Coating substrate by polymerization reaction of amine compound, and apparatus having polymer coated substrate

Abstract

To provide a technique for forming a polymer layer on a substrate by using a polymerization reaction.SOLUTION: The present invention provides a method for forming a polymer layer on the surface of a substrate by using a self-initiating monomer. A defect such as a pinhole in a metal layer can be filled by causing a polymerization reaction on the surface of the metal layer having the defect to form the polymer layer. The metal layer coated with the polymer layer can be used as an airtight material for blocking moisture or air.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a technique for forming a polymer layer on a substrate using a polymerization reaction. [Background technology]

[0002] Surface modification techniques that change the surface properties of a substrate are in demand in a variety of application technologies. However, the chemical treatments used to modify the surface of a substrate are often limited by the properties of the substrate. For example, to modify a surface using a nucleophilic reaction, the substrate must have sufficient nucleophilic reactants. To modify a surface using an electrophilic reaction, the substrate must have sufficient electrophilic reactants. Otherwise, an additional process is required to introduce nucleophilic or electrophilic functional groups into the substrate, which increases costs. A technology that can modify the surface of a substrate without complicating the process or significantly increasing costs would have diverse applications. Summary of the Invention

[0003] Various aspects of the invention are set out below in the form of examples.

[0004] Example 1 provides a metal laminate structure including a plastic film including at least one plastic material layer, a metal layer formed on the plastic film, and a polymer layer formed on the metal layer. The polymer layer is not formed by coating a prepolymerized polymer on the metal layer, but is formed by a polymerization reaction on the metal layer. The polymer layer includes a polymer obtained using at least one of the compounds belonging to Chemical Formulas 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11, and compounds Nos. 204-248, as a monomer. The polymer layer does not include a binder for adhering the polymer layer to the metal layer; rather, many polymers in the polymer layer are chemically bonded to the metal layer, adhering to the metal layer without a binder. JPEG2025138736000002.jpg180170 JPEG2025138736000003.jpg107170 JPEG2025138736000004.jpg155170 JPEG2025138736000005.jpg179170 JPEG2025138736000006.jpg179170 JPEG2025138736000007.jpg176170 JPEG2025138736000008.jpg198170

[0005] Example 2 provides a method for manufacturing a metal laminate structure, the method including the steps of providing an intermediate structure including a plastic film and a metal layer formed thereon, and performing a polymerization reaction on the metal layer of the intermediate structure to form a polymer layer. The metal laminate structure includes a plastic film, a metal layer formed on the plastic film, and a polymer layer formed on the metal layer, the polymer layer including a polymer obtained using at least one of the compounds of Chemical Formulas 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11 in Example 1 and the compounds of Compound Nos. 204-248 as a monomer, and the composition of the polymerization reaction does not include a binder, so that the polymer layer formed by the polymerization reaction does not include a binder.

[0006] Example 3 provides the method of Example 2, wherein the composition for the polymerization reaction does not contain any of a surfactant, a polymerization initiator, or a polymerization inhibitor, and the polymer layer formed as a result of the polymerization reaction does not contain any of a surfactant, a polymerization initiator, or a polymerization inhibitor.

[0007] Example 4 provides the method of Example 2, wherein the step of providing the intermediate structure includes the steps of providing a plastic film and a metal layer, and applying an adhesive between the plastic film and the metal layer and laminating them to provide an adhesive layer interposed between the plastic film and the metal layer.

[0008] Example 5 provides the method of example 2, wherein the step of providing the intermediate structure includes the steps of providing a plastic film and vapor depositing a metal to form a metal layer on the plastic film.

[0009] Example 6 provides the method of Example 5, wherein the step of providing the intermediate structure further includes a step of plasma treating the surface of the plastic film before performing the vapor deposition, and the metal vapor deposition is performed on the surface of the plastic film.

[0010] Example 7 provides the method of example 2, wherein the step of inducing a polymerization reaction includes contacting the metal layer of the intermediate structure with a polymerization reaction composition.

[0011] Example 8 provides a flexible laminate structure including a plurality of metal laminate structures, including a first metal laminate structure and a second metal laminate structure, and an adhesive layer interposed between the first metal laminate structure and the second metal laminate structure to bond the first metal laminate structure and the second metal laminate structure. The first metal laminate structure and the second metal laminate structure each include a plastic film including at least one plastic material layer, a metal layer formed on the plastic film, and a polymer layer formed on the metal layer, where the polymer layer is formed by polymerization on the metal layer rather than by coating a prepolymerized polymer on the metal layer. The polymer layer includes a polymer obtained from at least one of the compounds represented by formulas 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11 in Example 1 and the compounds represented by compound numbers 204-248 as monomers. The polymer layer does not contain a binder to attach the polymer layer to the metal layer, and many polymers in the polymer layer are chemically bonded to the metal layer, so that the polymer layer is adhered to the metal layer without a binder.

[0012] Example 9 provides a method for manufacturing a flexible laminate structure, including the steps of providing a first metal laminate structure and a second metal laminate structure, and applying and depositing an adhesive between the first metal laminate structure and the second metal laminate structure to form an adhesive layer interposed between the first metal laminate structure and the second metal laminate structure and laminating the first metal laminate structure and the second metal laminate structure. The first metal laminate structure and the second metal laminate structure each include a plastic film including at least one plastic material layer, a metal layer formed on the plastic film, and a polymer layer formed on the metal layer, and the polymer layer is formed by a polymerization reaction on the metal layer, rather than by coating a pre-polymerized polymer on the metal layer. The polymer layer includes a polymer obtained using at least one monomer selected from the compounds of Chemical Formulas 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11 in Example 1 and the compounds of Compound Nos. 204-248. The polymer layer does not include a binder for adhering the polymer layer to the metal layer, and multiple polymers in the polymer layer are chemically bonded to the metal layer, so that the polymer layer is adhered to the metal layer without a binder.

[0013] Example 10 provides an information display device including a display panel and a flexible laminate structure. The display panel includes a substrate and a display array. The substrate has a front surface and a rear surface. The display array is located on the rear surface of the substrate and bonded to the substrate with or without an intermediate element between the display array and the rear surface of the substrate. The flexible laminate structure is located on the display array and the rear surface of the substrate, enclosing the display array therebetween. The flexible laminate structure and the substrate are bonded in an airtight manner, so that the display array is sealed between the substrate and the flexible laminate structure. The flexible laminate structure includes a plurality of metal laminate structures, including a first metal laminate structure and a second metal laminate structure, and an adhesive layer interposed between the first metal laminate structure and the second metal laminate structure to bond the first metal laminate structure and the second metal laminate structure together. The first metal laminate structure and the second metal laminate structure each include a plastic film including at least one plastic material layer, a metal layer formed on the plastic film, and a polymer layer formed on the metal layer, where the polymer layer is formed by a polymerization reaction on the metal layer rather than by coating a prepolymerized polymer on the metal layer. The polymer layer includes a polymer obtained using at least one of the compounds represented by Chemical Formulas 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11 in Example 1 and Compound Nos. 204-248 as a monomer. The polymer layer does not include a binder for adhering the polymer layer to the metal layer, but rather adheres to the metal layer without a binder because a majority of the polymer in the polymer layer is chemically bonded to the metal layer.

[0014] Example 11 provides an information display device according to Example 10, wherein the plurality of metal laminate structures includes a third metal laminate structure, and the adhesive layer is referred to as a first adhesive layer and includes a second adhesive layer interposed between the second metal laminate structure and the third metal laminate structure to bond the second metal laminate structure and the third metal laminate structure together.

[0015] Example 12 is the information display device of Example 10, wherein the display array is sealed to form a display array of about 1×10 -8 g / m 2 / 1 / 10 to about 1 x 10 -6 g / m 2 To provide an information display device having a moisture permeability in the range of 1 / 100 psi.

[0016] Example 13 provides a method for manufacturing an information display device. The method includes the steps of providing a substrate having a front surface and a rear surface, a display array located on the rear surface of the substrate and coupled to the substrate with or without an intermediate element, providing a flexible laminate structure having a first surface and a second surface opposite the first surface, aligning the flexible laminate structure over the display array and the rear surface of the substrate so that the first surface of the flexible laminate faces the substrate and the second surface faces the opposite side of the substrate, and sealing an edge of the flexible laminate structure to an edge of a corresponding portion of a display panel so that the display array is sealed to prevent air communication between the substrate and the flexible laminate structure. The flexible laminate structure includes a plurality of metal laminate structures, including a first metal laminate structure and a second metal laminate structure, and an adhesive layer interposed between the first metal laminate structure and the second metal laminate structure to bond the first metal laminate structure and the second metal laminate structure together. The first metal laminate structure and the second metal laminate structure each include a plastic film including at least one plastic material layer, a metal layer formed on the plastic film, and a polymer layer formed on the metal layer, where the polymer layer is formed by a polymerization reaction on the metal layer rather than by coating a prepolymerized polymer on the metal layer. The polymer layer includes a polymer obtained using at least one of the compounds represented by Chemical Formulas 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11 in Example 1 and Compound Nos. 204-248 as a monomer. The polymer layer does not include a binder for adhering the polymer layer to the metal layer, but rather adheres to the metal layer without a binder because a majority of the polymer in the polymer layer is chemically bonded to the metal layer.

[0017] Example 14 provides a plastic packaging sheet including a plastic film having at least one plastic material layer, a metal layer formed on the plastic film by vapor deposition of a metal, and a polymer layer formed on the metal layer. The polymer layer is formed by a polymerization reaction on the metal layer, rather than by coating a prepolymerized polymer on the metal layer. The polymer layer includes polymers and oligomers obtained using at least one of the compounds of Chemical Formulas 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11 in Example 1 and compounds Nos. 204-248 as monomers. The metal layer has defect spaces extending through the thickness, and at least a portion of the defect spaces are filled with polymers and oligomers obtained from the monomers.

[0018] In Example 15, the same plastic sheet for packaging as in Example 14 was used, but the amount of the particles was about 1 × 10 -8 g / m 2 / 1 / 10 to about 1 x 10 -6 g / m 2 The present invention provides a packaging plastic sheet having a moisture permeability in the range of 1 / 100 psi.

[0019] Example 16 provides a method for airtight packaging of an item, including providing a plastic packaging bag having an opening, placing an item into the plastic packaging bag through the opening, and sealing the opening of the plastic packaging bag to prevent air from passing through, thereby providing an airtight package containing the item. The plastic packaging bag includes a plastic packaging sheet including a plastic film having at least one plastic material layer, a metal layer formed on the plastic film by vapor deposition of a metal, and a polymer layer formed on the metal layer. The polymer layer is not formed by coating a prepolymerized polymer on the metal layer, but is formed by a polymerization reaction on the metal layer. The polymer layer includes polymers and oligomers obtained from at least one of the compounds belonging to chemical formulas 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11 of Example 1 and compounds Nos. 204-248 as monomers. The metal layer has defects penetrating through its thickness, and at least a portion of the defects are filled with polymers and oligomers obtained from the monomers.

[0020] Example 17 is the method of example 16, wherein the airtight packaging contains about 1×10 -8 g / m 2 / 1 / 10 to about 1 x 10 -6 g / m 2 The present invention provides a method for producing a film having a moisture permeability in the range of 1 / 100 psi.

[0021] Example 18 provides the method or apparatus of any one of Examples 1 to 17, wherein the metal layer comprises a metal foil and the metal laminate structure comprises an adhesive layer between the metal layer and the plastic film.

[0022] Example 19 provides the method or apparatus of Examples 1 to 17, wherein the metal layer comprises a metal foil having a thickness of about 5 μm to about 200 μm, and the metal laminate structure comprises an adhesive layer between the metal layer and the plastic film.

[0023] Example 20 provides the method or apparatus of any one of Examples 1 to 17, wherein the metal layer comprises a metal-deposited layer formed on a plastic film, and no separate layer is interposed between the metal layer and the plastic film.

[0024] Example 21 provides the method or apparatus of Examples 1 to 17, wherein the metal layer comprises a vapor-deposited metal layer having a thickness of about 5 μm to about 200 μm formed on the plastic film, and no separate layer is interposed between the metal layer and the plastic film.

[0025] Example 22 provides the method or apparatus of Examples 1 to 17, wherein the polymer layer contains a substantial amount of one or more compounds selected from the group consisting of oligomers, tetramers, trimers, and dimers resulting from a polymerization reaction on the metal layer from at least one monomer, the substantial amount being such that commercially available polymer compositions having a particular molecular weight range do not contain significant amounts of oligomers, tetramers, trimers, and dimers.

[0026] Example 23 provides a method or apparatus according to any one of Examples 1 to 17, wherein the polymer layer comprises one or more selected from the group consisting of oligomers, tetramers, trimers, and dimers resulting from a polymerization reaction of at least one monomer on the metal layer, and the oligomers, tetramers, trimers, and dimers are chemically bonded to the plastic film, and the chemical bonding of the oligomers, tetramers, trimers, and dimers to the metal layer is such that this bonding would not occur when a prepolymerized polymer is coated on the metal layer.

[0027] Example 24 provides the method or apparatus of any one of Examples 1 to 17, wherein the metal layer has pinholes extending through the thickness of the metal layer, and at least one of an oligomer and a polymer occupies at least a portion of the pinhole space and is chemically bonded to the inner surface of the pinhole, such that chemical bonding of the oligomer, polymer, or inner surface of the pinhole does not occur when a prepolymerized polymer is coated on the metal layer.

[0028] Example 25 provides a method and apparatus in which, in the methods and apparatuses of Examples 1 to 17, the polymer layer is not obtained by coating a prepolymerized polymer on a metal layer, but is a commercially available polymer composition having a molecular weight within a specific range, and does not contain a polymerization inhibitor contained to inhibit polymerization or crosslinking reactions.

[0029] Example 26 provides a method and apparatus according to Examples 1 to 17, in which a pre-polymerized polymer is coated to form a polymer layer, but the polymer layer does not contain a surfactant that can be used to uniformly coat the pre-polymerized polymer on a metal surface.

[0030] Example 27 provides the method or apparatus of any one of Examples 1 to 17, except that the polymer layer does not contain a surfactant, a polymerization initiator, or a polymerization inhibitor.

[0031] Example 28 is the method or apparatus of Examples 1 to 17, wherein the polymer layer contains a substantial amount of one or more compounds selected from the group consisting of oligomers, tetramers, trimers, and dimers derived from the at least one monomer, the substantial amount being such that commercially available polymer compositions having a specific molecular weight range do not contain significant amounts of oligomers, tetramers, trimers, and dimers, and the polymer layer formed as a result of the polymerization reaction on the metal layer includes one or more selected from the group consisting of oligomers, tetramers, trimers, and dimers chemically bonded to a plastic film, such that the oligomers, tetramers, trimers, and dimers are present. The chemical bonding to the metal layer is of a nature that would not occur if a pre-polymerized polymer were coated onto the metal layer, the metal layer having pinholes extending through the thickness of the metal layer, and at least one of an oligomer and a polymer being chemically bonded to the inner surface of the pinhole while occupying at least a portion of the pinhole space, the chemical bonding of the oligomer, polymer, or inner surface of the pinhole being of a nature that would not occur if a pre-polymerized polymer were coated onto the metal layer, and the polymer layer is free of surfactants, polymerization initiators, and polymerization inhibitors.

[0032] Example 29 relates to the method or apparatus of Examples 1 to 17, wherein the metal layer comprises a metal foil, the metal laminate structure comprises an adhesive layer between the metal layer and the plastic film, the polymer layer comprises a substantial amount of one or more compounds selected from the group consisting of oligomers, tetramers, trimers, and dimers derived from the at least one monomer, the substantial amount being such that commercially available polymer compositions having a molecular weight within a specific range do not contain significant amounts of oligomers, tetramers, trimers, and dimers, and the polymer layer formed as a result of the polymerization reaction on the metal layer comprises one or more compounds selected from the group consisting of oligomers, tetramers, trimers, and dimers chemically bonded to the plastic film. The chemical bonding of the oligomer, tetramer, trimer, or dimer to the metal layer is of a nature that would not occur if a prepolymerized polymer were coated on the metal layer, the metal layer has pinholes extending through the thickness of the metal layer, and at least one of the oligomer and polymer is chemically bonded to the inner surface of the pinhole while occupying at least a portion of the pinhole space, the chemical bonding of the oligomer, polymer, or inner surface of the pinhole is of a nature that would not occur if a prepolymerized polymer were coated on the metal layer, and the polymer layer does not contain surfactants, polymerization initiators, or polymerization inhibitors.

[0033] Example 30 is the method or apparatus of Examples 1 to 17, wherein the metal layer comprises a metal vapor deposition layer, and there is no additional layer between the metal layer and the plastic film; the polymer layer comprises a substantial amount of one or more compounds selected from the group consisting of oligomers, tetramers, trimers, and dimers derived from the at least one monomer, the substantial amount being such that commercially available polymer compositions having a molecular weight within a specific range do not contain significant amounts of oligomers, tetramers, trimers, and dimers; and the polymer layer formed as a result of a polymerization reaction on the metal layer comprises one or more compounds selected from the group consisting of oligomers, tetramers, trimers, and dimers chemically bonded to the plastic film; The chemical bonding of oligomers, tetramers, trimers, and dimers to a metal layer is of a nature that would not occur when a prepolymerized polymer is coated on the metal layer, and the metal layer has pinholes extending through the thickness of the metal layer, and at least one of the oligomers and polymers is chemically bonded to the inner surface of the pinholes while occupying at least a portion of the pinhole space, and the chemical bonding of the oligomers, polymers, and inner surface of the pinholes is of a nature that would not occur when a prepolymerized polymer is coated on the metal layer, and the polymer layer does not contain surfactants, polymerization initiators, or polymerization inhibitors.

[0034] Example 31 provides a method or apparatus according to any one of Examples 1 to 17, wherein the polymer layer is referred to as a first polymer layer, and the metal laminate structure further includes a second polymer layer formed under the plastic film, the plastic film being interposed between the metal layer and the second polymer layer. The second polymer layer is not a prepolymerized polymer composition coating, but includes a polymer formed by polymerizing at least one monomer on the plastic film, but does not include a binder for adhering the second polymer layer to the plastic film.

[0035] Example 32 provides the method or apparatus of Example 31, wherein the first polymer layer has a thickness ranging from about 1 μm to about 20 μm.

[0036] Example 33 provides the method or apparatus of Example 31, wherein the first polymer layer formed as a result of the polymerization reaction on the metal layer contains a substantial amount of one or more compounds selected from the group consisting of oligomers, tetramers, trimers, and dimers derived from the at least one monomer, the substantial amount being such that commercially available polymer compositions having a particular molecular weight range do not contain significant amounts of oligomers, tetramers, trimers, and dimers.

