not the first coating layer was introduced.

In Example 4-1, after 1-vinylimidazole was coated on the Ti substrate, peaks for oxygen atoms, nitrogen atoms, and carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that 1-vinylimidazole was coated. The peak for the oxygen atom was determined to be due to a hydrophilic functional group such as a hydroxyl group present on the Ti substrate.

In Example 4-4, after (hydroxyethyl)methacrylate was coated on the Ti substrate, peaks for oxygen atoms and peaks for carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that (hydroxyethyl) methacrylate was coated.

Evaluation Example 4-2: Water (H ₂ O) Measurement of contact angle

In the process of manufacturing the coated substrates prepared in Examples 4-1 to 4-15 and Comparative Examples 4-1 to 4-3, a contact angle measuring instrument was used for the surface of the substrate after the first coating layer was formed at 25° C. of atmospheric pressure. The contact angle for water was measured.

Some of the measurement results are shown in Table 7 below. The contact angle is the angle between the interface between water and the substrate and the interface between water and air.

contact angle [°] Example 4-1 64.7 Example 4-4 53.5 Comparative Example 4-1 40.8

As shown in Table 7, the contact angle increased by introducing the first coating layer on the Ti substrate. Therefore, it was confirmed that the first coating layer was introduced on the Ti substrate.

Evaluation Example 4-3: Adhesion test

Adhesion tests were performed on the coated substrates prepared in Examples 4-1 to 4-15 and Comparative Examples 4-1 to 4-3. The adhesion test was evaluated by a Scotch Tape Test based on ASTM D3002 and D3359.

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at intervals of 1 mm to form a grid, and then Scotch tape was attached and peeled off on the grid-shaped coating layer to evaluate the area of the coating layer removed. .

The evaluation criteria are as follows.

5B: 0% of the removed area, 4B: less than 5% of the removed area, 3B: 5-15% of the removed area, 2B: 15-35% of the removed area, 1B: 35-65% of the removed area, 0B: removal 65% or more of the area covered

5B to 3B are excellent, and 2B to 0B are poor.

Some of the measurement results are shown in Table 8 below.

Adhesion evaluation Example 4-1 5B Example 4-3 5B Example 4-5 1B Example 4-6 5B Examples 4-8 5B Example 4-10 2B Example 4-11 5B Example 4-13 5B Example 4-14 2B Example 4-15 3B Comparative Example 4-1 0B Comparative Example 4-2 0B Comparative Example 4-3 0B

As shown in Table 8, the adhesion of the coating layers of Examples 4-1, 4-3, 4-11, 4-13, 4-16, and 4-18 in which 1-vinylimidazole was used was excellent as 5B. did

In Examples 4-5, 4-10, 4-14, and 4-15 in which (hydroxy)methacrylate was used, overall adhesive strength was improved compared to Comparative Examples 4-1 to 4-3, but 1-vinyl imide Compared to the sol, the adhesive strength was poor.

Therefore, it was confirmed that the adhesion between the Ti substrate and the second coating layer was improved by the introduction of the first coating layer.

Evaluation Example 4-4: ATR-FTIR analysis of Ti substrate to which the first coating layer and the second coating layer were introduced

In the manufacturing process of the substrates coated in Examples 4-1 to 4-15 and Comparative Examples 4-1 to 4-3, ATR on the surface of the substrate after the introduction of the first coating layer and the surface of the substrate after the introduction of the second coating layer -FTIR (Attenuated Total Reflection Fourier Transform Infrared) spectroscopy was performed to confirm whether the first coating layer and the second coating layer were formed.

Although not shown in the figure, a first coating layer is formed in Example 4-1, a first coating layer is formed in Example 4-4, a second coating layer is formed in Example 4-1, and Example 4-3 It was confirmed from the ATR-FTIR spectrum that the second coating layer was formed in

(Pb base)

Example 5-1

A coating layer was deposited in the same manner as in Example 1-1, except that a lead sheet was used instead of the aluminum foil.

Examples 5-2 to 5-15 and Comparative Examples 5-1 to 5-3

A coating layer was deposited in the same manner as in Examples 1-2 to 1-15 and Comparative Examples 1-1 to 1-3, except that a lead sheet was used instead of the aluminum foil.

Evaluation Example 5-1: XPS analysis of Pb substrate with first coating layer introduced

In the process of manufacturing the substrates coated in Examples 5-1 to 5-15 and Comparative Examples 5-1 to 5-3, XPS (X-ray Photoelectron Spectroscopy) analysis was performed on the surface of the substrate after the first coating layer was introduced. It was confirmed whether or not the first coating layer was introduced.

In Example 5-1, after 1-vinylimidazole was coated on the Pb substrate, peaks for oxygen atoms, nitrogen atoms, and carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that 1-vinylimidazole was coated. The peak for the oxygen atom was determined to be due to a hydrophilic functional group such as a hydroxyl group present on the Pb substrate. The peak for the nitrogen atom was small.

In Example 5-4, after (hydroxyethyl)methacrylate was coated on the Pb substrate, peaks for oxygen atoms and peaks for carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that (hydroxyethyl) methacrylate was coated.

Evaluation Example 5-2: Water (H ₂ O) Measurement of contact angle

In the process of manufacturing the coated substrates prepared in Examples 5-1 to 5-15 and Comparative Examples 5-1 to 5-3, a contact angle measuring instrument was used for the surface of the substrate after the first coating layer was formed at 25° C. of atmospheric pressure. The contact angle for water was measured.

Some of the measurement results are shown in Table 9 below. The contact angle is the angle between the interface between water and the substrate and the interface between water and air.

contact angle [°] Example 5-1 86.8 Example 5-4 51.2 Comparative Example 5-1 42.6

As shown in Table 9, the contact angle increased by introducing the first coating layer on the Pb substrate. Therefore, it was confirmed that the first coating layer was introduced on the Pb substrate.

In Example 5-1 coated with 1-vinylimidazole, the contact angle increased remarkably.

Evaluation Example 5-3: Adhesion Test

Adhesion tests were performed on the coated substrates prepared in Examples 5-1 to 5-15 and Comparative Examples 5-1 to 5-3. The adhesion test was evaluated by a Scotch Tape Test based on ASTM D3002 and D3359.

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at intervals of 1 mm to form a grid, and then Scotch tape was attached and peeled off on the grid-shaped coating layer to evaluate the area of the coating layer removed. .

The evaluation criteria are as follows.

5B: 0% of the removed area, 4B: less than 5% of the removed area, 3B: 5-15% of the removed area, 2B: 15-35% of the removed area, 1B: 35-65% of the removed area, 0B: removal 65% or more of the area covered

5B to 3B are excellent, and 2B to 0B are poor.

Some of the measurement results are shown in Table 10 below.

Adhesion evaluation Example 5-1 5B Example 5-3 5B Example 5-4 5B Example 5-5 5B Example 5-6 5B Example 5-8 5B Example 5-9 5B Examples 5-10 5B Example 5-11 5B Example 5-13 5B Example 5-14 5B Example 5-15 5B Comparative Example 5-1 2B Comparative Example 5-2 5B

As shown in Table 10, the adhesion of the coating layers of Examples 5-1, 5-4, 5-6, 5-9, 5-11, and 5-14 using parylene N was comparable to that of Comparative Example 5-1. The adhesion of the coating layer was improved.

The adhesion of the coating layer of Examples 5-3, 5-5, 5-8, 5-10, 5-13, and 5-15 using Parylene C and the adhesion of the coating layer of Comparative Example 5-2 were all excellent as 5B. did

Therefore, it was confirmed that the adhesion between the Pb substrate and the second coating layer was improved to an equal or higher level by the introduction of the first coating layer.

Evaluation Example 5-4: ATR-FTIR analysis of a Pb substrate to which the first coating layer and the second coating layer were introduced

In the process of manufacturing the substrates coated in Examples 5-1 to 5-15 and Comparative Examples 5-1 to 5-3, ATR on the surface of the substrate after the introduction of the first coating layer and the surface of the substrate after the introduction of the second coating layer -FTIR (Attenuated Total Reflection Fourier Transform Infrared) spectroscopy was performed to confirm whether the first coating layer and the second coating layer were formed.

Although not shown in the figure, a first coating layer is formed in Example 5-1, a first coating layer is formed in Example 5-4, a second coating layer is formed in Example 5-1, and Example 5-3 It was confirmed from the ATR-FTIR spectrum that the second coating layer was formed in

(SUS material)

Example 6-1

A coating layer was deposited in the same manner as in Example 1-1, except that a stainless steel substrate (SUS 304 sheet) was used instead of the aluminum foil.

Examples 6-2 to 6-15 and Comparative Examples 6-1 to 6-3

A coating layer was deposited in the same manner as in Examples 1-2 to 1-15 and Comparative Examples 1-1 to 1-3, except that a stainless steel substrate (SUS 304 sheet) was used instead of the aluminum foil.

Evaluation Example 6-1: XPS analysis of SUS substrate with first coating layer introduced

In the process of manufacturing the substrates coated in Examples 6-1 to 6-15 and Comparative Examples 6-1 to 6-3, XPS (X-ray Photoelectron Spectroscopy) analysis was performed on the surface of the substrate after the first coating layer was introduced. It was confirmed whether or not the first coating layer was introduced.

In Example 6-1, after 1-vinylimidazole was coated on the SUS substrate, peaks for oxygen atoms, nitrogen atoms, and carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that 1-vinylimidazole was coated. The peak for an oxygen atom was determined to be due to a hydrophilic functional group such as a hydroxyl group present on the SUS substrate.

In Example 6-4, after (hydroxyethyl)methacrylate was coated on the SUS substrate, peaks for oxygen atoms and peaks for carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that (hydroxyethyl) methacrylate was coated.