[0037] Example 34 provides the method or apparatus of Example 31, wherein the first polymer layer formed as a result of the polymerization reaction on the metal layer includes one or more selected from the group consisting of oligomers, tetramers, trimers, and dimers chemically bonded to the metal layer, and the chemical bonding of the oligomers, tetramers, trimers, or dimers to the metal layer is of a nature that would not occur when a pre-polymerized polymer is coated on the metal layer.

[0038] Example 35 provides the method or apparatus of Example 31, wherein the metal layer has pinholes extending through the thickness of the metal layer, and at least one of an oligomer and a polymer is chemically bonded to the inner surface of the pinhole while occupying at least a portion of the pinhole space, such that chemical bonding of the oligomer, polymer, or inner surface of the pinhole is not possible when a prepolymerized polymer is coated on the metal layer.

[0039] Example 36 provides a method and apparatus according to Example 31, wherein the first polymer layer is not obtained by coating a prepolymerized polymer on a metal layer, but is a commercially available polymer composition having a molecular weight within a specific range, and does not contain a polymerization inhibitor contained to inhibit polymerization or crosslinking reactions.

[0040] Example 37 provides a method and apparatus according to Example 31, wherein when a prepolymerized polymer is coated to form a first polymer layer, the first polymer layer does not contain a surfactant that can be used to uniformly coat the prepolymerized polymer on a metal surface.

[0041] Example 38 provides the method or apparatus of example 31, wherein the second polymer layer has a thickness ranging from about 1 μm to about 20 μm.

[0042] Example 39 provides the method or apparatus of Example 31, wherein the second polymer layer formed as a result of the polymerization reaction on the plastic film contains a substantial amount of one or more compounds selected from the group consisting of oligomers, tetramers, trimers, and dimers derived from the at least one monomer, the substantial amount being such that commercially available polymer compositions having a specific molecular weight range do not contain significant amounts of oligomers, tetramers, trimers, and dimers.

[0043] Example 40 provides the method or apparatus of Example 31, wherein the second polymer layer formed as a result of the polymerization reaction on the plastic film includes one or more selected from the group consisting of oligomers, tetramers, trimers, and dimers chemically bonded to the metal layer, and the chemical bonding of the oligomers, tetramers, trimers, or dimers to the plastic film is such that it would not occur when a pre-polymerized polymer is coated on a plastic film.

[0044] Example 41 provides the method or apparatus of Example 31, wherein the plastic film includes an engineering polymer layer having pores, and at least one of the oligomer and the polymer resides in at least one of the pores and is chemically bonded to the inner surface of the pores, such that the oligomer and the polymer are chemically bonded to the inner surface of the pores in a manner that would not occur when a prepolymerized polymer is coated on a plastic film.

[0045] Example 42 provides the method or apparatus of Example 31, wherein the second polymer layer has a large number of polymer molecules chemically bonded to the plastic film, such that the second polymer layer is attached to the plastic film without a binder.

[0046] Example 43 provides a method and apparatus according to Example 31, wherein the second polymer layer is not obtained by coating a prepolymerized polymer composition on a plastic surface, but is obtained by using a commercially available polymer composition having a molecular weight within a specific range and does not contain a polymerization inhibitor contained therein to inhibit polymerization or crosslinking reactions.

[0047] Example 44 provides a method and apparatus according to Example 31, except that when a pre-polymerized polymer is coated to form a second polymer layer, the second polymer layer does not contain a surfactant that can be used to uniformly coat the pre-polymerized polymer on the plastic layer.

[0048] Example 45 provides a separator for a secondary battery, comprising: a porous polyolefin layer having a first surface and a second surface; a first polymer layer formed on the first surface by a polymerization reaction on the porous polyolefin layer, rather than by coating the porous polyolefin layer with a prepolymerized polymer; and a second polymer layer formed on the second surface by a polymerization reaction on the porous polyolefin layer, rather than by coating the porous polyolefin layer with a prepolymerized polymer. The first polymer layer and the second polymer layer each comprise a polymer obtained using, as a monomer, at least one of the compounds represented by compound numbers 204-248 and the compounds represented by formulas 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11 of Example 1. JPEG2025138736000009.jpg176170 JPEG2025138736000010.jpg107170

[0049] Example 46 provides a secondary battery device including a cathode, an anode, a separator electrically positioned between the cathode and the anode, and an electrolyte. The separator includes a porous polyolefin layer having a first surface and a second surface, a first polymer layer formed on the first surface by a polymerization reaction on the porous polyolefin layer, and a second polymer layer formed on the second surface by a polymerization reaction on the porous polyolefin layer, but not by coating the porous polyolefin layer with a prepolymerized polymer. The first and second polymer layers do not include a binder for adhering the polymer layer to the porous polyolefin layer, but rather, the majority of the polymers in the polymer layer are chemically bonded to the porous polyolefin layer, thereby adhering to the porous polyolefin layer without a binder. The first and second polymer layers each include a polymer obtained from at least one of the compounds represented by Compound Nos. 204-248 in Example 45 and the compounds represented by Chemical Formulas 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11 in Example 1 as monomers.

[0050] Example 47 provides a method for preparing a separator for a secondary battery, the method including the steps of providing a porous polyolefin layer having a first surface and a second surface, and carrying out a polymerization reaction on the porous polyolefin layer to form a first polymer layer on the first surface and a second polymer layer on the second surface, wherein the composition of the polymerization reaction includes the compounds of Compound Nos. 204-248 of Example 45 and at least one monomer selected from the compounds of Formulas 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11 of Example 1.

[0051] Example 48 provides the device or method of any of Examples 45 to 47, wherein the porous polyolefin layer comprises a polyethylene or polypropylene nonwoven fabric layer.

[0052] Example 49 provides the device or method of any of Examples 45 to 47, wherein the porous polyolefin layer comprises a woven polyethylene or polypropylene layer.

[0053] Example 50 provides the apparatus or method of Examples 45-47, wherein the at least one monomer is selected from the group consisting of Compound Nos. 1-248. JPEG2025138736000011.jpg177170 JPEG2025138736000012.jpg178170 JPEG2025138736000013.jpg175170 JPEG2025138736000014.jpg177170 JPEG2025138736000015.jpg178170 JPEG2025138736000016.jpg253170 [Brief explanation of the drawings]

[0054] [Figure 1] 1 is a flowchart of a method for forming a polymer layer on a substrate surface according to one embodiment. [Figure 2] 1 illustrates the construction of a metal foil laminate according to an embodiment. [Figure 3] 1 illustrates the construction of a polymer-metal laminate according to one embodiment. [Figure 4] 1 illustrates a laminated structure of two polymer-metal foil laminates according to an embodiment. [Figure 5] 1 illustrates the structure of a metal vapor deposited plasma laminate according to an embodiment. [Figure 6] 1 illustrates the construction of a polymer-metal laminate according to one embodiment. [Figure 7] 1 illustrates the coating structure of an existing separation membrane. [Figure 8] 1 illustrates the structure of a coated separator according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0055] The present invention will now be described in more detail with reference to specific embodiments and drawings that disclose embodiments of the invention. However, not all embodiments of the invention are disclosed in the drawings. Identical elements and configurations are depicted using the same drawing numbers. The invention disclosed in this document may be embodied in various different forms, and the present invention should not be construed as being limited to only the embodiments illustrated and described herein. The embodiments disclosed in this document are provided to satisfy the requirements of the Patent Act. Those skilled in the art will recognize that various modifications can be readily conceived in light of the embodiments disclosed herein. The scope of the present invention is not limited to only the embodiments disclosed in this document, and modifications of these embodiments and other embodiments that can be readily conceived by those skilled in the art are to be understood as falling within the scope of the claims.

[0056] As used herein, the term "alkyl" includes straight chain, branched chain, or cyclic alkyl unless defined differently. The term "C1-C6 alkyl" means an alkyl containing 1 to 6 carbon atoms.

[0057] As used herein, unless otherwise defined, the term "alkoxy" means "alkyl-O-", and the term "C1-C6 alkoxy" means "C1-C6 alkyl-O-", where "alkyl" or "C1-C6 alkyl" are as defined above.

[0058] As used herein, the term "halo" includes fluoro, chloro, bromo and iodo.

[0059] As used herein, the term "oligomer" refers to a polymer consisting of a relatively small number of repeating units, generally 20 or fewer, where the repeating units may be identical or different molecules.

[0060] The term "(co)polymer" as used herein refers to both "polymer" and "copolymer," and refers to a polymer consisting of a greater number of repeating units than an oligomer. Copolymers formed by the bonding between different molecules are specifically referred to as "copolymers." Copolymers can take various forms, such as alternating copolymers, random copolymers, block copolymers, and graft copolymers.

[0061] I. Monomer An embodiment of the present invention provides a method for coating the surface of a substrate through a polymerization reaction using a compound having an amino group or a tautomer thereof as a monomer. The monomer compound having an amino group is a compound represented by Formulas 1 to 11.

[0062] Polymerization Reaction Mechanism The compounds of Formulas 1 to 11 are polymerized through a nucleophilic or electrophilic reaction with a substrate. This polymerization reaction can proceed without a polymerization initiator such as a radical initiator by initiating a polymerization reaction on the surface of a substrate having a nucleophile or on the surface of a substrate having an electrophile. The mechanisms of the nucleophilic and electrophilic reactions with a substrate will be described in detail below for each of the compounds of Formulas 1 to 11. These reaction mechanisms are provided merely to aid in understanding the present invention, and do not necessarily mean that the embodiments of the present invention must follow such reaction mechanisms.

[0063] Compound of Formula 1 Embodiments of the present invention provide aminoheterocyclic compounds of Formula 1: <Chemical formula 1> JPEG2025138736000017.jpg33143

[0064] L 11 ~L 16 In the above formula 1, L 11 ~L 16 are each independently a single bond or a double bond, and L 11 ~L 16 At least one of the groups is a double bond.

[0065] A 11 or A 16 A 11 or A 16 are each independently -C(R 11 R 12 )-, -N(R 13 )-, -O-, and -S-; A 11 or A 16 At least one of the -N(R 13 )-, -O- or -S-, and A 11 or A 16 At least one of the -C(R 11 R 12 )-.

[0066] R 11 ~R13 R 11 and R 12 are each independently selected from the group consisting of H, NH, ═NH, C-C alkyl, C-C alkoxy, halo, CN, carboxyl, formyl, OH, and SH, or together with the carbon atom connected thereto form a carbonyl or thiocarbonyl group; R 13 is hydrogen or NH2.

[0067] Single bond / double bond However, (a)L 11 ~L 16 Among these, two Ls adjacent to any L that is a double bond are single bonds, and A connected by Ls that are double bonds is not -O- or -S-; (b) L 11 ~L 16 A connected by any L that is a double bond is -C(R 11 R 12 )- or -N(R 13 )-, R bonded to the carbon or nitrogen atom 12 and R 13 does not exist, and (c)R 11 , R 12 and R 13 At least one of these is NH2.

[0068] Imine-enamine tautomers The compound of Formula 1 is an imine (or Schiff base) compound in an aqueous solution, and Equilibria can be formed between compounds in their imine-enamine tautomeric forms. Imine-enamine tautomers are nitrogen analogs of keto-enol tautomers. In both cases, a hydrogen atom is exchanged between a heteroatom and a carbon atom. For example, in the case of 4-aminopyridine, the following equilibria can be formed: <Reaction Scheme 1> JPEG2025138736000018.jpg32142

[0069] Nucleophilic Reactions Enamine tautomers behave similarly to enols, but the alpha carbon atom exhibits nucleophilic properties. The imine-enamine tautomerization reaction provides the imine with a potential reaction pathway stemming from the nucleophilic properties of the alpha carbon atom. In the case of 4-aminopyridine, the enamine form exhibits more aromatic properties than the imine form and is therefore more stable. Therefore, the smaller the imine:enamine tautomerization equilibrium ratio, the stronger the reactivity of the imine. In this case, a nucleophile attacks the 2-carbon atom of the imine, resulting in a nucleophilic reaction, as shown in Reaction Scheme 2 below. <Reaction Scheme 2> JPEG2025138736000019.jpg47148

[0070] Nucleophilic Polymerization Reactions According to the present invention, a chain polymerization reaction between imine-form compounds occurs simultaneously with, before, or after the nucleophilic reaction with a nucleophile on the substrate surface. During this reaction, the imine group at position 4 acts as a nucleophile and attacks the carbon at position 2 of another imine-form compound, resulting in a nucleophilic reaction. As a result of this reaction, the surface of the substrate is modified with the compound of Formula 1 or its tautomer, or their oligomer or (co)polymer, as shown in Formula 12 below. The degree of polymerization of the modified polymer can be controlled by adjusting the concentration ratio of the compound relative to the reactive sites on the substrate. For example, the higher the concentration of the compound relative to the reactive sites on the substrate, the higher the degree of polymerization of the modified polymer; and the lower the concentration of the compound relative to the reactive sites on the substrate, the lower the degree of polymerization of the modified polymer. <Chemical formula 12> JPEG2025138736000020.jpg42144

[0071] Electrophilic Polymerization Reactions On the other hand, when an electrophile is present on the substrate surface, it binds to the substrate surface through an electrophilic reaction with the imine group at position 4 of the imine-form compound, as illustrated in the following Reaction Scheme 3. Furthermore, as in the case of a nucleophilic reaction, a polymerization reaction between imine-form compounds occurs, and the substrate surface is modified with the compound of Formula 1 or its tautomer, or their oligomer or (co)polymer, as illustrated in the following Chemical Scheme 13. <Reaction Scheme 3> JPEG2025138736000021.jpg39143 <Chemical formula 13> JPEG2025138736000022.jpg49148

[0072] Compound of Formula 2 An embodiment of the present invention provides an aminoheterocyclic compound of Formula 2: <Chemical formula 2> JPEG2025138736000023.jpg25145

[0073] L 21 ~L 25 In the above formula 2, L 21 ~L 25 are each independently a single bond or a double bond, and L 21 ~L 25 At least one of the groups is a double bond.

[0074] A 21 or A 25 A 21 or A 25 are each independently -C(R 21 R 22 )-, -N(R 23 )-, -O-, and -S-; A 21 or A 25 At least one of the -N(R 23 )-, -O- or -S-, and A 21 or A 25At least one of the -C(R 21 R 22 )-.

[0075] R 21 ~R 23 R 21 and R 22 are each independently selected from the group consisting of H, NH, ═NH, C-C alkyl, C-C alkoxy, halo, CN, carboxyl, formyl, OH, and SH, or together with the carbon atom connected thereto form a carbonyl or thiocarbonyl group; R 23 is hydrogen or NH2.

[0076] Double bond / single bond However, (a)L 21 ~L 25 Among these, two Ls adjacent to any L that is a double bond are single bonds, and A connected by Ls that are double bonds is not -O- or -S-; (b) L 21 ~L 25 A connected by any L that is a double bond is -C(R 21 R 22 )- or -N(R 23 )-, R bonded to the carbon or nitrogen atom 22 and R 23 does not exist, and (c)R 21 , R 22 and R 23 At least one of these is NH2.

[0077] polymerization reaction In the case of the 5-membered aminoheterocyclic compound of Chemical Formula 2, the reaction occurs along the same pathway as the 6-membered aminoheterocyclic compound of Chemical Formula 1. For example, in the case of 4-aminoimidazole, an equilibrium is formed as shown in Reaction Scheme 4, and the imine form of the compound reacts with a nucleophile or electrophile on the substrate surface (Reaction Schemes 5 and 6), resulting in the substrate surface being modified with the compound of Chemical Formula 2 or its tautomer, or an oligomer or (co)polymer thereof, as shown in Chemical Formula 14 or Chemical Formula 15 below. <Reaction Scheme 4> JPEG2025138736000024.jpg25142 <Reaction Scheme 5> JPEG2025138736000025.jpg35141 <Chemical formula 14> JPEG2025138736000026.jpg46166 <Reaction Scheme 6> JPEG2025138736000027.jpg37165 <Chemical formula 15> JPEG2025138736000028.jpg38165

[0078] Compound of Formula 3 An embodiment of the present invention provides a vinylamino heterocycle compound of Formula 3: <Chemical formula 3> JPEG2025138736000029.jpg51166

[0079] L 31 ~L 36 In the formula 3, L 31 ~L 36 are each independently a single bond or a double bond.

[0080] A 31 or A 35 A 31 or A 35 are each independently -C(R 31 R 32 )-, -N(R 33 )-, -O-, and -S-; A 31 or A 35 At least one of the -N(R 33 )-, -O- or -S-, and A 31 or A 35At least one of the -C(R 31 R 32 )-.

[0081] R 31 ~R 34 R 31 and R 32 are each independently selected from the group consisting of H, NH, ═NH, C-C alkyl, C-C alkoxy, halo, CN, carboxyl, formyl, OH, and SH, or together with the carbon atom connected thereto form a carbonyl or thiocarbonyl group; R 33 is hydrogen or NH2, and R 34 is hydrogen.

[0082] Double bond / single bond However, (a)L 31 ~L 36 Among these, two Ls adjacent to any L that is a double bond are single bonds, and A connected by Ls that are double bonds is not -O- or -S-; (b) L 31 ~L 36 A connected by any L that is a double bond is -C(R 31 R 32 )- or -N(R 33 )-, R bonded to the carbon or nitrogen atom 32 and R 33 does not exist, and (c)L 31 or L 36 If is a double bond, R 34 does not exist.

[0083] Nucleophilic Reactions The vinyl group of the vinylamino heterocyclic compound of Formula 3 of the present invention provides a pathway for inducing a nucleophilic reaction with a nucleophile on the surface of a substrate. For example, in the case of 4-amino-2-ethenylpyridine, a nucleophilic reaction occurs between the vinyl group and a nucleophile on the surface of a substrate, as illustrated in Reaction Scheme 7 below. <Reaction Scheme 7> JPEG2025138736000030.jpg43143

[0084] Nucleophilic Polymerization Reactions According to the present invention, a chain polymerization reaction between vinyl heterocycle compounds occurs simultaneously with, before, or after the nucleophilic reaction with a nucleophile on the substrate surface. That is, the vinyl group acts as a nucleophile and attacks the vinyl group of another vinyl heterocycle compound, causing a nucleophilic reaction. As a result of this reaction, the surface of the substrate is modified with the compound of Formula 3 or its oligomer or (co)polymer, as shown in Formula 16 below. The degree of polymerization of the modified polymer can be controlled by adjusting the concentration ratio of the compound to the reactive sites on the substrate. For example, the higher the concentration of the compound relative to the reactive sites on the substrate, the higher the degree of polymerization of the modified polymer, and the lower the concentration of the compound relative to the reactive sites on the substrate, the lower the degree of polymerization of the modified polymer. <Chemical formula 16> JPEG2025138736000031.jpg34144

[0085] Electrophilic Polymerization Reactions On the other hand, when an electrophile is present on the substrate surface, it is bonded to the substrate surface through an electrophilic reaction with the vinyl group as shown in the following reaction formula 8. Also, as in the case of a nucleophilic reaction, a polymerization reaction between heterocyclic compounds having a vinyl group occurs, and the substrate surface is modified with the compound of formula 3 or its oligomer or (co)polymer as shown in the following formula 17. <Reaction Scheme 8> JPEG2025138736000032.jpg46166 <Chemical formula 17> JPEG2025138736000033.jpg55166

[0086] Compound of Formula 4 An embodiment of the present invention provides a vinylamino heterocycle compound of Formula 4: <Chemical formula 4> JPEG2025138736000034.jpg42166

[0087] L 41 ~L 45 In the formula 4, L 41 ~L 45 are each independently a single bond or a double bond.

[0088] A 41 or A 44 A 41 or A 44 are each independently -C(R 41 R 42 )-, -N(R 43 )-, -O-, and -S-; A 41 or A 44 At least one of the -N(R 43 )-, -O- or -S-, and A 41 or A 44 At least one of the -C(R 41 R 42 )-.

[0089] R 41 ~R 43 R 41 and R 42 are each independently selected from the group consisting of H, NH, ═NH, C-C alkyl, C-C alkoxy, halo, CN, carboxyl, formyl, OH, and SH, or together with the carbon atom connected thereto form a carbonyl or thiocarbonyl group; R 43 is hydrogen or NH2, and R 44 is hydrogen.

[0090] Single bond / double bond However, (a)L 41 ~L 45 Among these, two Ls adjacent to any L that is a double bond are single bonds, and A connected by Ls that are double bonds is not -O- or -S-; (b) L41 ~L 45 A connected by any L that is a double bond is -C(R 41 R 42 )- or -N(R 43 )-, R bonded to the carbon or nitrogen atom 42 and R 43 does not exist, and (c)L 41 or L 45 If is a double bond, R 44 does not exist.

[0091] polymerization reaction In the case of the 5-membered vinylamino heterocycle compound of Chemical Formula 4, the reaction occurs along the same pathway as the 6-membered vinylamino heterocycle compound of Chemical Formula 3. For example, in the case of 2-amino-5-ethenyl-1H-imidazole, it reacts with a nucleophile or electrophile on the substrate surface as shown in Reaction Schemes 9 and 10, respectively, to modify the substrate surface with the compound of Chemical Formula 4 or its oligomer or (co)polymer as shown in Chemical Formula 18 or Chemical Formula 19 below. <Reaction Scheme 9> JPEG2025138736000035.jpg37141 <Reaction Scheme 10> JPEG2025138736000036.jpg47165 <Chemical formula 18> JPEG2025138736000037.jpg37165 <Chemical formula 19> JPEG2025138736000038.jpg37148

[0092] Compound of Formula 5 An embodiment of the present invention provides an aminocycloalkene compound of Formula 5: <Chemical formula 5> JPEG2025138736000039.jpg41166

[0093] R 51 ~R 52 In the above formula 5, R 51 are each independently selected from the group consisting of H, -NH, halo, C-C alkyl, C-C alkoxy, CN, carboxyl, formyl, OH, and SH; R 52 are each independently selected from the group consisting of H, -NH, halo, C-C alkyl, C-C alkoxy, CN, carboxyl, formyl, OH, SH, and =NH, or together with the carbon atom connected thereto form a carbonyl or thiocarbonyl group, with the proviso that (a) R 51 and R 52 At least one of the groups is NH2, and (b) R 52 is NH2, halo, C1-C6 alkyl, C1-C6 alkoxy, CN, carboxyl, formyl, OH, or SH, then R 52 Further R attached to carbon such as 52 is H, and (c) R 52 When R is ═NH or forms a carbonyl or thiocarbonyl group together with the carbon atom connected thereto, 52 Further R attached to carbon such as 52 does not exist.

[0094] Imine-enamine tautomers The aminocycloalkene compound of Formula 5 of the present invention forms an equilibrium between the imine (or Schiff base) form of the compound and its enamine tautomer form in aqueous solution. The imine-enamine tautomer is the nitrogen analog of the keto-enol tautomer. In both cases, a hydrogen atom exchange occurs between a heteroatom and a carbon atom. For example, in the case of 3-iminocyclohex-1-en-1-amine, the following equilibrium is formed: <Reaction Scheme 11> JPEG2025138736000040.jpg26141

[0095] Nucleophilic Reactions Enamine tautomers behave similarly to enols, but the alpha carbon atom exhibits nucleophilic properties. The imine-enamine tautomerization reaction gives the imine a potential reaction pathway stemming from the nucleophilic nature of the alpha carbon atom. In the case of 3-iminocyclohex-1-en-1-amine shown above, the imine form exhibits even greater reactivity. In this case, a nucleophile attacks the 1-carbon atom of the imine, resulting in a nucleophilic reaction. <Reaction Scheme 12> JPEG2025138736000041.jpg38142

[0096] Nucleophilic Polymerization Reactions According to the present invention, a chain polymerization reaction between imine-form compounds occurs simultaneously with, before, or after the nucleophilic reaction with a nucleophile on the substrate surface. During this reaction, the imine group at position 3 acts as a nucleophile and attacks the carbon at position 1 of another imine-form compound, causing a nucleophilic reaction. As a result of this reaction, the surface of the substrate is modified with the compound of Formula 5 or its tautomer, or their oligomer or (co)polymer, as shown in Formula 20 below. The degree of polymerization of the modified polymer can be controlled by adjusting the concentration ratio of the compound relative to the reactive sites on the substrate. For example, the higher the concentration of the compound relative to the reactive sites on the substrate, the higher the degree of polymerization of the modified polymer; and the lower the concentration of the compound relative to the reactive sites on the substrate, the lower the degree of polymerization of the modified polymer. <Chemical formula 20> JPEG2025138736000042.jpg37141

[0097] Electrophilic Polymerization Reactions On the other hand, when an electrophile is present on the substrate surface, it binds to the substrate surface through an electrophilic reaction with the imine group at position 3 of the imine-form compound, as illustrated in the following reaction scheme 13. Similarly to the case of a nucleophilic reaction, a polymerization reaction between imine-form compounds occurs, and the substrate surface is modified with the compound of formula 5 or its tautomer, or their oligomer or (co)polymer, as illustrated in the following reaction scheme 21. <Reaction Scheme 13> JPEG2025138736000043.jpg42142 <Chemical formula 21> JPEG2025138736000044.jpg45166

[0098] Compound of Formula 6 An embodiment of the present invention provides an aminocycloalkene compound of Formula 6: <Chemical formula 6> JPEG2025138736000045.jpg32142

[0099] R 61 ~R 62 In the formula 6, R 61 are each independently selected from the group consisting of H, NH, halo, C-C alkyl, C-C alkoxy, CN, carboxyl, formyl, OH, and SH; R 62 are each independently selected from the group consisting of H, NH, halo, C-C alkyl, C-C alkoxy, CN, carboxyl, formyl, OH, SH, and ═NH, or together with the carbon atom connected thereto form a carbonyl or thiocarbonyl group, with the proviso that (a) R 61 and R 62 At least one of the groups is NH2, and (b) R 62 is NH2, halo, C1-C6 alkyl, C1-C6 alkoxy, CN, carboxyl, formyl, OH, or SH, then R 62 Further R attached to carbon such as62 is H, and (c) R 62 When R is ═NH or forms a carbonyl or thiocarbonyl group together with the carbon atom connected thereto, 62 Further R attached to carbon such as 62 does not exist.

[0100] polymerization reaction In the case of the 5-membered aminocycloalkene compound of Chemical Formula 6, the reaction occurs along the same pathway as the 6-membered aminocycloalkene of Chemical Formula 5. For example, in the case of 3-aminocyclopent-2-en-1-one, an equilibrium is formed as shown in Reaction Scheme 4, and the imine-form compound reacts with a nucleophile or electrophile on the substrate surface (Reaction Schemes 15 and 16), resulting in the substrate surface being modified with the compound of Chemical Formula 6 or its tautomer, or an oligomer or (co)polymer thereof, as shown in Chemical Formula 22 or Chemical Formula 23 below. <Reaction Scheme 14> JPEG2025138736000046.jpg36141 <Reaction Scheme 15> JPEG2025138736000047.jpg55166 <Chemical formula 22> JPEG2025138736000048.jpg48165 <Reaction Scheme 16> JPEG2025138736000049.jpg40155 <Chemical formula 23> JPEG2025138736000050.jpg41165

[0101] Compound of Formula 7 An embodiment of the present invention provides a vinylamino non-aromatic ring compound of Formula 7: <Chemical formula 7> JPEG2025138736000051.jpg43144

[0102] L 71 ~L 76 In the formula 7, L 71 ~L 76 are each independently a single bond or a double bond, and L 71 ~L 76 The number of double bonds is 0 to 2.

[0103] R 71 ~R 73 R 71 and R 72 are each independently selected from the group consisting of H, NH, ═NH, C-C alkyl, C-C alkoxy, halo, CN, carboxyl, formyl, OH, and SH, or together with the carbon atom connected thereto form a carbonyl or thiocarbonyl group; R 73 is selected from the group consisting of H, NH2, C1-C6 alkyl, C1-C6 alkoxy, halo, CN, carboxyl, formyl, OH, and SH.

[0104] Single bond / double bond However, (a)L 71 ~L 76 Among these, two Ls adjacent to any L that is a double bond are single bonds, and (b) L 71 ~L 76 R bonded to a carbon atom connected by any L that is a double bond 72 does not exist, and (c)L 71 or L 76 If is a double bond, R 73 does not exist, and (d)R 71 or R 72 is ═NH or forms a carbonyl or thiocarbonyl group together with the carbon atom connected thereto, R 71 or R 72 does not exist, and (e)R 71 ~R 73 At least one of these is NH2.

[0105] Nucleophilic Reactions The vinyl group of the vinylamino non-aromatic ring compound of the present invention represented by Formula 7 provides a pathway for inducing a nucleophilic reaction with a nucleophile on the surface of a substrate. For example, in the case of 1-amino-4-ethenylcyclohexane, a nucleophilic reaction between a nucleophile on the surface of a substrate and the vinyl group occurs as shown in Reaction Scheme 17 below. <Reaction Scheme 17> JPEG2025138736000052.jpg45144

[0106] Nucleophilic Polymerization Reactions According to the present invention, a chain polymerization reaction between vinylamino non-aromatic ring compounds occurs simultaneously with, before, or after the nucleophilic reaction with a nucleophile on the substrate surface. That is, the vinyl group acts as a nucleophile and attacks the vinyl group of another vinylamino non-aromatic ring compound, causing a nucleophilic reaction. As a result of this reaction, the surface of the substrate is modified with the compound of Formula 7 or its oligomer or (co)polymer, as shown in Formula 24 below. The degree of polymerization of the modified polymer can be controlled by adjusting the concentration ratio of the compound to the reactive sites on the substrate. For example, the higher the concentration of the compound relative to the reactive sites on the substrate, the higher the degree of polymerization of the modified polymer, and the lower the concentration of the compound relative to the reactive sites on the substrate, the lower the degree of polymerization of the modified polymer. <Chemical formula 24> JPEG2025138736000053.jpg35143

[0107] Electrophilic Polymerization Reactions On the other hand, when an electrophile is present on the substrate surface, it is bonded to the substrate surface through an electrophilic reaction with the vinyl group, as illustrated in the following reaction formula 18. Also, as in the case of a nucleophilic reaction, a polymerization reaction between an amino non-aromatic ring compound having a vinyl group occurs, and the substrate surface is modified with the compound of formula 7 or its oligomer or (co)polymer, as illustrated in the following reaction formula 25. <Reaction Scheme 18> JPEG2025138736000054.jpg41141 <Chemical formula 25> JPEG2025138736000055.jpg37166

[0108] Compound of Formula 8 An embodiment of the present invention provides a vinylamino non-aromatic ring compound of Formula 8: <Chemical formula 8> JPEG2025138736000056.jpg41143

[0109] L 81 ~L 85 In the formula 8, L 81 ~L 85 are each independently a single bond or a double bond, and L 81 ~L 85 The number of double bonds is 0 to 1.

[0110] R 81 ~R 83 R 81 and R 82 are each independently selected from the group consisting of H, NH, ═NH, C-C alkyl, C-C alkoxy, halo, CN, carboxyl, formyl, OH, and SH, or together with the carbon atom connected thereto form a carbonyl or thiocarbonyl group; R 83 is selected from the group consisting of H, NH2, C1-C6 alkyl, C1-C6 alkoxy, halo, CN, carboxyl, formyl, OH, and SH.

[0111] Single bond / double bond However, (a)L 81 ~L 85 Among these, two Ls adjacent to any L that is a double bond are single bonds, and (b) L 81 ~L 85 R bonded to a carbon atom connected by any L that is a double bond82 does not exist, and (c)L 81 or L 85 If is a double bond, R 83 does not exist, and (d)R 81 or R 82 is ═NH or forms a carbonyl or thiocarbonyl group together with the carbon atom connected thereto, R 81 or R 82 does not exist, and (e)R 81 ~R 83 At least one of these is NH2.

[0112] polymerization reaction In the case of the 5-membered vinylamino non-aromatic ring compound of Chemical Formula 8, the reaction occurs along the same pathway as the 6-membered vinylamino non-aromatic ring compound of Chemical Formula 7. For example, in the case of 1-amino-3-ethenylcyclopentane, the vinyl group of the compound reacts with a nucleophile or electrophile on the substrate surface, and the substrate surface is modified with the compound of Chemical Formula 8 or its oligomer or (co)polymer, as illustrated in Chemical Formula 26 or Chemical Formula 27 below. <Reaction Scheme 19> JPEG2025138736000057.jpg37142 <Reaction Scheme 20> JPEG2025138736000058.jpg48166 <Chemical formula 26> JPEG2025138736000059.jpg41143 <Chemical formula 27> JPEG2025138736000060.jpg37148

[0113] Compound of Formula 9 An embodiment of the present invention provides a furfurylamine of Formula 9. <Chemical formula 9> JPEG2025138736000061.jpg17142

[0114] polymerization reaction Furfurylamine of Formula 9 is expected to undergo a chain polymerization reaction between furfurylamine compounds simultaneously with, before, or after a nucleophilic reaction with a nucleophile on the substrate surface. As can be predicted from its structure, the polymerization reaction between furfurylamines appears to follow a Diels-Alder reaction pathway. Furthermore, copolymerization reactions between furfurylamine and other compounds having double bonds also involve a Diels-Alder reaction between two double bonds in the furan ring of furfurylamine and a double bond of the other compound. However, these predicted reaction pathways are merely intended to aid in the understanding of the present invention, and the scope of the present invention is not constrained or particularly limited by these reaction pathways themselves.

[0115] Compound of Formula 10 An embodiment of the present invention provides an unsaturated acyclic amine compound of Formula 10: <Chemical formula 10> JPEG2025138736000062.jpg31144

[0116] X a In the formula 10, X a is -NH2, -N=CH-OH, or -N=O.

[0117] R a1 ~R a3 R a1 is hydrogen, C1-C6 alkyl, or -CN, and R a2 and R a3 are each independently hydrogen, C1-C6 alkyl, -CN, -OH, -NH2, -NH-OH, or -C(O)R a4 and -C(O)OR a5 (where R a4 and R a5 is hydrogen or C1-C6 alkyl).

[0118] polymerization reaction According to the present invention, it is expected that a chain polymerization reaction between unsaturated acyclic amine compounds occurs simultaneously with, before, or after the nucleophilic reaction with a nucleophile on the substrate surface (see the following reaction schemes 21 and 22). However, such predicted reaction pathways are merely intended to aid in the understanding of the present invention, and the scope of the present invention is not restricted or particularly limited by such reaction pathways themselves. <Reaction Scheme 21> JPEG2025138736000063.jpg37141 <Reaction Scheme 22> JPEG2025138736000064.jpg40145 <Chemical formula 28> JPEG2025138736000065.jpg39145

[0119] Compound of Formula 11 An embodiment of the present invention provides an amine compound of Formula 11: <Chemical formula 11> JPEG2025138736000066.jpg40142

[0120] R b1 In the formula 11, R b1 is a substituent selected from the group consisting of H, NH2, and NH-acyl.

[0121] Imine-enamine tautomers The compound of Formula 11 forms an equilibrium between the imine (or Schiff base) form of the compound and its enamine tautomer form in aqueous solution. The imine-enamine tautomer is the nitrogen analog of the keto-enol tautomer. In both cases, a hydrogen atom exchange occurs between a heteroatom and a carbon atom. For example, the following equilibrium is formed: <Reaction Scheme 24> JPEG2025138736000067.jpg29143

[0122] Nucleophilic Reactions Enamine tautomers behave similarly to enols, but the alpha carbon atom exhibits nucleophilic properties. The imine-enamine tautomerization reaction provides the imine with a potential reaction pathway stemming from the nucleophilic properties of the alpha carbon atom. The enamine form exhibits more aromatic properties than the imine form and is therefore more stable. Therefore, the smaller the imine:enamine tautomerization equilibrium ratio, the stronger the reactivity of the imine. In this case, a nucleophile attacks the imine carbon atom, resulting in a nucleophilic reaction, as shown in Reaction Scheme 25 below. <Reaction Scheme 25> JPEG2025138736000068.jpg30170

[0123] Nucleophilic Polymerization Reactions According to the present invention, a chain polymerization reaction between imine-form compounds occurs simultaneously with, before, or after the nucleophilic reaction with a nucleophile on the substrate surface. During this reaction, the imine group at position 4 acts as a nucleophile and attacks the carbon at position 2 of another imine-form compound, resulting in a nucleophilic reaction. As a result of this reaction, the surface of the substrate is modified with the compound of formula 11, its tautomer, or their oligomer or (co)polymer, as shown in Formula 11 below. The degree of polymerization of the modified polymer can be controlled by adjusting the concentration ratio of the compound relative to the reactive sites on the substrate. For example, the higher the concentration of the compound relative to the reactive sites on the substrate, the higher the degree of polymerization of the modified polymer; whereas, the lower the concentration of the compound relative to the reactive sites on the substrate, the lower the degree of polymerization of the modified polymer. <Chemical formula 29> JPEG2025138736000069.jpg29141

[0124] Electrophilic Polymerization Reactions On the other hand, when an electrophile is present on the substrate surface, it binds to the substrate surface through an electrophilic reaction with the imine group at position 4 of the imine-form compound, as illustrated in the following reaction scheme 26. Furthermore, as in the case of a nucleophilic reaction, a polymerization reaction between imine-form compounds occurs, and the substrate surface is modified with the compound of formula 11 or its tautomer, or their oligomer or (co)polymer, as illustrated in the following reaction scheme 30. <Reaction Scheme 26> JPEG2025138736000070.jpg32145 <Chemical formula 30> JPEG2025138736000071.jpg30142

[0125] Other monomer compounds There are compounds having an amino group that can be used as a monomer in the method of coating the surface of a substrate, even though they do not belong to Formulas 1 to 11 above. These are referred to as "other monomer compounds." Other monomer compounds can be used together with or instead of the compounds of Formulas 1 to 11 herein.