Evaluation Example 6-2: Water (H ₂ O) Measurement of contact angle

In the process of manufacturing the coated substrates prepared in Examples 6-1 to 6-15 and Comparative Examples 6-1 to 6-3, a contact angle measuring instrument was used for the surface of the substrate after the first coating layer was formed at 25° C. of atmospheric pressure. The contact angle for water was measured.

Some of the measurement results are shown in Table 11 below. The contact angle is the angle between the interface between water and the substrate and the interface between water and air.

contact angle [°] Example 6-1 75.6 Example 6-4 54.6 Comparative Example 6-1 85.0

As shown in Table 11, the contact angle decreased by introducing the first coating layer on the SUS substrate. Therefore, it was confirmed that the first coating layer was introduced on the SUS substrate.

Evaluation Example 6-3: Adhesion test

Adhesion tests were performed on the coated substrates prepared in Examples 6-1 to 6-15 and Comparative Examples 6-1 to 6-3. The adhesion test was evaluated by a Scotch Tape Test based on ASTM D3002 and D3359.

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at intervals of 1 mm to form a grid, and then Scotch tape was attached and peeled off on the grid-shaped coating layer to evaluate the area of the coating layer removed. .

The evaluation criteria are as follows.

5B: 0% of the removed area, 4B: less than 5% of the removed area, 3B: 5-15% of the removed area, 2B: 15-35% of the removed area, 1B: 35-65% of the removed area, 0B: removal 65% or more of the area covered

5B to 3B are excellent, and 2B to 0B are poor.

Some of the measurement results are shown in Table 12 below.

Adhesion evaluation Example 6-1 3B Example 6-3 3B Example 6-4 2B Example 6-6 5B Examples 6-8 5B Examples 6-9 2B Examples 6-10 2B Examples 6-11 5B Examples 6-13 5B Examples 6-14 3B Examples 6-15 4B Comparative Example 6-1 0B Comparative Example 6-2 0B Comparative Example 6-3 0B

As shown in Table 12, the adhesive strength of the coating layers of Examples 6-1, 6-3, 6-6, 6-8, 6-11, and 6-13 using 1-vinylimidazole was the coating layer of the comparative example. Compared to the adhesion of the improved.

The adhesive strength of the coating layers of Examples 6-4, 6-9, 6-10, 6-14, and 6-15 using (2-hydroxyethyl) methacrylate was improved compared to that of the coating layers of Comparative Examples, but 1 - It was sluggish compared to the coating layer containing vinylimidazole.

Therefore, it was confirmed that the adhesion between the SUS substrate and the second coating layer was improved by the introduction of the first coating layer.

Evaluation Example 6-4: ATR-FTIR analysis of SUS substrate to which the first coating layer and the second coating layer were introduced

In the manufacturing process of the substrates coated in Examples 6-1 to 6-15 and Comparative Examples 6-1 to 6-3, ATR on the surface of the substrate after the introduction of the first coating layer and the surface of the substrate after the introduction of the second coating layer -FTIR (Attenuated Total Reflection Fourier Transform Infrared) spectroscopy was performed to confirm whether the first coating layer and the second coating layer were formed.

Although not shown in the figure, a first coating layer is formed in Example 6-1, a first coating layer is formed in Example 6-4, a second coating layer is formed in Example 6-1, and Example 6-3 It was confirmed from the ATR-FTIR spectrum that the second coating layer was formed in

(glass substrate)

Example 7-1

A coating layer was deposited in the same manner as in Example 1-1, except that a glass sheet was used instead of the aluminum foil.

Examples 7-2 to 7-15 and Comparative Examples 7-1 to 7-3

A coating layer was deposited in the same manner as in Examples 1-2 to 1-15 and Comparative Examples 1-1 to 1-3, except that a glass sheet was used instead of the aluminum foil.

Example 7-16: Sealing of Electronic Devices

Instead of the aluminum foil, a transparent sealing layer was deposited in the same manner as in Example 7-1, except that a 500 mm × 500 mm glass substrate having an organic light emitting device (OLED) attached thereon was used. The sealing layer thickness was about 3 μm.

The organic light emitting device includes a pair of ITO electrodes and an organic layer disposed between the ITO electrodes. The ITO electrode is a transparent conductive electrode coated with indium tin oxide (ITO) on a glass substrate.

It was confirmed that the sealing layer formed a conformal coating layer along the surface of the organic light emitting device and the substrate.

Therefore, it was confirmed that a three-dimensional sealing layer was formed on the electrode and the glass substrate of the organic light emitting device to seal the organic light emitting device.

Comparative Example 7-4: Sealing of electronic elements

The organic light emitting device was sealed in the same manner as in Examples 7-16, except that the step of depositing the first coating layer containing 1-vinylimidazole was omitted and only the second coating layer containing parylene N was deposited. did

Evaluation Example 7-1: XPS analysis of the glass substrate to which the first coating layer was introduced

In the process of manufacturing the substrates coated in Examples 7-1 to 7-15 and Comparative Examples 7-1 to 7-3, XPS (X-ray Photoelectron Spectroscopy) analysis was performed on the surface of the substrate after the first coating layer was introduced. It was confirmed whether or not the first coating layer was introduced.