[0126] Examples of monomer compounds The compounds of Formulas 1 to 11 and other monomer compounds may each be selected from one or more of the compounds listed in Table 1 below. [Table 1] JPEG2025138736000073.jpg178170 JPEG2025138736000074.jpg179170 JPEG2025138736000075.jpg176170 JPEG2025138736000076.jpg202170

[0127] II. Substrate As shown in the diagram from above, the compounds of Formulas 1 to 11 can undergo polymerization through both nucleophilic and electrophilic reactions, and can therefore undergo polymerization by reacting with a substrate surface having a nucleophile or a substrate having an electrophile on its surface. Therefore, the compounds of Formulas 1 to 11 can react with the surface of various substrates to form a polymer layer on the surface. Such substrates may include, but are not limited to, glass, wood, stone, metal, ceramic, natural and synthetic polymers, etc.

[0128] metal substrate The substrate may be one or more selected from the group consisting of iron, copper, aluminum, zinc, tin, silver, gold, titanium, tungsten, nickel, molybdenum, cobalt, magnesium, and alloys thereof.

[0129] Ceramic substrate The substrate may be zinc oxide, zirconium oxide, titanium oxide, aluminum borate, iron oxide, calcium carbonate, barium carbonate, lead oxide, tin oxide, cerium oxide, lithium oxide, calcium oxide, magnesium oxide, trimanganese tetroxide, niobium oxide, tantalum oxide, tungsten oxide, antimony oxide, aluminum phosphate, calcium silicate, zirconium silicate, ITO (tin-containing indium oxide), titanium silicate, barium titanate, strontium titanate, calcium titanate, montmorillonite, saponite, vermicular The lithium ion-exchange material may be one or more selected from the group consisting of lithium ion, ...

[0130] natural polymer substrate The substrate may be one or more selected from the group consisting of starch, cellulose, chitosan, chitin, gelatin, pectin, carrageenan, dextran, collagen, hyaluronic acid, alginate, gluten, fibrin, and agarose.

[0131] Synthetic polymer substrate The substrate can be a general purpose thermoplastic polymer, a thermoset polymer, an engineering polymer, an elastomer, or the like. For example, the substrate may be one or more selected from the group consisting of polyolefins including polyethylene, polypropylene, polymethylpentene, polybutene-1, etc.; polyolefin elastomers including polyisobutylene, ethylene-propylene rubber, ethylene-propylene-diene rubber (EPDM), etc.; halogenated polyolefins including polyvinyl chloride, polyvinylidene chloride, polychlorotrifluoroethylene, polyvinylidene fluoride, polytetrafluoroethylene, etc.; polystyrene, polyvinyl alcohol, polyacetal, polyvinyl acetate, polyacrylonitrile, polybutadiene, polyisoprene, phenolic resins, epoxy resins, polyamides, polyesters including polyethylene terephthalate and polybutylene terephthalate, etc.; polyimides, polyamideimides, polyetherimides, polyacrylates, polyurethanes, polysiloxanes, polynaphthalenes, polythiophenes, polyanilines, polyparaphenylene sulfide, polychloroprene, styrene-butadiene rubber, nitrile rubber, silicone rubber, and copolymers thereof.

[0132] Substrate shape The substrate may be in the form of a film, powder, bead, plate, rod, tube, or any three-dimensional shape. If necessary, only a portion of the substrate may be modified by contacting only a portion of the substrate with a compound of Formula 1 to Formula 11.

[0133] III. Formation of a polymer layer on the substrate surface As explained above, the compounds of Formulas 1 to 11 can react and bond with a substrate surface to form a polymer layer on the substrate surface through a chain polymerization reaction. The polymer layer formed on the substrate surface can change the properties (e.g., hydrophilicity) of the substrate surface, making the specific substrate more suitable for any application. Furthermore, because the polymer layer is formed by bonding to the substrate surface in monomer units, it can also fill defects such as small cavities and cracks in the substrate and improve the physical properties of the substrate, such as moisture permeability and strength. Furthermore, because it is chemically bonded to the substrate surface, no adhesive is required, and the polymer layer is firmly bonded to the substrate surface and does not easily peel off compared to conventional coatings.

[0134] Method in Figure 1 As shown in FIG. 1, according to one embodiment of the present invention, a method for forming a polymer layer on a substrate surface using one or more of the compounds of Formulas 1 to 11 as monomers includes step 120 of providing a solution containing the monomers, step 140 of initiating a polymerization reaction of the monomers on the substrate surface, step 160 of polymerizing the monomers on the substrate surface to form a polymer layer, and step 180 of rinsing and drying.

[0135] Monomer solution production 1, one or more of the compounds of Formulas 1 to 11 are added to a solvent to prepare a monomer-containing reactive composition solution, which is referred to as a "monomer solution."

[0136] Acidity (pH) In the substrate modification method, the monomer solution can be acidic, neutral, or basic. For example, the pH of the monomer solution can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14. The pH of the monomer solution can fall within a range obtained by selecting two of the values ​​listed in the immediately preceding sentence. For example, the pH of the monomer can range from about 3 to 10, or from about 7 to 13.

[0137] solvent For example, pure water, a buffer solution (weakly acidic, neutral, or basic), NaOH solution (0.01 M, 0.1 M, or 1 M), 50 mM-500 mM borate buffer (pH 9), or 15 to 20% DMEA (N,N-dimethylamine: CAS598-56-1; salt-free, pH 13 to 14) can be used as the solvent, but the solvent is not particularly limited thereto.

[0138] concentration The monomer concentration is not particularly limited and can be adjusted appropriately depending on the solute, solvent, and other reaction conditions used. For example, the monomer concentration in the monomer solution can be about 0.1, 0.2, 0.3, 0.5, 0.7, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or 10 mg / mL. The monomer concentration in the monomer solution can fall within a range obtained by selecting two of the values ​​listed in the immediately preceding sentence. For example, the monomer concentration can be in the range of about 0.1 to 5 mg / mL or about 0.5 to 7 mg / mL.

[0139] one or more monomers Two or more types of monomers can be added to the monomer solution to form a polymer layer on the substrate surface that is a copolymer of two or more types of monomers.

[0140] Polymerization reaction begins In step 140 of FIG. 1, the monomer solution is contacted with the substrate surface to initiate the polymerization reaction.

[0141] Contact method Any known coating method can be used as long as the substrate surface can be sufficiently contacted with the monomer solution for a certain period of time. For example, a container large enough to accommodate the substrate can be filled with the monomer solution, and then the substrate can be placed in the monomer solution. Alternatively, spin coating, spray coating, etc. can be used. The monomer solution can be contacted with a portion of the substrate, the entire substrate, a cross section, or both surfaces.

[0142] Initiation of the polymerization reaction The polymerization reaction usually proceeds without a separate initiator, but can also proceed with the addition of an initiator in some cases. The polymerization reaction proceeds at a temperature lower than the boiling point of the solvent, usually between 0 and 90°C.

[0143] No initiator According to one embodiment of the present invention, the polymerization reaction of a monomer can be initiated without the addition of a separate initiator, such as a radical initiator. For example, at least some of the compounds of Formulas 1 to 11 are self-initiating monomers that can initiate a polymerization reaction by reacting with a substrate surface without the need for a separate initiator. For example, the polymerization composition may not contain known radical initiators such as azo compounds such as AIBN (Azobisisobutyronitrile) and ABCN (1,1'-Azobis(cyclohexane-carbonitrile)), or organic peroxides such as di-tert-butyl peroxide ((CH3)3C-OOC(CH3)3) and benzoyl peroxide ((PhCOO)2).

[0144] polymerization reaction In step 160 of FIG. 1, a polymerization reaction is allowed to proceed to form a polymer layer on the substrate surface.

[0145] Polymerization through contact According to one embodiment, simply contacting the substrate with the monomer solution for a certain period of time at a certain temperature allows the monomer to react with the substrate surface to form a polymer layer.

[0146] Monomer solution contact time The time period for which the substrate is in contact with the monomer solution can be about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 42, 44, 46, 48, 50, 52, 54, 56, 68, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, or 80 hours. The time period for which the substrate is in contact with the monomer solution can fall within a range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, the polymerization reaction time may be in the range of about 2 to about 10 hours, about 6 to about 12 hours, or about 8 to about 24 hours.

[0147] Monomer solution temperature The polymerization reaction proceeds at a temperature below the boiling point of the solvent used. The temperature of the monomer solution is adjusted to approximately 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100°C. This temperature can fall within the range obtained by selecting two of the numbers listed in the previous sentence. For example, the temperature of the polymerization reaction composition can fall within the range of approximately 20 to approximately 70°C, approximately 40 to approximately 90°C, or approximately 10 to approximately 30°C.

[0148] catalyst If a catalyst can be used, it can be added to promote the reaction, but it is not necessarily required.

[0149] Mixing The polymerization reaction composition can be stirred to activate the bonding reaction with the substrate or the polymerization reaction.

[0150] Oligomer Polymerization reactions produce polymers of various sizes, as well as oligomers and dimers. Polymers and oligomers can be produced by contacting the monomer solution with the substrate.

[0151] Polymerization reaction complete After the polymerization reaction is complete, the substrate is removed from the reaction vessel and the liquid components of the polymerization reaction composition remaining on the surface of the polymer layer or substrate are removed by wiping or touching the surface with absorbent paper or an absorbent pad. Before or after wiping off the liquid components, the substrate may be washed with water or another cleaning solution. If washing is performed, the liquid on the surface is wiped off.

[0152] Baking Step According to one embodiment, after the polymerization reaction is completed and the substrate is washed with water or another cleaning solution, it can be baked. Baking can be performed in a high-temperature, dry environment using an oven or other suitable equipment. Baking can evaporate any solvent remaining in the polymer layer, partially crosslink the polymers formed in the polymer layer, and cure and harden the polymer layer.

[0153] Baking time The baking time is not particularly limited and can be appropriately selected and adjusted by those skilled in the art depending on the specific compound and substrate used. For example, the baking time can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24 hours. The baking time can fall within a range obtained by selecting two of the values ​​listed in the immediately preceding sentence. For example, the baking time can range from about 1 to 9 hours or from 3 to 24 hours.

[0154] Baking Temperature Baking is performed at a temperature that does not denature the substrate, and can be appropriately selected and adjusted by those skilled in the art depending on the specific type of compound and type of substrate used. For example, the baking temperature can be 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100°C. The baking temperature can fall within a range obtained by selecting two of the values ​​listed in the immediately preceding sentence. For example, the baking temperature can be in the range of about 50 to 90°C or 60 to 100°C.

[0155] Washing and drying In step 180 of FIG. 1, the baked substrate is washed to remove unbonded or unpolymerized monomer compounds and impurities. Washing can be performed with an acidic solution and / or a basic solution. For example, the substrate can be washed with an acidic solution, washed with water, and then washed again with a basic solution and washed with water. Alternatively, the substrate can be washed with a basic solution, washed with water, and then washed again with an acidic solution and washed with water. After washing, the substrate is dried at room temperature or at an elevated temperature to obtain a substrate on which a polymer layer has been formed.

[0156] Use of prepolymerized polymers According to one embodiment of the present invention, a solution containing a pre-polymerized polymer ("polymer solution") may be used in one or more of the above steps. For example, after the polymerization reaction and before the baking process, the substrate may be further reacted with the polymer solution. In this case, the pre-polymerized polymer may be added to the polymer layer obtained by the polymerization reaction to promote cross-linking.

[0157] IV. Polymer layer formed on the substrate surface Polymer layer morphology Through the above method, a polymer layer is formed on a portion or the entire surface of the substrate. The polymer layer can be bonded to the substrate surface through a chemical bond. For example, at least a portion of the polymer molecules of the polymer layer can be attached to the substrate surface through a covalent bond. The polymer layer can be formed on the entire surface, a portion, a cross section, or both surfaces of the substrate.

[0158] Polymer Layer Thickness The thickness of the polymer layer formed on the substrate surface by the above method is not particularly limited and can be appropriately selected and adjusted by those skilled in the art depending on the specific compound type, substrate type, and reaction conditions used. For example, the thickness of the polymer layer can be 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.4, 2.8, 3.2, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, or 15 μm. The thickness of the polymer layer can fall within a range obtained by selecting two of the values ​​listed in the immediately preceding sentence. For example, the thickness of the polymer layer can be in the range of about 0.05 to 5 μm, or 1 to 15 μm.

[0159] Effect of polymer layer The present invention relates to a polymer layer formed by the substrate-independent attachment of a monomer, its oligomer, or (co)polymer, and a method for forming the same, which can be used for chemical surface coating of various substrates. In particular, it is possible to impart suitable hydrophilicity to the surface of hydrophobic materials used in applications requiring hydrophilicity, or to modify the surface in the opposite direction. Furthermore, it is possible to improve the adhesive strength between interfaces by modifying the chemical properties of one interface, or to increase the separation yield and reliability of biochemicals by using a modifying compound appropriately selected to match the properties of the biochemicals to be immobilized and / or separated. Therefore, the industrial fields in which the present invention can be used are limitless.

[0160] V. OLED panel sealing structure Existing OLED panel sealing structure Known sealing structures and methods for OLED panels include technologies using glass frit and invar. When the organic light-emitting materials used in OLED panels come into contact with oxygen or water vapor, they oxidize, degrading their luminescence performance. Therefore, these sealing technologies use airtight materials and structures that prevent oxygen and water vapor from the air from entering the interior of OLED display products. However, technologies using glass frit and invar are not suitable for use in large or flexible OLED panels.

[0161] Flexible Encapsulation Apparatus The idea of ​​flexible encapsulation structures has been proposed for application to large-sized and flexible OLED panels. Aluminum oxide flexible encapsulation structures, which are made by laminating aluminum oxide layers and polymer layers alternately several times, are being researched, and flexible encapsulation structures that use silicon nitride instead of aluminum oxide are also being researched.

[0162] Aluminum oxide laminate sealing structure When aluminum oxide is deposited using atomic layer deposition (ALD) technology, it is possible to form a dense aluminum oxide layer that is difficult for oxygen and water vapor to pass through. Aluminum oxide has excellent interfacial adhesion with most engineering polymers, and when laminated with a polymer layer, it is theoretically possible to create a flexible OLED panel encapsulation structure.

[0163] Manufacturing of aluminum oxide-polymer laminates Aluminum oxide-polymer laminates can be formed by alternately laminating aluminum oxide layers and polymer layers. For example, an aluminum oxide layer can be formed on a polymer substrate using ALD technology, and then a polymer layer can be coated on top of that to form a polymer layer. Repeating this process of forming another aluminum oxide layer on top of that using ALD technology and then a polymer layer on top of that can produce a flexible encapsulating structure with alternately laminated aluminum oxide layers and polymer layers.

[0164] Disadvantages of the aluminum oxide layer manufacturing process Aluminum oxide thin films tend to crack easily before being laminated with polymer layers multiple times. To create an encapsulation structure for a large OLED panel, aluminum oxide thin films must be produced over a large area, but a drawback of large-area aluminum oxide thin films is that they can crack during transportation and handling, even when attached to a polymer substrate. While ALD technology can deposit aluminum oxide layers with a density suitable for OLED encapsulation, it requires a vacuum chamber and takes a long time for deposition, increasing process costs.

[0165] Silicon nitride laminate flexible sealing structure Silicon nitride layer laminated flexible encapsulation structures, which are made by alternately laminating silicon nitride layers and polymer layers, can also theoretically be used in OLED panels. Aluminum oxide layers of a quality suitable for encapsulating OLED panels can only be formed using ALD deposition technology, but silicon nitride layers can be formed using Plasma Enhanced Chemical Vapor Deposition (PECVD) technology. While the silicon nitride layer obtained using PECVD deposition technology is less dense than the aluminum oxide layer made using ALD deposition technology, PECVD deposition has the advantage of being much faster than ALD in deposition speed.

[0166] Disadvantages of the silicon nitride layer manufacturing process PECVD deposition technology also requires a vacuum chamber, making the process expensive. Furthermore, silicon nitride does not have as strong an interfacial adhesion to the polymer layer as aluminum oxide. To improve the adhesion of the polymer layer, the surface of the polymer layer must be treated with plasma, but the plasma process requires a vacuum chamber, making the process even more expensive.

[0167] Metal layer formation using ALD It is also possible to create flexible encapsulation structures by laminating metal layers alternately with polymer layers several times instead of metal oxides or nitrides, such as aluminum oxide or silicon nitride. ALD technology can be applied to a variety of metals to form metal layers. However, using ALD technology increases process costs. Furthermore, metals generally have many defects in their crystalline structure, which means they have higher permeability to oxygen and water molecules (water vapor) than metal oxides or nitrides made using the same process. Therefore, if ALD technology is used, and all other conditions are the same, metal oxide layers are preferred over metal layers.

[0168] Formation of metal layers using vapor deposition For metals with low boiling points, vapor deposition can form metal layers several hundred nanometers thick. Vapor deposition is less expensive than ALD, but it still requires the use of a vacuum chamber and takes a considerable amount of time.

[0169] VI. Metal foil laminate Flexible sealing structure using metal foil According to implementations of the present invention, a flexible encapsulation structure (or flexible laminate) that can be used in OLED panels is provided by laminating several pre-fabricated metal foils alternately with polymers. The metal foil is manufactured by forming a thin melt of molten metal and then cooling it to solidify. The production cost is much lower than using ALD or vapor phase deposition techniques.

[0170] Metal Foil Laminate To manufacture a flexible encapsulation structure by laminating metal foil, metal foil sheets must be transported and handled. However, attaching the metal foil to a plastic film with a certain degree of mechanical strength is more convenient and improves workability. This is especially true when a large area of ​​metal foil must be used. To do this, a plastic film is first provided and an adhesive layer is formed on one side of it. The metal foil is then placed on the adhesive layer and pressed together to form a metal laminate with a plastic layer-adhesive layer-metal layer structure. This type of metal laminate using metal foil is called a "metal foil laminate" to distinguish it from the metal laminates of other embodiments. Metal foil laminates can be manufactured in various areas depending on the size of the OLED panel.

[0171] Metal foil Metal foils are distinguished from thin films of metal oxides and metal nitrides. A thin oxide film is formed on the surface of metal foil that is in contact with air, but when a cross section of the foil is cut through the thickness, the central part of the cross section is primarily metal. In the case of metal oxides and metal nitrides, the central part of the cross section is also metal oxide or metal nitride.