In Example 7-1, after 1-vinylimidazole was coated on the glass substrate, peaks for oxygen atoms, nitrogen atoms, and carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that 1-vinylimidazole was coated. The peak for the oxygen atom was determined to be due to a hydrophilic functional group such as a hydroxyl group present on the glass substrate.

In Example 7-4, after (hydroxyethyl)methacrylate was coated on the glass substrate, peaks for oxygen atoms and peaks for carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that (hydroxyethyl) methacrylate was coated. Peaks for carbon atoms were significantly reduced compared to those for oxygen atoms.

Evaluation Example 7-2: Water (H ₂ O) Measurement of contact angle

In the process of manufacturing the coated substrates prepared in Examples 7-1 to 7-15 and Comparative Examples 7-1 to 7-3, a contact angle measuring instrument was used for the surface of the substrate after the first coating layer was formed at 25° C. of atmospheric pressure. The contact angle for water was measured.

Some of the measurement results are shown in Table 13 below. The contact angle is the angle between the interface between water and the substrate and the interface between water and air.

contact angle [°] Example 7-1 38.7 Example 7-4 56.5 Comparative Example 7-1 24.7

As shown in Table 13, the contact angle increased by introducing the first coating layer onto the glass substrate. Therefore, it was confirmed that the first coating layer was introduced on the glass substrate.

Evaluation Example 7-3: Adhesion Test (I)

Adhesion tests were performed on the coated substrates prepared in Examples 7-1 to 7-15 and Comparative Examples 7-1 to 7-3. The adhesion test was evaluated by a Scotch Tape Test based on ASTM D3002 and D3359.

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at intervals of 1 mm to form a grid, and then Scotch tape was attached and peeled off on the grid-shaped coating layer to evaluate the area of the coating layer removed. .

The evaluation criteria are as follows.

5B: 0% of the removed area, 4B: less than 5% of the removed area, 3B: 5-15% of the removed area, 2B: 15-35% of the removed area, 1B: 35-65% of the removed area, 0B: removal 65% or more of the area covered

5B to 3B are excellent, and 2B to 0B are poor.

Some of the measurement results are shown in Table 14 below.

Adhesion evaluation Example 7-1 3B Example 7-3 5B Example 7-4 5B Example 7-5 5B Example 7-6 5B Examples 7-8 5B Examples 7-9 5B Examples 7-10 5B Examples 7-11 5B Examples 7-13 5B Examples 7-14 5B Examples 7-15 5B Comparative Example 7-1 0B Comparative Example 7-2 0B Comparative Example 7-3 0B

As shown in Table 14, the adhesive strength of the coating layers of Examples was excellent as 3B or more, and the adhesive strength of the coating layers of Comparative Examples 2-1 and 2-2 was 0B or less, which was poor.

Therefore, it was confirmed that the adhesion between the glass substrate and the second coating layer was remarkably improved by the introduction of the first coating layer.

Evaluation Example 7-4: Adhesion test (II)

An adhesion test was performed on the sealing layer of the electronic device manufactured in Example 7-16 and the electronic device manufactured in Comparative Example 7-4 in the same manner as in Evaluation Example 7-3.

It was confirmed that the sealing layer of the electronic device of Example 7-16 had improved adhesion to the electronic device compared to the sealing layer of the electronic device of Comparative Example 7-4.

Evaluation Example 7-5: ATR-FTIR analysis of the glass substrate to which the first coating layer and the second coating layer were introduced

In the manufacturing process of the substrates coated in Examples 7-1 to 7-15 and Comparative Examples 7-1 to 7-3, ATR on the surface of the substrate after the introduction of the first coating layer and the surface of the substrate after the introduction of the second coating layer -FTIR (Attenuated Total Reflection Fourier Transform Infrared) spectroscopy was performed to confirm whether the first coating layer and the second coating layer were formed.

Although not shown in the drawing, a first coating layer is formed in Example 7-1, a first coating layer is formed in Example 7-4, a second coating layer is formed in Example 7-1, and Example 7-3 It was confirmed from the ATR-FTIR spectrum that the second coating layer was formed in

(Ni base)

Example 8-1

A coating layer was deposited in the same manner as in Example 1-1, except that nickel foil was used instead of the aluminum foil.

Examples 8-2 to 8-15 and Comparative Examples 8-1 to 8-3

A coating layer was deposited in the same manner as in Examples 1-2 to 1-15 and Comparative Examples 1-1 to 1-3, except that nickel foil was used instead of the aluminum foil.

Evaluation Example 8-1: XPS analysis of Ni substrate with first coating layer introduced

In the manufacturing process of the substrates coated in Examples 8-1 to 8-15 and Comparative Examples 8-1 to 8-3, XPS (X-ray Photoelectron Spectroscopy) analysis was performed on the surface of the substrate after the first coating layer was introduced. It was confirmed whether or not the first coating layer was introduced.

In Example 8-1, after 1-vinylimidazole was coated on the Ni substrate, peaks for oxygen atoms, nitrogen atoms, and carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that 1-vinylimidazole was coated. The peak for the oxygen atom was determined to be due to a hydrophilic functional group such as a hydroxyl group present on the Ni substrate. Peaks for nitrogen atoms were insignificant.

In Example 8-4, after (hydroxyethyl)methacrylate was coated on the Ni substrate, peaks for oxygen atoms and peaks for carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that (hydroxyethyl) methacrylate was coated.

Evaluation Example 8-2: Water (H ₂ O) Measurement of contact angle

In the manufacturing process of the coated substrates prepared in Examples 8-1 to 8-15 and Comparative Examples 8-1 to 8-3, a contact angle measuring instrument was used for the surface of the substrate after the first coating layer was formed at 25° C. of atmospheric pressure. The contact angle for water was measured.

Some of the measurement results are shown in Table 15 below. The contact angle is the angle between the interface between water and the substrate and the interface between water and air.

contact angle [°] Example 8-1 66.9 Example 8-4 55.4 Comparative Example 8-1 87.1

As shown in Table 15, the contact angle decreased by introducing the first coating layer on the Ni substrate. Therefore, it was confirmed that the first coating layer was introduced on the Ni substrate.

Evaluation Example 8-3: Adhesion test

Adhesion tests were performed on the coated substrates prepared in Examples 8-1 to 8-15 and Comparative Examples 8-1 to 8-3. The adhesion test was evaluated by a Scotch Tape Test based on ASTM D3002 and D3359.

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at intervals of 1 mm to form a grid, and then Scotch tape was attached and peeled off on the grid-shaped coating layer to evaluate the area of the coating layer removed. .

The evaluation criteria are as follows.

5B: 0% of the removed area, 4B: less than 5% of the removed area, 3B: 5-15% of the removed area, 2B: 15-35% of the removed area, 1B: 35-65% of the removed area, 0B: removal 65% or more of the area covered

5B to 3B are excellent, and 2B to 0B are poor.

Some of the measurement results are shown in Table 16 below.

Adhesion evaluation Example 8-1 5B Example 8-3 5B Example 8-5 1B Example 8-6 5B Example 8-8 5B Examples 8-9 4B Examples 8-10 2B Examples 8-11 5B Examples 8-13 5B Examples 8-14 5B Examples 8-15 2B Comparative Example 8-1 0B Comparative Example 8-2 0B Comparative Example 8-3 0B

As shown in Table 16, the adhesion of the coating layers of Examples 8-1, 8-3, 8-6, 8-8, 8-11, and 8-13 using 1-vinylimidazole was excellent as 5B. did The adhesive strength of the coating layer of Comparative Example was poor as 0B.

The adhesive strength of the coating layers of Examples 8-5, 8-9, 8-10, 8-14, and 8-15 using (2-hydroxyethyl) methacrylate was improved compared to that of the coating layers of Comparative Examples, but 1 - It was sluggish compared to the coating layer containing vinylimidazole.

Therefore, it was confirmed that the adhesion between the Ni substrate and the second coating layer was improved by the introduction of the first coating layer.

Evaluation Example 8-4: ATR-FTIR analysis of Ni substrate with first coating layer and second coating layer introduced

In the process of manufacturing the substrates coated in Examples 8-1 to 8-15 and Comparative Examples 8-1 to 8-3, ATR on the surface of the substrate after the introduction of the first coating layer and the surface of the substrate after the introduction of the second coating layer -FTIR (Attenuated Total Reflection Fourier Transform Infrared) spectroscopy was performed to confirm whether the first coating layer and the second coating layer were formed.

Although not shown in the figure, a first coating layer is formed in Example 8-1, a first coating layer is formed in Example 8-4, a second coating layer is formed in Example 8-1, and Example 8-3 It was confirmed from the ATR-FTIR spectrum that the second coating layer was formed in

(Zn base)

Example 9-1

A coating layer was deposited in the same manner as in Example 1-1, except that zinc foil was used instead of the aluminum foil.

Examples 9-2 to 9-15 and Comparative Examples 9-1 to 9-3

A coating layer was deposited in the same manner as in Examples 1-2 to 1-15 and Comparative Examples 1-1 to 1-3, except that zinc foil was used instead of the aluminum foil.

Evaluation Example 9-1: XPS analysis of Zn substrate with first coating layer introduced

In the process of manufacturing the substrates coated in Examples 9-1 to 9-15 and Comparative Examples 9-1 to 9-3, XPS (X-ray Photoelectron Spectroscopy) analysis was performed on the surface of the substrate after the first coating layer was introduced. It was confirmed whether or not the first coating layer was introduced.