[0172] metal A variety of metal foils are available for the metal foil laminate, including aluminum, copper, tin, zinc, magnesium, stainless steel, nickel, chromium, tungsten, and the like.

[0173] Metal foil thickness The thickness of the metal foil is typically from a few micrometers to several hundred micrometers. More specifically, it can be about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22.5, 25, 27.5, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, or 400 μm. The thickness of the metal foil can fall within the range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, the metal foil can have a thickness ranging from about 3 to about 100 μm, from about 10 to about 50 μm, from about 20 to about 100 μm, or from about 50 to about 200 μm.

[0174] Internal defects in metals All metals have defects in their internal crystalline structure. Not only that, but defects can be added during the manufacturing, transportation, and storage processes. These defects come in a variety of shapes and sizes. When a cross section of a metal is cut, these defects will appear as depressions with depth in the cross section. Metal foil is no different. If the defect is small compared to the thickness of the metal foil, it will appear as a depression with depth in the thickness direction.

[0175] Pinholes in metal foil If the defects are large compared to the thickness of the metal foil, they may appear as holes, i.e., pinholes, that penetrate through the thickness. Pinholes formed in the metal layer of a metal foil laminate can become channels through which air can enter and exit. If they cannot be sealed or filled, it is difficult to provide an effective sealing structure due to the high permeability of the metal foil laminate to oxygen and water molecules.

[0176] Pinhole size The size of pinholes that occur in metal foils can become even larger as the foil becomes thicker. Pinholes with diameters ranging from a few nanometers to a few micrometers are not uncommon. However, when the metal foil is hundreds of micrometers thick, pinholes with diameters of 10 micrometers or more can occur.

[0177] Plastic film structure The plastic film used to manufacture the airtight packaging material can be composed of a single layer or multiple layers. A multiple layer structure is a structure in which layers of different materials are adjacent to each other and in which layers of the same material are repeated several times.

[0178] Plastic film thickness The thickness of the plastic film can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22.5, 25, 27.5, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 425, 450, 474, or 500 μm. The thickness of the plastic film can fall within a range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, the plastic film may have a thickness ranging from about 10 to about 50 μm, or from about 20 to about 100 μm.

[0179] Plastic film material Plastic films can be made from a variety of engineering polymers. Single or multiple layers of plastic film can each contain one or more of the following polymeric materials: polypropylene (PP), polyethylene terephthalate (PET), polyethylene (PE), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polystyrene (PS), nylon, polycarbonate (PC), polyvinyl acetate (PVA), polyvinyl alcohol (PVOH), poly(ethylene-vinyl acetate) (EVA), poly(ethylene-vinyl alcohol) (EVOH), poly(methyl methacrylate) (PMMA), acrylic resin, Kapton, UPILEX, and polyimide resin.

[0180] glue The adhesive layer for metal foil laminates can be any material that can bond plastic film and metal foil. Examples include epoxy resins, acrylic resins, and polyurethane resins. Examples include diglycidyl ether of bisphenol A (DGEBA), epoxyphenol novolak (EPN), epoxycresol novolak (ECN), poly(methyl acrylate), poly(methyl methacrylate) (PMMA), poly(n-butyl acrylate), poly(n-butyl methacrylate), poly(n-dodecyl acrylate), poly(n-dodecyl methacrylate), and poly(hydroxyethyl methacrylate) (HEMA). Polyurethane resins are also available, such as those obtained by reacting isocyanates with polyols.

[0181] Crimping Adhesive is applied to one side of a plastic film, and metal foil is placed on top of that to create a three-layer structure of plastic film-adhesive-metal foil, which is then pressed together as it passes through a pressure roller to form a completed metal foil laminate.

[0182] Metal foil laminate construction FIG. 2 illustrates the structure of a metal foil laminate (101) and illustrates defects such as pinholes in the metal layer (103). The metal foil laminate (101) has a basic structure of a plastic (105) layer - adhesive layer (107) - metal layer (103) in that order, but one or more functional layers can be added between the plastic layer and the metal layer if necessary. An adhesive layer can be added between the plastic or metal layer and the additional functional layer. In this document (excluding the claims), "metal foil laminate" means a structure in the order of plastic layer - adhesive layer - metal layer, even if a specific structure is mentioned, and may or may not include a functional layer.

[0183] VII. Polymer-metal foil laminates produced by polymerization reaction Contacting the metal foil laminate with the polymerization reaction composition solution A polymerization reaction vessel or reservoir large enough to accommodate a metal foil laminate is prepared. The vessel is filled with a polymerization reaction composition solution. The metal foil laminate is then brought into contact with the polymerization reaction composition solution in the vessel, causing a polymerization reaction to occur on the surface of the metal foil laminate.

[0184] Metal foil laminate is supported in the composition solution When the metal foil laminate is placed in the polymerization reaction vessel, only the side of the metal layer can be in contact with the composition solution, while the side of the plastic layer cannot. Alternatively, the entire metal foil laminate can be immersed in the solution so that both sides are in contact with the solution. Placing multiple metal foil laminates together in a single polymerization reaction vessel and carrying out the polymerization reaction can also increase process productivity. Multiple metal foil laminates can be stacked in the composition solution, or a spacing structure can be inserted between adjacent metal foil laminates to maintain a distance between them so that the composition solution can enter between them.

[0185] Continuous Process The process of contacting the metal foil laminate with the polymerization reaction composition in the polymerization reaction vessel can be a continuous process. The metal foil laminate is unwound from a roll and moved into the polymerization reaction vessel, where it is immersed in the polymerization reaction composition. As it moves while immersed in the polymerization reaction composition, a polymer layer is formed on the surface of the metal foil laminate through the polymerization reaction, and it continues to move as it leaves the polymerization reaction vessel.

[0186] Polymer layer generated from the surface by polymerization reaction When the polymerization reaction composition solution and the metal layer surface of the metal foil laminate are in contact for a sufficient time for the polymerization reaction to occur, a polymerization reaction occurs on the metal layer surface, producing a polymer layer. When both sides of the metal foil laminate are immersed in the composition solution, a polymer layer is produced on each of the metal layer surface and the plastic layer surface. The metal foil laminate with the produced polymer layer is then cured and hardened in a baking process, for example, by forming crosslinks between adjacent polymers within the polymer layer.

[0187] Polymer Layer Thickness The thickness of the polymer layer can be about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.5, 1.6, 1.8, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 20, 25, or 30 μm. The thickness of the polymer layer can fall within a range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, the polymer layer can have a thickness falling within the range of about 0.5 to about 3 μm or about 1 to about 5 μm. Even when the surface of the metal layer and the surface of the plastic layer are simultaneously contacted with the polymerization reaction composition and then separated, the thickness of the resulting polymer layer can differ due to the different rates of initiation and progression of the polymerization reaction on these two surfaces.

[0188] Polymer-Metal Foil Laminate FIG. 3 illustrates a polymer-metal laminate (109) with a polymer layer (113)-plastic layer (105)-adhesive layer (107)-metal layer (103)-polymer layer (111) structure obtained as a result of the polymerization reaction. If the polymerization reaction does not proceed on the surface of the plastic layer, the polymer layer (113) is omitted, resulting in a structure of plastic layer (105)-adhesive layer (107)-metal layer (103)-polymer layer (111). This polymer-metal laminate manufactured using a metal foil laminate is called a "polymer-metal laminate" to distinguish it from the polymer-metal laminates of other embodiments. If necessary, one or more functional layers can be added between the plastic layer and the metal layer. Furthermore, if necessary, one or more functional layers can be added between the plastic layer and the polymer layer. If a functional layer is added, an adhesive layer can be added to one or both of them. In this document (excluding claims), a "polymer-metal foil laminate" refers to a laminate having a structure in the order of plastic layer-adhesive layer-metal layer-polymer layer or polymer layer-plastic layer-adhesive layer-metal layer-polymer layer, even if a specific structure is mentioned, and may or may not have a functional layer.

[0189] Polymerization reaction to fill pinholes The polymerization reaction not only produces a polymer layer on the surface of the metal layer, but also fills or seals pinholes formed in the metal layer. When the polymerization reaction composition penetrates into the pinhole and causes a polymerization reaction on the inner surface of the pinhole, the resulting polymer or oligomer fills all or part of the internal space of the pinhole (115, 117 in Figure 3). The polymer or oligomer that fills all or part of the internal space of the pinhole can then extend outside the pinhole and connect with the polymer layer formed on the metal surface (117 in Figure 3). The polymer layer formed on the metal surface outside the pinhole also covers and seals the pinhole.

[0190] VIII. Flexible Encapsulation Structures Using Polymer-Metal Foil Laminates Airtightness of polymer-metal foil laminates The lower the gas transmission rate (GTR) and water vapor transmission rate (WVTR) of a polymer-metal foil laminate, the better. The water vapor transmission rate of a single polymer-metal foil laminate is approximately 1 x 10 -6 , 2 × 10 -6 , 3×10 -6 , 4×10 -6 , 5×10 -6 , 6×10 -6 , 7×10 -6 , 8×10 -6 , 9×10 -6 , 1×10 -5 , 2 × 10 -5 , 3×10 -5 , 4×10 -5 , 5×10 -5 , 6×10 -5 , 7×10 -5 , 8×10 -5 , 9×10 -5 , 1×10 -4 , 2 × 10 -4 , 3×10 -4 , 4×10 -4 , 5×10 -4 , 6×10 -4 , 7×10 -4 , 8×10-4 , 9×10 -4 , 1×10 -3 , 2 × 10 -3 , 3×10 -3 , 4×10 -3 , 5×10 -3 , or 6 x 10 -3 g / m 2 / day. The moisture permeability of a single polymer-metal foil laminate can fall within the range obtained by selecting two of the numbers listed in the previous sentence. For example, the moisture permeability is approximately 1 × 10 -5 to about 1×10 -4 g / m 2 / day range, approximately 5 × 10 -5 to about 5×10 -4 g / m 2 Can belong to the / day range.

[0191] Lamination of two polymer-metal foil laminates Figure 4 illustrates a structure in which two polymer-metal foil laminates are laminated together. Adhesive (119) is applied to one side of polymer-metal foil laminate (109A), and one side of another polymer-metal foil laminate (109B) is placed on top of it to create a structure of [polymer-metal foil laminate (109A)]-[adhesive (119)]-[polymer-metal foil laminate (109B)]. This structure is then laminated together by pressing.

[0192] Several laminations A laminate with three laminated polymer-metal foil laminates can be created by applying adhesive between two laminated polymer-metal foil laminates and one laminated polymer-metal foil laminate and pressing them together. A laminate with four laminated polymer-metal foil laminates can be created by adhesively bonding two laminated polymer-metal foil laminates together. By repeating the same process, a laminate with the desired number of laminated polymer-metal foil laminates can be created.

[0193] Various structures of laminated laminations When two polymer-metal foil laminates are laminated together, various lamination structures can be produced depending on which sides are laminated together and whether the polymer layer is present on both sides or only on one side. Examples of these structures are shown below. (1) [polymer layer-plastic layer-adhesive layer-metal layer-polymer layer]-[adhesive layer]-[polymer layer-plastic layer-adhesive layer-metal layer-polymer layer] (2) [polymer layer-plastic layer-adhesive layer-metal layer-polymer layer]-[adhesive layer]-[polymer layer-metal layer-adhesive layer-plastic layer-polymer layer] (3) [polymer layer-metal layer-adhesive layer-plastic layer-polymer layer]-[adhesive layer]-[polymer layer-plastic layer-adhesive layer-metal layer-polymer layer] (4) [plastic layer-adhesive layer-metal layer-polymer layer]-[adhesive layer]-[polymer layer-plastic layer-adhesive layer-metal layer-polymer layer] (5) [plastic layer-adhesive layer-metal layer-polymer layer]-[adhesive layer]-[polymer layer-metal layer-adhesive layer-plastic layer-polymer layer] (6) [polymer layer-metal layer-adhesive layer-plastic layer]-[adhesive layer]-[polymer layer-plastic layer-adhesive layer-metal layer-polymer layer] (7) [polymer layer-metal layer-adhesive layer-plastic layer]-[adhesive layer]-[polymer layer-metal layer-adhesive layer-plastic layer-polymer layer] (8) [plastic layer-adhesive layer-metal layer-polymer layer]-[adhesive layer]-[plastic layer-adhesive layer-metal layer-polymer layer] (9) [plastic layer-adhesive layer-metal layer-polymer layer]-[adhesive layer]-[polymer layer-metal layer-adhesive layer-plastic layer] (10) [polymer layer-metal layer-adhesive layer-plastic layer]-[adhesive layer]-[plastic layer-adhesive layer-metal layer-polymer layer] One or more functional layers can be added between two polymer-metal foil laminates, between a plastic layer and a metal layer, or between a polymer layer and a plastic layer. The functional layers can, but do not necessarily, require an adhesive layer on one or both sides.

[0194] Flexible sealing structure using metal foil A single polymer-metal foil laminate made using metal foil provides considerable airtightness by itself and can be used to seal devices or objects that require airtightness, such as display devices. Flexible laminates made by laminating two or more polymer-metal foil laminates can be used as flexible sealing structures for devices or objects that require even higher airtightness, such as OLED panels. Flexible sealing structures according to embodiments have a structure in which 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 15, 16, 17, 18, 19, or 20 polymer-metal foil laminates are laminated together.

[0195] Attaching a flexible encapsulation structure to an OLED panel An unfinished OLED product is provided, with an OLED panel formed on the front glass or plastic. The back of the unfinished OLED product is covered with a flexible encapsulation structure with an area corresponding to the size of the unfinished OLED product. The edges of the flexible encapsulation structure and the back edge of the unfinished OLED product are attached to each other in an airtight manner, sealing the inside.

[0196] Gas tightness of flexible sealing structures The encapsulation structure of OLED panel products has a moisture permeability of 1 x 10 -6 g / m 2 / day. Flexible sealing structures using polymer-metal foil laminates are made by laminating several polymer-metal foil laminates, which have metal foil pinholes filled by a polymerization reaction, significantly reducing oxygen and water vapor permeability. When several polymer-metal foil laminates are laminated together, the gas permeation path becomes complicated, and the gas permeability drops sharply to 1 x 10 -6 g / m 2 / day. Flexible sealing structures made by laminating two or more polymer-metal foil laminates have a moisture permeability of about 1×10 -9 , 2 × 10 -9 , 3×10 -9 , 4×10 -9 , 5×10 -9 , 6×10 -9 , 7×10 -9 , 8×10 -9 , 9×10 -9 , 1×10 -8 , 2 × 10 -8 , 3×10 -8 , 4×10 -8 , 5×10 -8 , 6×10 -8 , 7×10 -8 , 8×10 -8 , 9×10 -8 , 1×10 -7 , 2 × 10 -7 , 3×10 -7 , 4×10 -7 , 5×10 -7 , 6×10 -7 , 7×10 -7 , 8×10 -7 , 9×10 -7 , or 1 × 10 -6 g / m 2 / day. The moisture permeability of a flexible sealing structure made of two or more polymer-metal foil laminated sheets can fall within the range obtained by selecting two of the numbers listed in the previous sentence. For example, the moisture permeability is approximately 1 x 10 -8 to about 1×10 -6 g / m 2 / day range, approximately 5 × 10 -5 to about 5×10 -7 g / m2 Can belong to the / day range.

[0197] Heat dissipation function of flexible sealing structures Flexible encapsulation structures using polymer-metal foil laminates have multiple metal layers that can transfer heat generated by the OLED panel to the edges of the product. Installing heat dissipation structures such as heat dissipation pins on the edges of the OLED product and connecting them to the metal layers of the encapsulation structure provides an effective heat dissipation system.

[0198] IX. Airtight plastic film Airtight plastic film that blocks gas permeation A variety of plastic films are used as packaging materials for goods. In many cases, these plastic films have pores that allow air and other gases to pass through. Packaging materials used for foods that lose freshness when exposed to oxygen or foods that become damp when exposed to water vapor have a metal layer, such as aluminum, formed on the plastic film to block the passage of air and water vapor. Packaging materials with a metal gas-permeable barrier layer formed on a plastic film are used not only for food but also for other items that must be protected from the passage of oxygen, water vapor, and other gases during storage.

[0199] Metal foil film formation using vapor deposition For metals with low boiling points, vapor deposition technology can be used to form metal layers several hundred nanometers thick. By lowering the pressure in the vapor deposition chamber, vapor deposition of metals can be performed at relatively low temperatures. This allows metals to be deposited on organic substrates at low temperatures that do not damage the substrate.

[0200] Pinholes and their size in vapor-deposited metal layers. Pinholes exist in metal layers vapor-deposited onto plastic films. Some pinholes are caused by defects in the metal's crystalline structure, while others are caused by the state of the plastic film surface or foreign matter during vapor deposition. When metal is vapor-deposited onto a hydrophobic plastic film, pinholes form that are much larger than those formed by defects in the metal's crystalline structure. Pinholes that form in vapor-deposited metal layers range in diameter from a few nanometers to several hundred micrometers.

[0201] Pinhole size and airtightness The smaller the number and size of pinholes in the metal layer, the lower the permeability of gases such as oxygen and water vapor through the packaging material, resulting in higher airtightness. Highly airtight plastic packaging materials can maintain the inherent properties of the packaged items for a long period of time, making them versatile for use. However, if the pinholes are too large, they will not function as a gas barrier packaging material. Areas with large pinholes that significantly impair airtightness should be removed, and the remaining portion should be used as a gas barrier packaging material.

[0202] Pinholes detected by naked eye observation One method for detecting pinholes is to expose one side of the packaging material with a metal layer to light and measure the amount of light transmitted through the other side of the packaging material. The easiest way is to determine that there is a pinhole when light transmission is observed with the naked eye, and remove the area or do not use it for packaging. This method can ensure that there are no large pinholes with diameters of tens to hundreds of nanometers, and the number of pinholes is 1x10 -1 g / m 2 It is possible to ensure a moisture permeability of less than / day.

[0203] Pinholes that are difficult to detect with the naked eye In the metal layer formed on the plastic film by vapor deposition, some pinholes can be seen with the naked eye, but there can also be small pinholes that are difficult to see with the naked eye. In order to provide a highly airtight packaging material, a solution is needed to deal with pinholes that cannot be seen with the naked eye.

[0204] X. Metallized plastic laminate Airtight plastic packaging material According to an embodiment of the present invention, a polymerization reaction is carried out on the surface of a metal layer formed on a plastic film by vapor deposition. A polymer layer is formed on the surface of the metal layer through the polymerization reaction, filling pinholes that are visible to the naked eye as well as pinholes that are too small to be seen with the naked eye. By filling the pinholes in the metal layer in this way, a plastic packaging material with higher airtightness than a plastic packaging material that provides a portion containing pinholes that are visible to the naked eye can be provided.

[0205] Metallized plastic laminate First, a metal laminate is created by vapor-depositing a metal onto the surface of a plastic film substrate. The surface of the plastic film can be plasma-treated before vapor deposition to enhance interfacial adhesion with the metal. This metal laminate, fabricated by vapor-depositing a metal onto a plastic film, is called a "vapor-deposited metal-plastic laminate" to distinguish it from the metal laminates of other embodiments. Figure 5 illustrates the basic structure of a vapor-deposited metal-plastic laminate (121) with a plastic film (125) and a metal layer (123), and illustrates defects such as pinholes in the metal layer (123).

[0206] Plastic film structure The plastic film used as the substrate for vapor deposition can be composed of a single layer or multiple layers. A multiple layer structure is a structure in which layers of different materials are adjacent to each other and in which layers of the same material can be repeated.

[0207] Plastic film material Plastic films can be made from a variety of engineering polymers. Single or multiple layers of plastic film can each contain one or more of the following polymeric materials: polypropylene (PP), polyethylene terephthalate (PET), polyethylene (PE), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polystyrene (PS), nylon, polycarbonate (PC), polyvinyl acetate (PVA), polyvinyl alcohol (PVOH), poly(ethylene-vinyl acetate) (EVA), poly(ethylene-vinyl alcohol) (EVOH), poly(methyl methacrylate) (PMMA), acrylic resin, Kapton, UPILEX, and polyimide resin.

[0208] Plastic film thickness The thickness of the plastic film can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 68, 50, 52.5, 55, 57.5, 60, 62.5, 65, 67.5, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 220, 240, 260, 280, or 300 μm. The thickness of the plastic film can fall within a range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, the plastic film may have a thickness ranging from about 5 to about 40 μm, such as from about 10 to about 30 μm.

[0209] Metal layer of metallized plastic laminate The metals deposited on the surface of the plastic film by vapor deposition include aluminum, copper, tin, zinc, magnesium, stainless steel, nickel, chromium, tungsten, etc. When these metals are exposed to air, a thin oxide film forms on their surface.

[0210] Metal layer thickness The thickness of the metal layer formed by vapor deposition can range from a few nanometers to several hundred nanometers, specifically, about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52.5, 55, 57.5, 60, 62.5, 65, 67.5, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, or 200 nm. The thickness of the metal layer can fall within the range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, the thickness of the metal layer ranges from about 10 to about 30 μm, and from about 20 to about 100 nm.

[0211] XI. Polymer-Metal-Plastic Laminate Production by Polymerization Reaction The metallized plastic laminate is brought into contact with the polymerization reaction composition solution. A polymerization reaction composition solution is filled into a polymerization reaction vessel or reservoir large enough to accommodate a vapor-deposited metal-plastic laminate. The vapor-deposited plastic laminate is then brought into contact with the polymerization reaction composition solution in the vessel. A polymerization reaction occurs on the surface of the vapor-deposited plastic laminate.

[0212] Metal-deposited plastic laminate is supported in the composition solution When placing the metal-vapor-deposited plastic laminate in a polymerization reaction vessel, only the metal side can be in contact with the composition solution, with the plastic film side not in contact, or the entire metal-vapor-deposited plastic laminate can be supported so that both sides are completely immersed in the solution. Placing multiple metal-vapor-deposited plastic laminates in the composition solution together in one polymerization reaction vessel and carrying out the polymerization reaction can also increase process productivity. Multiple metal-vapor-deposited plastic laminates can be stacked in the composition solution, or a spacing structure can be inserted between adjacent metal-vapor-deposited plastic laminates to maintain a distance between them so that the composition solution can enter between them.

[0213] Continuous Process The process of contacting the metal-deposited plastic laminate with the polymerization reaction composition in the polymerization reaction vessel can be carried out in a continuous process, and the same method as the process of contacting the metal foil laminate with the polymerization reaction composition can be applied.

[0214] Polymer layer formation by surface polymerization reaction When the polymerization reaction composition solution and the metal layer surface of the metal-vapor-deposited plastic laminate are in contact for a time sufficient for the polymerization reaction to occur, a polymerization reaction occurs on the metal layer surface, producing a polymer layer. When the metal-vapor-deposited plastic laminate is supported so that both sides are immersed in the composition solution, a polymer layer is produced on each of the metal layer surface and the plastic layer surface. The metal-vapor-deposited plastic laminate with the produced polymer layer is then cured and hardened in a subsequent baking process, for example, by forming crosslinks between adjacent polymers within the polymer layer.

[0215] polymer layer The polymerization reaction produces polymers of various sizes, including dimers, trimers, tetramers, and oligomers. Some of the dimers, trimers, tetramers, oligomers, and polymers produced may form chemical bonds with the surface of the substrate. As a result, the polymer layer contains polymers of various sizes, including dimers, trimers, tetramers, and oligomers.

[0216] The thickness of the polymer layer can be about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.5, 1.6, 1.8, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 20, 25, or 30 μm. The thickness of the polymer layer can fall within a range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, the polymer layer can have a thickness ranging from about 0.5 to about 3 μm or from about 1 to about 5 μm. Even when the surface of the metal layer and the surface of the plastic layer are simultaneously contacted with the polymerization reaction composition and then separated, the resulting thickness of the polymer layer can differ due to the different rates of initiation and progression of the polymerization reaction on these two surfaces.

[0217] Polymer-Metal-Plastic Laminate FIG. 6 illustrates the polymer-metal laminate 131 with a polymer layer (129)-plastic layer (125)-metal layer (123)-polymer layer (127) structure obtained as a result of the polymerization reaction. If the polymerization reaction does not proceed on the surface of the plastic layer, a structure of plastic layer (125)-metal layer (123)-polymer layer (127) is obtained in which the polymer layer (129) is omitted. This polymer-metal laminate manufactured using a metal-deposited plastic laminate can be used in the same manner as in other embodiments. -To distinguish it from a metal laminate, it is called a "polymer-metal-plastic laminate." If necessary, one or more functional layers may be added to either or both sides of the polymer layer. If a functional layer is added, an adhesive layer may be added to either or both sides. In this document (excluding claims), even if a specific structure is mentioned, a "polymer-metal-plastic laminate" has a structure in the order of plastic layer-metal layer-polymer layer or polymer layer-plastic layer-metal layer, and may or may not have a functional layer.

[0218] Polymerization reaction to fill pinholes The polymerization reaction not only produces a polymer layer on the surface of the metal layer, but also fills or seals pinholes formed in the metal layer. When the polymerization reaction composition penetrates the inner surface of the pinhole and causes a polymerization reaction on the inner surface of the pinhole, the resulting polymer or oligomer fills all or part of the inner space of the pinhole (133, 135 in FIG. 6). The polymer or oligomer that fills all or part of the inner space of the pinhole can then extend outside the pinhole and connect with the polymer layer formed on the metal surface (135 in FIG. 6). Furthermore, the polymer layer formed on the metal surface outside the pinhole covers and seals the pinhole.

[0219] XII. GAS-TIGHT PLASTIC PACKAGING MATERIAL Packaging of goods using airtight plastic packaging materials Polymer-metal-plastic laminates can be used as airtight plastic packaging materials either by themselves or after undergoing additional processing and processes. Additional processing and processes can include printing or adding functional layers. To use them to package goods, the polymer-metal-plastic laminate is folded like a bag or two polymer-metal-plastic laminates are stacked and the edges are sealed to create a flexible container into which goods can be placed. An item that requires airtight storage is placed inside the container, and then sealed using various sealing techniques to prevent air from passing through. There are many types of goods that require airtight storage, including food and electronic components, and there are no restrictions.

[0220] airtight packaging Plastic packaging materials using polymer-metal-plastic laminates have significantly reduced gas permeability by filling metal foil pinholes with a polymerization reaction. The moisture permeability of this plastic packaging material is 1 x 10 -8 , 2 × 10 -8 , 3×10 -8 , 4×10 -8 , 5×10 -8 , 6×10 -8 , 7×10 -8 , 8×10 -8 , 9×10 -8 , 1×10 -7 , 2 × 10 -7 , 3×10 -7 , 4×10 -7 , 5×10 -7 , 6×10 -7 , 7×10 -7 , 8×10 -7 , 9×10 -7 , 1×10 -6 , 2 × 10 -6 , 3×10 -6 , 4×10 -6 , 5×10 -6 , 6×10 -6 , 7×10 -6 , 8×10 -6 , 9×10 -6 , 1×10 -5 , 2 × 10 -5, 3×10 -5 , 4×10 -5 , 5×10 -5 , 6×10 -5 , 7×10 -5 , 8×10 -5 , 9×10 -5 , or 1 × 10 -4 g / m 2 / day. The moisture permeability of plastic packaging materials using polymer-metal-plastic laminates can be found in the range obtained by selecting two of the numbers listed in the previous sentence. For example, the moisture permeability is approximately 1 x 10 -7 to about 1×10 -6 g / m 2 / day range, approximately 5 × 10 -7 to about 5×10 -5 g / m 2 Can belong to the / day range.

[0221] XIII. Flexible sealing structures using polymer-metal-plastic laminates Lamination of two polymer-metal-plastic laminates Adhesive is applied to one side of a polymer-metal-plastic laminate, and one side of another polymer-metal-plastic laminate is placed on top of it to create a structure of [polymer-metal-plastic laminate] - [adhesive] - [polymer-metal-plastic laminate]. This structure is then laminated together.

[0222] Several laminations A laminate with three laminated polymer-metal-plastic laminates can be created by applying adhesive between two laminated polymer-metal-plastic laminates and one laminated polymer-metal-plastic laminate and laminating them under pressure. A laminate with four laminated polymer-metal-plastic laminates can be created by adhesively laminating two laminated polymer-metal-plastic laminates. By repeating the same process, a laminate with the desired number of laminated polymer-metal-plastic laminates can be created.

[0223] Various structures of laminated laminations When two polymer-metal-plastic laminates are laminated, various lamination structures can be produced depending on which sides are laminated together and whether the polymer layer is present on both sides or only on one side. One or more functional layers can be added where adhesive is needed. A functional layer can, but does not necessarily, require an adhesive layer on one or both sides.

[0224] Flexible sealing structures using polymer-metal-plastic laminates The polymer-metal-plastic laminate itself or a laminate of two or more polymer-metal-plastic laminates can be used as a flexible encapsulation structure for OLEDs. The flexible encapsulation structure according to the embodiment has a structure in which 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 15, 16, 17, 18, 19, or 20 polymer-metal-plastic laminates are laminated together.

[0225] Attaching a flexible encapsulation structure to an OLED panel The flexible encapsulation structure is attached to the rear surface of the OLED product in the same manner as described for the flexible encapsulation structure using a polymer-metal foil laminate to seal the inside.

[0226] Gas tightness of flexible sealing structures The OLED flexible encapsulation structure using polymer-metal-plastic laminate is made by laminating two or more polymer-metal-plastic laminates, which have pinholes in the vapor-deposited metal layer filled by a polymerization reaction, significantly reducing gas permeability. When several polymer-metal-plastic laminates are laminated together, the gas permeation path becomes complicated, causing a rapid decrease in gas permeability to 1 x 10 -6 g / m 2 / day. The moisture permeability of a flexible sealing structure made by laminating two or more polymer-metal-plastic laminates is approximately 1 × 10 -9 , 2 × 10 -9 , 3×10 -9 , 4×10 -9 , 5×10 -9 , 6×10 -9 , 7×10 -9 , 8×10 -9 , 9×10 -9 , 1×10 -8 , 2 × 10 -8 , 3×10 -8 , 4×10 -8 , 5×10 -8 , 6×10 -8 , 7×10 -8 , 8×10 -8 , 9×10 -8 , 1×10 -7 , 2 × 10 -7 , 3×10 -7 , 4×10 -7 , 5×10 -7 , 6×10 -7 , 7×10 -7 , 8×10 -7 , 9×10 -7 , or 1 × 10 -6 g / m 2 / day. The moisture permeability of a flexible sealing structure made of two or more polymer-metal foil laminated sheets can fall within the range obtained by selecting two of the numbers listed in the previous sentence. For example, the moisture permeability is approximately 1 x 10 -8 to about 1×10 -6 g / m 2 / day range, approximately 5 × 10 -5 to about 5×10 -7 g / m 2 Can belong to the / day range.

[0227] Heat dissipation function of flexible sealing structures Flexible encapsulation structures using polymer-metal-plastic laminates have multiple metal layers that can transfer heat generated by the OLED panel to the edge of the product. Installing a heat dissipation structure such as a heat dissipation pin on the edge of the OLED product and connecting it to the metal layer of the encapsulation structure provides an effective heat dissipation system.

[0228] XIV. Polymerization Reactions Polymerization reaction that forms a polymer layer on the surface Forming a polymer layer on the surface of the metal layer and plastic layer of metal laminates, such as metal foil laminates and metal-plastic laminates, is a polymerization reaction using monomers of Chemical Formulas 1-11. The monomers of Chemical Formulas 1-11 are believed to react with nucleophilic or electrophilic functional groups on the substrate surface, bonding to the substrate surface and initiating the polymerization reaction. However, not all polymers, such as polymers and oligomers, obtained as a result of the polymerization reaction bond to the substrate surface. Furthermore, the polymerization reactions and their results described in the claims do not necessarily have to be embodied by such reaction mechanisms.

[0229] Polymerization Reaction Composition The polymerization reaction composition that proceeds on the metal surface of metal laminates, such as metal foil laminates and metal-plastic laminates, contains a monomer and a solvent. When the polymerization reaction composition is reused for a subsequent polymerization reaction, it may further contain a prepolymerized oligomer or polymer. A base, acid, or buffer solution may be added to adjust the pH. In some cases, it may also contain a polymerization initiator.

[0230] monomer The monomer used in the polymerization reaction is a self-initiating monomer, which spontaneously initiates the polymerization reaction, and this monomer is a basic compound, which is a compound of Formula 1-11.

[0231] Two or more monomers The polymerization reaction occurring on the surface of the aluminum thin film can be a polymerization reaction using two or more monomers, such as a copolymer of 3,4-diaminopyridine and 2,6-diaminopyridine, which is a cross-addition copolymer between isomeric compounds with similar structures, a copolymer of 2,5-diaminopyridine and 3-amino-2-cyclohexen-1-one, or a copolymer of 2,4,6-triaminopyrimidine and methyl 3-aminocrotonate, which is a cross-addition copolymer between monomers with significantly different structures, or a Diels-Alder copolymer of furfurylamine and methyl 3-aminocrotonate.

[0232] Monomer concentration of polymerization reaction composition In the composition for polymerization reaction, the concentration of the monomer is about 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17.5, 18, 18.5, 19, 19.5, or 20 mg / mL. The concentration of the monomer can fall within the range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, the monomer concentration can fall within the range of about 2.0 to about 5.0, or the range of about 1.0 to about 7.0.

[0233] Basic Composition According to one embodiment, the pH of the polymerization reaction composition is adjusted to a basic value of 8 or more. Although the monomers of the compounds of Formulas 1 to 11 themselves are basic, a basic substance such as sodium hydroxide (0.01M, 0.1M, or 1M, etc.), 15-20% DMEA (N,N-dimethylethylamine, CAS 598-56-1) or 15-20% 2-dimethylaminoethanol (CAS 108-01-0) (pH around 13), or boric acid / sodium borate buffer solution (pH around 9) can be added to adjust the pH of the composition.

[0234] Polymerization inhibitor The compounds of Formulas 1 to 11 are self-initiating monomers that undergo polymerization without an initiator, but they are not monomers that undergo rapid polymerization. Therefore, unlike other polymerization monomers that contain polymerization inhibitors, the compounds of Formulas 1 to 11 are often stored and distributed without polymerization inhibitors. When such monomers are used, the polymerization composition does not contain a polymerization inhibitor.

[0235] No initiator The polymerization reaction can proceed without a separate initiator. In the case of polymer-metal laminates used in OLED encapsulation structures, the presence of an initiator in the polymer layer can have adverse effects on the organic light-emitting layer of the OLED. Therefore, the polymerization reaction composition does not contain a polymerization initiator such as a radical initiator or photoinitiator. This is because the monomers of Formula 1-11 are self-initiating monomers that undergo polymerization without an initiator. Depending on the material on the substrate surface, polymerization can easily occur without an initiator. For example, when polymerization is carried out on the surface of a metal substrate, the reaction is initiated by the reaction of the monomer with hydroxyl groups derived from the oxide film formed on the metal surface.

[0236] When an initiator is included Although the monomers of formulas 1-11 are self-initiating, an initiator can be used to promote the polymerization reaction depending on the material on the substrate surface. If the final product contains an initiator, the polymerization reaction composition can also contain the initiator. For example, an initiator can be included when forming a polymer layer on a battery separator. Examples of compounds that can be used as initiators include AIBN (Azobisisobutyronitrile), ABCN (1,1'-Azobis(cyclohexane-carbonitrile)), di-tert-butyl peroxide, and benzoyl peroxide. These initiators generate radical intermediates at a certain temperature, which react with the monomer to initiate polymerization.

[0237] Temperature of the polymerization reaction composition The polymerization reaction proceeds at a temperature below the boiling point of the solvent used. The temperature of the polymerization reaction composition is adjusted to about 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100°C. This temperature can fall within a range obtained by selecting two of the numbers listed in the previous sentence. For example, the temperature of the polymerization reaction composition can fall within the range of about 20 to about 70°C, about 40 to about 90°C, or about 10 to about 30°C.

[0238] Contact time with the polymerization reaction composition The time for which the metal laminate is contacted with the polymerization reaction composition can be about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 42, 44, 46, 48, 50, 52, 54, 56, 68, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, or 80 hours. The time for which the metal laminate is contacted with the polymerization reaction composition can fall within a range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, the polymerization reaction time may be in the range of about 2 to about 10 hours, about 6 to about 12 hours, or about 8 to about 24 hours.

[0239] polymer layer The polymerization reaction produces polymers of various sizes, including dimers, trimers, tetramers, and oligomers. Some of the dimers, trimers, tetramers, oligomers, and polymers produced may form chemical bonds with the surface of the substrate. As a result, the polymer layer contains polymers of various sizes, including dimers, trimers, tetramers, and oligomers.

[0240] Removal of liquid remaining on the surface of a metal laminate on which a polymer layer has been formed Once a polymer layer is formed on the surface of the metal laminate upon contact with the polymerization reaction composition in the polymerization reaction vessel, the laminate is removed from the polymerization reaction vessel. The surface is then wiped with or touched with absorbent paper or an absorbent pad to remove any liquid components of the polymerization reaction composition remaining on the polymer layer or laminate surface. Before or after wiping off the liquid components, the surface may be washed with water or another cleaning solution. If washing is performed, the liquid on the surface is wiped off.