In Example 9-1, after 1-vinylimidazole was coated on the Zn substrate, peaks for oxygen atoms, nitrogen atoms, and carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that 1-vinylimidazole was coated. The peak for the oxygen atom was determined to be due to a hydrophilic functional group such as a hydroxyl group present on the Zn substrate. In Example 9-4, after (hydroxyethyl)methacrylate was coated on the Zn substrate, peaks for oxygen atoms and peaks for carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that (hydroxyethyl) methacrylate was coated.

Evaluation Example 9-2: Water (H ₂ O) Measurement of contact angle

In the process of manufacturing the coated substrates prepared in Examples 9-1 to 9-15 and Comparative Examples 9-1 to 9-3, a contact angle measuring instrument was used for the surface of the substrate after the first coating layer was formed at 25° C. of atmospheric pressure. The contact angle for water was measured.

Some of the measurement results are shown in Table 17 below. The contact angle is the angle between the interface between water and the substrate and the interface between water and air.

contact angle [°] Example 9-1 73.6 Example 9-4 51.7 Comparative Example 9-1 76.5

As shown in Table 17, the contact angle decreased by introducing the first coating layer on the Zn substrate. Therefore, it was confirmed that the first coating layer was introduced on the Zn substrate.

Evaluation Example 9-3: Adhesion test

Adhesion tests were performed on the coated substrates prepared in Examples 9-1 to 9-15 and Comparative Examples 9-1 to 9-3. The adhesion test was evaluated by a Scotch Tape Test based on ASTM D3002 and D3359.

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at intervals of 1 mm to form a grid, and then Scotch tape was attached and peeled off on the grid-shaped coating layer to evaluate the area of the coating layer removed. .

The evaluation criteria are as follows.

5B: 0% of the removed area, 4B: less than 5% of the removed area, 3B: 5-15% of the removed area, 2B: 15-35% of the removed area, 1B: 35-65% of the removed area, 0B: removal 65% or more of the area covered

5B to 3B are excellent, and 2B to 0B are poor.

Some of the measurement results are shown in Table 18 below.

Adhesion evaluation Example 9-1 5B Example 9-3 5B Example 9-5 1B Example 9-6 5B Examples 9-8 5B Examples 9-9 3B Examples 9-10 5B Examples 9-11 5B Examples 9-13 5B Examples 9-14 4B Examples 9-15 5B Comparative Example 9-1 0B Comparative Example 9-2 0B Comparative Example 9-3 0B

As shown in Table 18, the adhesion of the coating layers of Examples 9-1, 9-3, 9-6, 9-8, 9-11, and 9-13 using 1-vinylimidazole was excellent as 5B. did The adhesive strength of the coating layer of Comparative Example was poor as 0B.

The adhesive strength of the coating layers of Examples 9-5, 9-9, 9-10, 9-14, and 9-15 using (2-hydroxyethyl) methacrylate was improved compared to that of the coating layers of Comparative Examples, but 1 - It was sluggish compared to the coating layer containing vinylimidazole.

Therefore, it was confirmed that the adhesion between the Zn substrate and the second coating layer was improved by the introduction of the first coating layer.

Evaluation Example 9-4: ATR-FTIR analysis of a Zn substrate introduced with a first coating layer and a second coating layer

In the process of manufacturing the substrates coated in Examples 9-1 to 9-15 and Comparative Examples 9-1 to 9-3, ATR on the surface of the substrate after the introduction of the first coating layer and the surface of the substrate after the introduction of the second coating layer -FTIR (Attenuated Total Reflection Fourier Transform Infrared) spectroscopy was performed to confirm whether the first coating layer and the second coating layer were formed.

Although not shown in the drawings, a first coating layer is formed in Example 9-1, a first coating layer is formed in Example 9-4, a second coating layer is formed in Example 9-1, and Example 9-3 It was confirmed from the ATR-FTIR spectrum that the second coating layer was formed in

(alloy substrate)

Example 10-1

A coating layer was deposited in the same manner as in Example 1-1, except that a cobalt-chromium-tungsten-nickel-magnesium alloy (Co-Cr-W-Ni-Mg alloy) used as a substrate for stents was used instead of aluminum foil. did

Examples 10-2 to 10-15 and Comparative Examples 10-1 to 10-3

Examples 1-2 to 1-15 and Comparative Examples 1-1 to 1-, except that the cobalt-chrome-tungsten-nickel-magnesium alloy (Co-Cr-W-Ni-Mg alloy) was used instead of the aluminum foil. A coating layer was deposited in the same manner as in 3.

Evaluation Example 10-1: XPS Analysis of Alloy Substrate Incorporating the First Coating Layer

In the process of manufacturing the substrates coated in Examples 10-1 to 10-15 and Comparative Examples 10-1 to 10-3, XPS (X-ray Photoelectron Spectroscopy) analysis was performed on the surface of the substrate after the first coating layer was introduced. It was confirmed whether or not the first coating layer was introduced.