[0241] baking After removing the liquid from the surface, the polymer layer is baked in an oven to evaporate the liquid components remaining in the polymer layer, crosslink the polymers formed in the polymer layer, and harden the polymer layer.

[0242] Baking Temperature Baking is performed at a temperature low enough not to denature the plastic layer, and is typically performed at approximately 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, or 150°C. The baking temperature can be within a range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, baking can be performed at a temperature ranging from approximately 50 to approximately 100°C or from approximately 60 to approximately 110°C.

[0243] Baking time Baking is performed for approximately 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 hours. The baking time can fall within a range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, baking is performed for approximately 2 to 5 hours, or approximately 4 to 6 hours.

[0244] Washing and drying After baking, the product is washed to remove any residual materials remaining in the polymer layer. The polymer layer contains components of the polymerization reaction composition and materials formed as a result of the polymerization reaction. Some of these materials are firmly bound to the metal surface, plastic surface, and the polymers attached to these surfaces, while others are loosely bound. Washing with an acidic or basic cleaning solution can remove any residual materials loosely bound to the polymer layer. After washing, the product is dried. Drying can be done in an oven.

[0245] Reuse of the polymerization reaction resultant composition After the polymerization reaction is complete, the polymer-metal laminate (e.g., a polymer-metal foil laminate or a polymer-metal-plastic laminate) is removed from the polymerization vessel. The resulting composition contains a mixture of monomers that did not participate in the reaction and polymers, oligomers, and dimers produced as a result of the polymerization reaction. This composition containing polymers, oligomers, and dimers is not discarded but can be used in the next polymerization reaction. That is, a new metal laminate is added to the composition remaining from the previous polymerization reaction, and a polymerization reaction is then carried out to produce a polymer-metal laminate. In this case, the polymers, oligomers, and dimers already present in the composition can be included in the resulting polymer layer, and these polymers, oligomers, and dimers can also participate in the polymerization reaction to produce larger polymers or oligomers. Before the next polymerization reaction of the metal laminate, necessary ingredients can be added to adjust the concentration, pH, etc. of the monomers in the composition.

[0246] XV. Filling pinholes in the metal layer through polymerization capillary action The polymerization reaction composition solution that comes into contact with the surface of the metal laminate metal layer penetrates into defects such as pinholes and depressions, and is absorbed or seeped into the defects by capillary action.

[0247] Polymerization reactions at defects and pinholes in metals Monomers or oligomers that enter defects or pinholes in the metal layer interact with the inner surface of the pinhole and grow into oligomers or polymers, filling the pinhole.Even if the entire space of the pinhole formed through the metal layer, i.e., the entire space from the entrance on one side of the metal layer to the entrance on the other side of the pinhole, is not completely filled, the oligomers or polymers fill or block part of the space, making it difficult for air or moisture to pass through.

[0248] Melts into the metal surface Depending on the acidity of the polymerization composition solution, when this solution comes into contact with the surface of the metal layer, the metal and metal oxide on the outermost surface of defects contained in the metal layer can dissolve in the composition solution. In particular, in the case of defects such as pinholes, which have a structure where the thickness of the metal layer suddenly thins or disappears, some of the metal atoms dissolve, causing a smoothing phenomenon that smooths the abrupt structure of the defect, and this can also widen the entrance side of the defect.

[0249] Effect of smoothing defects Smoothing allows the monomer to penetrate deep into defects such as pinholes, allowing the polymerization reaction to proceed deep into the defects, allowing the polymer or oligomer to fill the defects. Even if the polymerization reaction does not proceed deep into the defects, the opening of the bond gradually widens, allowing the polymerization reaction to proceed there, allowing the polymer or oligomer to fill the defect to a certain depth near the opening of the defects. When the polymer or oligomer fills the defect near the opening or deep inside, it has the effect of making it difficult for gases such as oxygen and water vapor to pass through the metal layer in the thickness direction.

[0250] Controlling the polymerization reaction for smoothing Depending on the acidity of the polymerization reaction composition solution, the smoothing phenomenon continues while the composition solution is in contact with the surface of the metal layer. The degree of smoothing can be controlled by adjusting the acidity of the polymerization reaction composition. The start of the polymerization reaction can also be controlled so that the polymerization reaction occurs after the smoothing phenomenon occurs at defects in the metal layer. Alternatively, the metal foil laminate can be placed in an acidic or basic solution (not a polymerization reaction composition solution) of the appropriate acidity to cause the smoothing phenomenon, and then placed in the composition solution in a polymerization reaction vessel to proceed with the polymerization reaction.

[0251] XVI. Different from coating prepolymerized polymers Method for forming a polymer layer on a surface According to implementations of the present invention, the surface of the metal layer and the surface of the plastic film are contacted with a polymerization composition to initiate a polymerization reaction, thereby forming a polymer layer on the surface. An easier method of forming a polymer layer on the surface of a substrate is to coat the surface with a pre-polymerized polymer. Forming a polymer layer through a polymerization reaction differs from coating with a pre-polymerized polymer in some respects.

[0252] Prepolymerized polymer Commercially available pre-polymerized polymers sold as products usually have a specific molecular weight range. This is because the same polymer may need to be used with different molecular weights depending on the application. These sold polymers are almost free of very small molecular weight impurities such as monomers, dimers, trimers, and tetramers that are present in the resulting mixture as a result of the polymerization reaction during the manufacturing process. Polymers labeled as having a specific molecular weight range (not oligomers) have had a significant amount of oligomers of 10-20 monomers removed from the resulting mixture as a result of the polymerization reaction during the manufacturing process.

[0253] Pre-polymerized polymer is coated on the surface Polymers, which have very high molecular weights, can be easily coated by dissolving them in a solvent, applying the coating solution to the surface of a substrate, and then evaporating the solvent. The coating solution used to coat a surface with a prepolymerized polymer requires the addition of other materials in addition to the solvent and polymer.

[0254] Pre-polymerized polymer is coated on the surface - surfactant To form a polymer layer of a certain thickness on a surface, the coating liquid must spread evenly over the surface of the substrate. To ensure that the coating liquid spreads evenly over the surface of the substrate, a surfactant is added to the coating liquid. As a result, when a prepolymerized polymer is coated on a surface, the resulting coating layer contains a surfactant.

[0255] Pre-polymerized polymer is coated on the surface - binder Depending on the characteristics of the substrate surface and polymer, and the structure of the substrate surface, such as its roughness, the polymer coating layer may not adhere well to the substrate surface. To improve adhesion to the substrate surface, a binder is added to the coating solution. In particular, most polymers have low bonding strength with metal surfaces. Therefore, to coat a prepolymerized polymer on a metal surface, a binder such as epoxy resin, polyurethane resin, silicone resin, vinyl resin, or acrylic resin is added to the coating solution. As a result, the resulting polymer coating layer contains a binder.

[0256] Coating the surface with pre-polymerized polymer - oligomer The polymer layer formed by coating a prepolymerized polymer onto a substrate surface is almost free of very small molecular weight compounds and oligomers such as monomers, dimers, trimers, and tetramers. This is because prepolymerized polymers that are labeled as having a specific range of molecular weight rarely contain these small compounds as they are impurities.

[0257] Pre-polymerized polymer - does not form chemical bonds and does not penetrate pinholes When coating a prepolymerized polymer, the polymer does not form a strong chemical bond with the metal surface. Prepolymerized polymers made from the compounds of Formulas 1 to 11 also do not bond well to the metal surface. This is why a binder is necessary. Furthermore, when coating a prepolymerized polymer, the polymer is unlikely to penetrate pinholes in the metal. This is because the polymer has a considerable size and length, and it does not take much time for the coating and evaporation of the coating solution.

[0258] Polymerization reaction occurring on the substrate surface According to an embodiment of the present invention, a polymerization reaction occurs when a polymerization reaction composition contacts the surface of a substrate, such as a metal or plastic film. The compounds of Formulae 1 to 11 interact with the surface of the substrate and chemically bond to the surface of the substrate. Furthermore, the compounds of Formulae 1 to 11 grow into dimers, trimers, tetramers, and oligomers through a chain polymerization reaction to form polymers. As a result, the composition resulting from the polymerization reaction contains polymers of various sizes and one or more of the dimers, trimers, tetramers, and oligomers. When this composition is reused on a subsequent substrate, the resulting composition can contain even more polymers of various sizes.

[0259] Polymer layers produced by polymerization reactions - monomers, dimers, trimers, tetramers, oligomers The polymer layer produced through a polymerization reaction on a substrate surface according to an embodiment of the present invention contains a mixture of polymers and oligomers of various sizes, including one or more of monomers, dimers, trimers, and tetramers. This polymer layer does not contain a particularly high purity of polymers with a specific range of molecular weights, but rather contains polymers with various molecular weights, and therefore contains a significant amount of oligomers. Although the monomers, dimers, trimers, and tetramers can be removed during the washing process, if they form chemical bonds with the substrate surface, they will remain in the polymer layer in significant amounts. Ultimately, the amount of any one of the monomers, dimers, trimers, and tetramers present in the polymer layer is significantly different from that of a polymer layer obtained by coating a commercially available pre-polymerized polymer.

[0260] Polymer layer by polymerization reaction - surfactant In carrying out a polymerization reaction on a substrate surface according to an embodiment of the present invention, a surfactant, which is used when coating a pre-polymerized polymer, is not required. The polymer layer formed by carrying out a polymerization reaction without a surfactant does not contain a surfactant. However, a surfactant can be added to the polymerization composition, and the resulting polymer layer can contain a surfactant.

[0261] Polymer layer by polymerization reaction - binder When a polymerization reaction is carried out on the surface of a substrate according to an embodiment of the present invention, a substantial number of monomers, dimers, trimers, tetramers, oligomers, and polymers are chemically bonded to the surface. Therefore, this polymerization reaction does not require a binder, which is used when coating a pre-polymerized polymer. A polymer layer produced by carrying out a polymerization reaction without a binder does not contain a binder. However, a binder can be added to the polymerization composition, and the resulting polymer layer can contain a binder.

[0262] Polymerization reaction to fill pinholes The polymerization reaction according to the present invention not only produces a polymer layer on the surface of the metal substrate, but also fills or seals pinholes formed in the metal layer. The monomers or oligomers contained in the polymerization reaction composition enter the metal pinholes, interact with the inner surface to form chemical bonds, and grow through the polymerization reaction to fill part or all of the inner space of the pinholes. The polymers or oligomers formed in the pinholes can extend outside the pinholes and connect with the oligomers or polymers formed outside the pinholes.

[0263] XVII. Separator coating Lithium-ion battery separator The separator forms a physical layer between the anode and cathode of a lithium-ion battery to prevent short circuits caused by direct contact between the two electrodes. To achieve this, the separator must ensure electrochemical and thermal stability, and must also maintain a certain level of mechanical strength. At the same time, the separator must allow lithium ions from the electrolyte to pass through, generating current. To facilitate this, the separator must be porous, thin, and have a high affinity for the electrolyte.

[0264] Polyolefin material Lithium-ion battery separators are typically microporous polymer membranes made from polyolefin materials such as polyethylene or polypropylene. Polyethylene and polypropylene offer suitable electrochemical stability and mechanical strength for separators. However, the low hydrophilicity of polyolefin materials results in low affinity for the electrolyte, which increases resistance during ion conduction and reduces battery performance.

[0265] coating To solve the above problems, active research is being conducted to improve the hydrophilicity of polyolefin-based separators, and representative methods include ceramic coating and polymer coating.

[0266] ceramic coating Currently, a common method is to ensure the heat resistance and increase the hydrophilicity of polyolefin separation membranes by coating the cross section or both sides of the polyolefin separation membrane with a highly heat-resistant ceramic layer. For example, a common method is to prepare a slurry containing a mixture of inorganic particles such as aluminum oxide and an organic binder, and then coat this on the surface of the polyolefin separation membrane using a method such as tip coating. In this case, as shown in Figure 7, a ceramic layer 1040 containing inorganic particles is formed on the surface of the polyolefin separation membrane 1020, creating a structure in which the separation membrane 1020 is sandwiched between the ceramic layers 1040.

[0267] Disadvantages of ceramic coating When ceramic is coated over the entire separator to form the ceramic layer, the pores are blocked, reducing air permeability and increasing resistance during ion conduction, which can negatively impact battery performance. To prevent or mitigate this, a process for forming pores in the coating layer is essential. Furthermore, the low surface energy of polyolefin-based separators results in poor adhesion to the ceramic coating layer, which can easily cause the inorganic coating layer to detach partially during secondary battery assembly or within the battery. If the ceramic layer detaches easily, battery safety is reduced and defects due to slitting or foreign matter generated during the assembly process increase. To address these shortcomings, processes such as inorganic particle processing and multi-layer coating have been developed, but the introduction of additional processes increases unit costs.

[0268] polymer coating As an alternative to ceramic coating, polymer coating of separation membranes is currently being studied extensively due to its accessibility and ease of mass production. Fluorine-based polymers such as PVdF (polyvinylidene difluoride) and PVdF-HFP (polyvinylidene fluoride-co-hexafluoropropylene) are being studied as surface coatings for polyolefin separation membranes.

[0269] Disadvantages of polymer coatings Like ceramics, polymer coating can clog pores and reduce breathability when applied to the entire separator. Furthermore, while a hydrophilic polymer must be used to improve hydrophilicity, polyolefin-based materials are hydrophobic, resulting in poor adhesion between the polymer layer and the polyolefin-based separator, and the coated layer can detach during charging and discharging, resulting in poor battery performance and reduced safety.

[0270] Separation membrane substrate One embodiment of the present invention provides a method for forming a polymer layer on a separator using a polymerization reaction of a monomer instead of the ceramic coating or polymer coating. The separator substrate on which the polymer layer is formed can be any separator material known to be suitable for lithium-ion batteries. For example, the separator substrate can be selected from various microporous polymer membranes.

[0271] Separation membrane substrate material Any material can be used for the separator as long as it has good insulating properties and can ensure the basic physical properties required for a separator in a lithium-ion battery. For example, the separator material can be one or more selected from the group consisting of commonly used polyethylene and polypropylene, as well as PVdF, polyester, polyacrylonitrile (PAN), polyethylene terephthalate (PET), etc.

[0272] Separation membrane substrate structure Separation membranes have a macroscopically rigid yet microscopically porous structure. For example, they may have a structure in which pores are formed in a thin film formed by a method such as extrusion, or they may have a woven or nonwoven structure. For example, the separation membrane substrate may have a woven structure of polyethylene fibers or a woven form of polypropylene fibers.

[0273] stomata The separator must contain a sufficient number of pores to facilitate lithium ion conduction through its thickness, and the more uniform their size, the better. For example, the separator may have a porosity of 30-60%, and the average pore diameter may be 0.01, 0.02, 0.03, 0.05, 0.07, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.60, 0.70, 0.80, 0.90, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.7, 1.9, 2.1, 2.4, 2.7, or 3 μm. The average pore diameter may fall within a range obtained by selecting two of the values ​​listed in the immediately preceding sentence. The pores have an interconnected structure, allowing lithium ions to be conducted from one side of the separator to the other side through its thickness.

[0274] Separation membrane thickness A thin separator is preferred to facilitate lithium ion conduction in the thickness direction, but a certain thickness is necessary for safety. For example, the separator thickness can be 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, or 60 μm. The separator thickness can fall within the range obtained by selecting two of the values ​​listed in the previous sentence.

[0275] XVIII. Coating membrane production by polymerization reaction Preparing the composition solution The composition solution for preparing the coated separator may be the same as or similar to the monomer solution. For example, the composition solution may include compounds of Formulas 1 to 11. The composition solution may further include an organic or inorganic filler to increase the stability of the separator.

[0276] Contacting the separation membrane with the composition solution A polymerization reaction vessel (vessel or reservoir) large enough to accommodate the separation membrane is prepared. The vessel is filled with a polymerization reaction composition solution. The separation membrane is then brought into contact with the composition solution in the vessel. A polymerization reaction occurs on the surface of the separation membrane in contact with the composition solution, producing a polymer layer.

[0277] Separation membrane supported in composition solution When the separation membrane is placed in a polymerization reaction vessel, only one side can be in contact with the composition solution and the other side can be left uncontacted, or the entire separation membrane can be supported so that both sides are completely immersed in the solution. Multiple separation membranes can also be supported in the composition solution together in one polymerization reaction vessel to carry out the polymerization reaction and increase the productivity of the process. Multiple separation membranes can be supported in the composition solution so that they can be stacked, or a structure can be inserted between adjacent separation membranes to maintain a distance so that the composition solution can enter between them.

[0278] A coated separation membrane with a polymer layer formed on the surface When a polymerization reaction is initiated in the composition solution that comes into contact with the surface of the separation membrane, a polymer is produced on the surface of the separation membrane. This polymer forms a polymer layer on the surface of the separation membrane, and macroscopically, a polymer layer is formed in the order separation membrane-polymer layer. A separation membrane with such a polymer layer formed is called a "coated separation membrane."

[0279] Coated separator membrane with polymer layers on both sides When the polymerization reaction is carried out while the separation membrane is immersed in the composition solution on both sides, a polymer layer can be formed on both sides. Macroscopically, a polymer layer is formed in the order of polymer = separation membrane - polymer layer.

[0280] polymer layer The polymerization reaction produces polymers of various sizes, as well as oligomers and dimers, and as a result, the polymer layer of the coating separator may contain polymers of various sizes, as well as oligomers and dimers.

[0281] Polymerization reaction in pores A portion of the composition solution that contacts the surface of the separator can enter some of the pores of the separator. The monomer that enters the pores of the separator undergoes a polymerization reaction, bonding with at least a portion of the inner surface of the separator surrounding the pores and forming a polymer layer on at least a portion of the inner surface of the pores. Figure 8 illustrates an example of a polymer layer formed on the inner surface of the pores of a porous separator. As shown in Figure 8, polymer layer 1140 formed on the inner surface surrounding pores 1160 of porous separator 1120 improves the hydrophilicity of the pores and improves the conductivity of lithium ions dissolved in the electrolyte.

[0282] Washing and drying Once the polymerization reaction is complete, the coated separator is removed from the container and washed with water or other cleaning solutions to remove unwanted materials from the surface. After washing, the separator is dried.

[0283] XIX. Coated Separator Membrane Adhesion of the polymer layer This method does not involve dissolving a prepolymerized polymer in a solvent and applying it to the surface of the separation membrane, but rather involves polymerizing a monomer on the surface of the separation membrane to form a polymer layer, which provides excellent adhesion between the separation membrane surface and the polymer layer.