In Example 10-1, after 1-vinylimidazole was coated on the alloy substrate, peaks for oxygen atoms, nitrogen atoms, and carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that 1-vinylimidazole was coated. The peak for the oxygen atom was determined to be due to a hydrophilic functional group such as a hydroxyl group present on the alloy substrate. The peaks for nitrogen atoms were small.

In Example 10-4, after (hydroxyethyl)methacrylate was coated on the alloy substrate, peaks for oxygen atoms and peaks for carbon atoms were confirmed on the surface of the substrate. Therefore, it was confirmed that (hydroxyethyl) methacrylate was coated.

Evaluation Example 10-2: Water (H ₂ O) Measurement of contact angle

In the manufacturing process of the coated substrates prepared in Examples 10-1 to 10-15 and Comparative Examples 10-1 to 10-3, the surface of the substrate after the first coating layer was formed at 25° C. of atmospheric pressure using a contact angle measuring instrument. The contact angle for water was measured.

Some of the measurement results are shown in Table 19 below. The contact angle is the angle between the interface between water and the substrate and the interface between water and air.

contact angle [°] Example 10-1 70.3 Example 10-4 68.8 Comparative Example 10-1 86.4

As shown in Table 19, the contact angle decreased as the first coating layer was introduced onto the alloy substrate. Therefore, it was confirmed that the first coating layer was introduced on the alloy substrate.

Evaluation Example 10-3: Adhesion test

Adhesion tests were performed on the coated substrates prepared in Examples 10-1 to 10-15 and Comparative Examples 10-1 to 10-3. The adhesion test was evaluated by a Scotch Tape Test based on ASTM D3002 and D3359.

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at intervals of 1 mm to form a grid, and then Scotch tape was attached and peeled off on the grid-shaped coating layer to evaluate the area of the coating layer removed. .

The evaluation criteria are as follows.

5B: 0% of the removed area, 4B: less than 5% of the removed area, 3B: 5-15% of the removed area, 2B: 15-35% of the removed area, 1B: 35-65% of the removed area, 0B: removal 65% or more of the area covered

5B to 3B are excellent, and 2B to 0B are poor.

Some of the measurement results are shown in Table 20 below.

Adhesion evaluation Example 10-1 5B Example 10-3 5B Example 10-4 4B Example 10-5 2B Example 10-6 5B Example 10-8 5B Example 10-9 5B Examples 10-10 2B Examples 10-11 5B Examples 10-13 5B Examples 10-14 5B Examples 10-15 5B Comparative Example 10-1 0B Comparative Example 10-2 0B Comparative Example 10-3 0B

As shown in Table 20, the adhesion of the coating layers of Examples 10-1, 10-3, 10-6, 10-8, 10-11, and 10-13 using 1-vinylimidazole was excellent as 5B. did The adhesive strength of the coating layer of Comparative Example was poor as 0B.

The adhesive strength of the coating layers of Examples 10-5, 10-9, 10-10, 10-14, and 10-15 using (2-hydroxyethyl) methacrylate was improved compared to the adhesive strength of the coating layers of Comparative Examples, but 1 - It was sluggish compared to the coating layer containing vinylimidazole.

Therefore, it was confirmed that the adhesion between the alloy substrate and the second coating layer was improved by the introduction of the first coating layer.

Evaluation Example 10-4: ATR-FTIR analysis of an alloy substrate to which the first coating layer and the second coating layer were introduced

In the manufacturing process of the substrates coated in Examples 10-1 to 10-15 and Comparative Examples 10-1 to 10-3, ATR on the surface of the substrate after the first coating layer was introduced and the surface of the substrate after the second coating layer was introduced -FTIR (Attenuated Total Reflection Fourier Transform Infrared) spectroscopy was performed to confirm whether the first coating layer and the second coating layer were formed.

Although not shown in the figure, a first coating layer is formed in Example 10-1, a first coating layer is formed in Example 10-4, a second coating layer is formed in Example 10-1, and Example 10-3 It was confirmed from the ATR-FTIR spectrum that the second coating layer was formed in

Claims (11)

providing a base substrate on one side of which electronic devices are disposed, within a vacuum enclosure;
disposing a first coating layer on the electronic device by supplying at least one of a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, and an aromatic cyclic compound having an unsaturated functional group and a polar functional group;
Sealing the electronic device by disposing a second coating layer containing a parylene-based polymer on the first coating layer by supplying parylene-based radicals derived from a parylene-based precursor to the first coating layer; manufacturing a sealed electronic device including method. The method of claim 1, wherein the terminal substituent connected to the oxygen atom of the non-fluorine-based acrylic compound contains 5 or less carbon atoms,
The aromatic heterocyclic compound containing the unsaturated functional group and the aromatic ring compound containing the unsaturated functional group and the polar functional group are 5 membered rings or 6 membered rings,
The aromatic heterocyclic compound includes at least one heteroatom selected from nitrogen, oxygen, and sulfur,
1 to 4 heteroatoms included in the aromatic heterocyclic compound,
The aromatic ring compound is free of heteroatoms,
The unsaturated functional group is a functional group containing a double bond or a triple bond,
The method of manufacturing a sealed electronic device, wherein the polar functional group is a functional group containing an oxygen or sulfur atom. The method of claim 1, wherein the aromatic heterocyclic compound containing an unsaturated functional group is a compound represented by Formulas 1 to 9 below,
A method for manufacturing a sealed electronic device, wherein the aromatic ring compound including the unsaturated functional group and the polar functional group is a compound represented by Formulas 10 to 11 below:
<Formula 1><Formula2><Formula3>

<Formula 4><Formula5><Formula7>

<Formula 7><Formula8><Formula9>

<Formula 10><Formula11>

In the above expressions,
R ₁ to R ₁₄ are each independently selected from hydrogen, an alkyl group having 1 to 5 carbon atoms, a vinyl group, an allyl group, or a propargyl group;
At least one of R ₁ to R ₄ is a vinyl group, an allyl group, or a propalyl group;
At least one of R ₆ , R ₇ and R ₉ is a vinyl group, an allyl group, or a propalyl group;
At least one of R ₁₀ to R ₁₄ is a vinyl group, an allyl group, or a propalyl group.
R ₁₅ to R ₂₅ are each independently selected from hydrogen, an alkyl group having 1 to 5 carbon atoms, a hydroxy group, a thiol group, a vinyl group, an allyl group, or a propargyl group;
At least one of R ₁₅ to R ₂₀ is a vinyl group, an allyl group, or a propalgyl group, and at least the other is a hydroxyl group or a thiol group;
At least one of R ₂₁ to R ₂₆ is a vinyl group, an allyl group, or a propalyl group, and at least the other is a hydroxy group or a thiol group. The method of manufacturing a sealed electronic device according to claim 1, wherein the fluorine-free acrylic compound is a compound represented by Formula 20 below:
<Formula 20>

In the above formula,
R ₂₇ is hydrogen, a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxymethyl group, or a 2-hydroxyethyl group;
R ₂₈ is hydrogen or a methyl group. The method of claim 1 , wherein the first coating layer self-assembles at least one of a non-fluorine-based acrylic compound chemically adsorbed on the electronic device, an aromatic heterocyclic compound having an unsaturated functional group, and an aromatic cyclic compound having an unsaturated functional group and a polar functional group. Contains a self-assembled layer,
The second coating layer includes a parylene-based polymer grafted to an unsaturated functional group included in the first coating layer,
In the step of disposing the second coating layer, no separate catalyst or initiator is used other than the parylene-based bulb,
The method of manufacturing a sealed electronic device, wherein the first coating layer and the second coating layer are conformal coating layers. The method of manufacturing a sealed electronic device according to claim 1, wherein the parylene-based precursor comprises at least one selected from dimers represented by the following Chemical Formulas 10 to 17:
<Formula 12><Formula13><Formula14><Formula15>

<Formula 16><Formula17><Formula18><Formula19>

The method of claim 1, wherein the parylene-based polymer is Parylene N, Parylene C, Parylene D, Parylene AF-4, Parylene HT, Parylene VT-4, Parylene CF, Parylene A, Parylene AM , Parylene H, Parylene SR, Parylene HR, and Parylene NR, a method for manufacturing a sealed electronic device comprising at least one selected from. According to claim 1,
The vaporization temperature of at least one of the non-fluorine-based acrylic compound, the heterocyclic compound containing an unsaturated functional group, and the aromatic cyclic compound containing an unsaturated functional group and a polar functional group is 25 to 150 ° C,
The vaporization temperature of the parylene-based precursor is 100 ~ 200 ℃, the thermal decomposition temperature of the parylene-based precursor is 500 ~ 750 ℃,
The method of manufacturing a sealed electronic device, wherein the temperature of the electronic device and the base substrate is 20 to 40 ° C. The method of claim 1, wherein the thickness of the first coating layer is 100 nm or less, and the thickness of the second coating layer is 100 nm to 500 μm,
The electronic device and the base substrate independently include at least one selected from metal, metalloid, metal oxide, metal nitride, glass, organic-inorganic composite, polymer, fiber, paper, and wood, and the electronic device and the base substrate A method for manufacturing a sealed electronic device, each of which is a flexible substrate or a non-flexible substrate. a base substrate on one surface of which an electronic device is disposed;
Including; sealing layer for sealing the electronic device,
The sealing layer is a first coating layer; And a second coating layer disposed on the first coating layer; includes,
The first coating layer includes at least one selected from a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, an aromatic cyclic compound having an unsaturated functional group and a polar functional group, and derivatives thereof,
wherein the second coating layer comprises a parylene-based polymer. 11. The method of claim 10, wherein the electronic device is an organic light emitting device (OLED), a liquid crystal display (LCD), a charge-coupled device (CCD), a microelectromechanical sensor (micro-electro-mechanical sensors, MEMS), and organic or inorganic photoelectric conversion devices based on thin-film solar cells.

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