[0284] Pores and polymer layers The pores in the separator are channels that conduct lithium ions. Therefore, if the coating layer fills or blocks the pores in the separator, lithium ion conductivity decreases, resulting in reduced battery performance. In the above example, the separator is supported on or in contact with a polymerization reaction composition containing a monomer, rather than a polymer solution, and a polymerization reaction occurs. This allows the monomer to spread across the surface of the separator at the molecular level while the polymer is formed. This minimizes pore blockage by the polymer layer compared to coating the polymer itself in a solvent. In addition, the hydrophilic polymer layer formed around the pores helps lithium ions pass through the pores and conduct.

[0285] effect According to an embodiment of the present invention, a coated separator is provided that has significantly improved ionic conductivity by forming a hydrophilic polymer layer on the separator surface. At the same time, the polymer layer enhances the thermal stability and physical properties of the separator. Furthermore, by forming a polymer layer by bonding with the separator in monomer units, the polymer is strongly bonded to the separator, reducing the risk of the coating separating even after repeated charging and discharging. Furthermore, by forming a polymer layer by bonding with the separator in monomer units, it is possible to coat separators with a woven structure instead of thin-film structures. Furthermore, the monomer can penetrate into nano-sized pores, forming a hydrophilic polymer layer inside the pores. A polymer layer with these advantages can be formed through a relatively simple and inexpensive process.

[0286] XX. Polymerization Reactions on Separation Membrane Surfaces Polymerization Reaction Composition The polymerization reaction composition that occurs on the metal surface of the separator contains a monomer and a solvent, and may further contain an oligomer or polymer formed by prepolymerizing the monomer. A base, acid, or buffer solution may be added to adjust the pH. In some cases, a polymerization initiator may also be included. The composition solution may further contain organic or inorganic fillers to increase the stability of the separator.

[0287] monomer The monomers used in the polymerization reaction are self-initiating monomers, which spontaneously initiate the polymerization reaction, and are basic compounds, such as compounds of Chemical Formulas 1 to 11.

[0288] Two or more monomers The polymerization reaction occurring on the surface of the separation membrane can be a polymerization reaction using two or more monomers, such as a copolymer of 3,4-diaminopyridine and 2,6-diaminopyridine, which is a cross-addition copolymer between isomeric compounds with similar structures, a copolymer of 2,5-diaminopyridine and 3-amino-2-cyclohexen-1-one, or a copolymer of 2,4,6-triaminopyrimidine and methyl 3-aminocrotonate, which is a cross-addition copolymer between monomers with significantly different structures, or a copolymer formed by Diels-Alder polymerization between furfurylamine and methyl 3-aminocrotonate.

[0289] Monomer concentration of polymerization reaction composition In the polymerization reaction composition, the monomer concentration is about 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17.5, 18, 18.5, 19, 19.5, or 20 mg / mL. The monomer concentration can fall within a range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, the monomer concentration can fall within a range of about 2.0 to about 5.0 mg / mL or a range of about 1.0 to about 7.0 mg / mL.

[0290] Basic Composition According to one embodiment, the pH of the polymerization reaction composition is adjusted to a basic value of 8 or more. Although the monomers of the compounds of Formulas 1 to 11 themselves are basic, a basic substance such as sodium hydroxide (0.01M, 0.1M, or 1M, etc.), 15-20% DMEA (N,N-dimethylethylamine, CAS 598-56-1) or 15-20% 2-dimethylaminoethanol (CAS 108-01-0) (pH around 13), or boric acid / sodium borate buffer solution (pH around 9) can be added to adjust the pH of the composition.

[0291] initiator According to one embodiment, the composition for the polymerization reaction does not include a radical initiator or a photoinitiator, but according to another embodiment, an initiator may be included.

[0292] Initiation of the polymerization reaction The polymerization reaction usually proceeds without a separate initiator, but can also proceed with the addition of an initiator in some cases. The polymerization reaction proceeds at a temperature lower than the boiling point of the solvent, usually between 0 and 90°C. When the polymerization reaction proceeds without an initiator, the polymerization reaction begins when the nucleophilic functional groups on the substrate surface react with the unsaturated bonds of the compounds of Formulas 1 to 11.

[0293] When an initiator is included Although the compound monomers of Formulas 1 to 11 are self-initiating, depending on the material on the substrate surface, it may be necessary to use an initiator to initiate the polymerization reaction. Examples of compounds that can be used as initiators include AIBN (Azobisisobutyronitrile), ABCN (1,1'-Azobis(cyclohexane-carbonitrile)), di-tert-butyl peroxide, and benzoyl peroxide. These initiators generate radical intermediates at specific temperatures, which react with the monomers to initiate the polymerization reaction. For example, when AIBN is used as the initiator, the temperature can be 40, 45, 50, 55, 60, 65, or 70°C.

[0294] Temperature of the polymerization reaction composition The polymerization reaction proceeds at a temperature below the boiling point of the solvent used. The temperature of the polymerization reaction composition is adjusted to about 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100°C. This temperature can fall within a range obtained by selecting two of the numbers listed in the previous sentence. For example, the temperature of the polymerization reaction composition can fall within the range of about 20 to about 70°C, about 40 to about 90°C, or about 10 to about 30°C.

[0295] Contact time with the polymerization reaction composition The time for which the separation membrane substrate is in contact with the polymerization reaction composition can be about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 42, 44, 46, 48, 50, 52, 54, 56, 68, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, or 80 hours. The time for which the separation membrane substrate is in contact with the polymerization reaction composition can fall within a range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, the polymerization reaction time may be in the range of about 2 to about 10 hours, about 6 to about 12 hours, or about 8 to about 24 hours.

[0296] Removal of liquid remaining on the surface of the separation membrane on which the polymer layer is formed When a polymer layer is formed on the surface of the separation membrane upon contact with the polymerization reaction composition in the polymerization reaction vessel, the membrane is removed from the polymerization reaction vessel. The surface is then wiped with or touched with absorbent paper or an absorbent pad to remove any liquid components of the polymerization reaction composition remaining on the polymer layer or the surface of the separation membrane. Before or after wiping off the liquid components, the membrane may be washed with water or another cleaning solution. When washing, the liquid on the surface is wiped off.

[0297] baking After removing the liquid from the surface, the polymer layer is baked in an oven to evaporate the liquid components remaining in the polymer layer, crosslink the polymers formed in the polymer layer, and harden the polymer layer.

[0298] Baking Temperature Baking is performed at a low temperature that does not denature the separation membrane substrate, and is typically performed at about 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, or 150°C. The baking temperature can be within a range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, baking can be performed at a temperature in the range of about 50 to about 100°C or about 60 to about 110°C.

[0299] Baking time Baking is performed for approximately 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 hours. The baking time can fall within a range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, baking is performed for approximately 2 to 5 hours, or approximately 4 to 6 hours.

[0300] Polymer Layer Thickness The thickness of the polymer layer can be about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.5, 1.6, 1.8, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 20, 25, or 30 μm. The thickness of the polymer layer can fall within a range obtained by selecting two of the numbers listed in the immediately preceding sentence. For example, the polymer layer can have a thickness ranging from about 0.5 to about 3 μm, or from about 1 to about 5 μm.

[0301] Washing and drying After baking, the product is washed to remove any residual materials remaining in the polymer layer. The polymer layer contains components of the polymerization reaction composition and materials formed as a result of the polymerization reaction. Some of these materials are firmly bound to the metal surface, plastic surface, and the polymers attached to these surfaces, while others are loosely bound. Washing with an acidic or basic cleaning solution can remove any residual materials loosely bound to the polymer layer. After washing, the product is dried. Drying can be done in an oven.

[0302] Reuse of the polymerization reaction resultant composition Once the polymerization reaction is complete, the coated separation membrane is removed from the polymerization vessel. The resulting composition contains a mixture of unreacted monomers and polymers, oligomers, and dimers produced as a result of the polymerization reaction. This composition containing polymers, oligomers, and dimers can be reused in the next polymerization reaction without being discarded. That is, a new separation membrane is supported on the composition remaining from the previous polymerization reaction, and a polymerization reaction is then initiated to produce a coated separation membrane. In this case, the polymers, oligomers, and dimers already present in the composition can be included in the resulting polymer layer, and these polymers, oligomers, and dimers can further participate in the polymerization reaction to produce larger polymers or oligomers. Before the next polymerization reaction for the separation membrane, necessary ingredients can be added to adjust the concentration and pH of the monomers in the composition.

[0303] XXI. Experimental Examples The following describes experiments embodying various embodiments of the present invention, and the scope of protection of the present invention is in no way limited to the following experimental examples.

[0304] Experiment 1: 2,5-diaminopyridine modification on glass slides 2,5-Diaminopyridine was added to a pH 9.0 borate buffer (50 mM) to prepare a solution with a concentration of 1 mg / 1 mL. A glass slide was immersed in the solution and incubated at 90°C for 20 hours. The glass slide was removed and placed in an oven at 60°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 60°C for 5 minutes. The glass slide was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 60°C for 5 minutes.

[0305] Comparative Example 1 A glass slide of the same specifications as used in Example 1 was immersed in a pH 9.0 borate buffer (50 mM) and incubated at 90°C for 20 hours. The glass slide was removed and placed in an oven at 60°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 60°C for 5 minutes. The glass slide was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 60°C for 5 minutes.

[0306] Example 2: 2,5-diaminopyridine modification on aluminum plate The modified sample was prepared in the same manner as in Example 1, except that an aluminum plate was used.

[0307] Comparative Example 2 A comparative sample was prepared in the same manner as in Comparative Example 1, except that an aluminum plate was used.

[0308] Example 3: 2,5-diaminopyridine modification on PMMA 2,5-Diaminopyridine was added to a pH 9.0 borate buffer (50 mM) to prepare a solution with a concentration of 1 mg / 1 mL. A polymethyl methacrylate (PMMA) film was immersed in the solution and incubated at 90°C for 24 hours. The film was removed and placed in an oven at 60°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 60°C for 5 minutes. The film was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 60°C for 5 minutes.

[0309] Comparative Example 3 A polymethyl methacrylate (PMMA) film of the same specifications as used in Example 1 was immersed in a pH 9.0 borate buffer (50 mM) and incubated at 90°C for 24 hours. The PMMA film was removed and placed in an oven at 60°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 60°C for 5 minutes. The PMMA film was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 60°C for 5 minutes.

[0310] Example 4: 2,5-diaminopyridine modification on PC A surface-modified film was prepared in the same manner as in Example 3, except that a polycarbonate (PC) film was used.

[0311] Comparative Example 4 A sample was prepared in the same manner as in Comparative Example 3, except that a polycarbonate (PC) film was used.

[0312] Example 5: 2,5-diaminopyridine modification on PI A surface-modified film was prepared in the same manner as in Example 3, except that a polyimide (PI) film was used.

[0313] Comparative Example 5 A sample was prepared in the same manner as in Comparative Example 3, except that a polyimide (PI) film was used.

[0314] Example 6: 3,4-Diaminopyridine modification on PMMA 3,4-Diaminopyridine was added to 25 mL of 0.1 M NaOH aqueous solution to prepare a 1 mg / mL solution. A 5 x 5 cm polymethyl methacrylate (PMMA) film was immersed in the solution and incubated at 80°C for 22 hours. The film was removed and washed with 15% isopropyl alcohol for 20 seconds, then washed with a sufficient amount of water and dried at 60°C for 5 minutes.

[0315] Comparative Example 6 A 5 × 5 cm polymethyl methacrylate (PMMA) film identical to that used in Example 6 was immersed in 0.1 M NaOH aqueous solution (25 mL) and subjected to a constant temperature treatment at 80°C for 22 hours. The film was then removed, washed with a sufficient amount of water, and dried at 60°C for 5 minutes.

[0316] Example 7: 3,4-Diaminopyridine modification on PMMA 3,4-Diaminopyridine was added to 25 mL of 0.1 M NaOH aqueous solution to prepare a 1 mg / mL solution. A 5 x 5 cm polymethyl methacrylate (PMMA) film was immersed in the solution and incubated at 90°C for 22 hours. The film was removed and washed with 15% isopropyl alcohol for 20 seconds, then washed with a sufficient amount of water and dried at 60°C for 5 minutes.

[0317] Comparative Example 7 This is the same sample as Comparative Example 6.

[0318] Example 8: 3,4-diaminopyridine modification on PI A 1 mg / mL solution was prepared by adding 3,4-diaminopyridine to a pH 9.0 borate buffer (500 mM). A polyimide (PI) film was immersed in the solution and incubated at 80°C for 24 hours. The film was then removed and placed in an oven at 60°C for 3 hours, after which it was washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 60°C for 5 minutes. The film was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 60°C for 5 minutes.

[0319] Comparative Example 8 The same polyimide (PI) film as used in Example 8 was used as is without any treatment.

[0320] Example 9: 2-amino-3-formylpyridine modification on PI 2-Amino-3-formylpyridine was added to a pH 9.0 borate buffer (500 mM) to prepare a 1 mg / mL solution. A polyimide (PI) film was immersed in the solution and incubated at 80°C for 24 hours. The film was removed and placed in an oven at 60°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 60°C for 5 minutes. The film was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 60°C for 5 minutes.

[0321] Comparative Example 9 This is the same sample as Comparative Example 8.

[0322] Contact angle measurement A Ramehart Instrument goniometer (Model 300) in New Jersey, USA was used to measure the contact angle. A 2 μl droplet of sample solution (15% aqueous dimethylethanolamine solution) was placed on the sample surface on the goniometer sample stage using a microsyringe. After taking a side view of the contact state between the sample droplet placed on the goniometer sample stage and the sample surface, the contact angle was measured using the goniometer's DropImage software to obtain quantitative information on the contact angle.

[0323] The contact angles of the sample films of Examples 1-9 and Comparative Examples 1-9 were measured by the above method, and the results are shown in Tables 2 to 9. [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9] [Table 10]

[0324] Example 10: 4-Vinylpyridine modification on PI A 1 mg / mL solution was prepared by adding 4-vinylpyridine to a pH 9.0 borate buffer (500 mM). A polyimide (PI) film was immersed in the solution and incubated at 80°C for 24 hours. The film was then removed and placed in an oven at 60°C for 3 hours, after which it was washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 60°C for 5 minutes. The film was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 60°C for 5 minutes.

[0325] Comparative Example 10 A polyimide (PI) film of the same specifications as that used in Example 10 was used as is without any treatment.

[0326] The contact angles of the sample films of Example 10 and Comparative Example 10 were measured by the above method, and the results are shown in Table 1. [Table 11]

[0327] Example 11: 3-amino-2-cyclohexen-1-one coating on glass slides A 1 mg / mL solution was prepared by adding 3-amino-2-cyclohexen-1-one to a pH 9.0 borate buffer (50 mM). A glass slide was immersed in the solution and incubated at 90°C for 20 hours. The glass slide was removed and placed in a 60°C oven for 3 hours, then washed with NaOH solution for 20 seconds. It was then rinsed with a sufficient amount of water and dried at 60°C for 5 minutes. The glass slide was then rinsed again with HCl solution for 20 seconds, rinsed with a sufficient amount of water, and dried at 60°C for 5 minutes.

[0328] Comparative Example 11 A glass slide of the same specifications as used in Example 11 was immersed in a pH 9.0 borate buffer (50 mM) and incubated at 90°C for 20 hours. The glass slide was removed and placed in an oven at 60°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 60°C for 5 minutes. The glass slide was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 60°C for 5 minutes.

[0329] Example 12: 3-amino-2-cyclohexen-1-one coating on aluminum plate A coating sample was prepared in the same manner as in Example 11, except that an aluminum plate was used.

[0330] Comparative Example 12 A sample was prepared in the same manner as in Comparative Example 11, except that an aluminum plate was used.

[0331] Example 13: 3-amino-2-cyclohexen-1-one coating on PI A 1 mg / mL solution was prepared by adding 3-amino-2-cyclohexen-1-one to a pH 9.0 borate buffer (500 mM). A polyimide (PI) film was immersed in the solution and incubated at 80°C for 24 hours. The film was then removed and placed in an oven at 60°C for 3 hours, after which it was washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 60°C for 5 minutes. The film was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 60°C for 5 minutes.

[0332] Comparative Example 13 A polyimide (PI) film of the same specifications as used in Example 13 was immersed in a pH 9.0 borate buffer (500 mM) and incubated at 80°C for 24 hours. The film was removed and placed in an oven at 60°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 60°C for 5 minutes. The film was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 60°C for 5 minutes.

[0333] Example 14: 3-amino-2-cyclohexen-1-one coating on PET Two 1 mg / mL solutions were prepared by adding 3-amino-2-cyclohexen-1-one to 100 mM and 500 mM pH 9.0 borate buffer. A polyethylene terephthalate (PET) film was immersed in the solution and incubated at 80°C for 24 hours. The film was then removed and placed in a 60°C oven for 3 hours, after which it was washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 60°C for 5 minutes. The film was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 60°C for 5 minutes. The sample using 100 mM borate buffer was designated Example 14-1, and the sample using 500 mM borate buffer was designated Example 14-2.

[0334] Comparative Example 14 A PET film of the same specifications as that used in Example 14 was used as is without any treatment.

[0335] The contact angles of the sample films of Examples 11-14 and Comparative Examples 11-14 were measured by the above method, and the results are shown in Tables 12 to 15. [Table 12] [Table 13] [Table 14] [Table 15]

[0336] Example 15: 1-ethenylcyclopentan-1-amine modification on glass slides 1-Ethenylcyclopentan-1-amine was added to a pH 9.0 borate buffer (50 mM) to prepare a 1 mg / mL solution. A glass slide was immersed in the solution and incubated at 90°C for 20 hours. The glass slide was removed and placed in a 60°C oven for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 60°C for 5 minutes. The glass slide was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 60°C for 5 minutes.

[0337] Comparative Example 15 A glass slide of the same specifications as used in Example 15 was immersed in a pH 9.0 borate buffer (50 mM) and incubated at 90°C for 20 hours. The glass slide was removed and placed in an oven at 60°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 60°C for 5 minutes. The glass slide was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 60°C for 5 minutes.

[0338] Example 16: 1-ethenylcyclopentan-1-amine modification on polyimide film A surface-modified film was prepared in the same manner as in Example 15, except that a polyimide (PI) film was used.

[0339] Comparative Example 16 A sample was prepared in the same manner as in Comparative Example 15, except that a polyimide (PI) film was used.

[0340] The contact angles of the sample films of Examples 15-16 and Comparative Examples 15-16 were measured by the above method, and the results are shown in Tables 16 and 17. [Table 16] [Table 17]

[0341] Example 17a: Furfurylamine modification on glass slides in a weakly basic solution at room temperature Furfurylamine was added to a pH 9.0 borate buffer (50 mM) to prepare a solution with a concentration of 1 mg / 1 mL. A glass slide was immersed in the solution at room temperature for 20 hours. The glass slide was then removed and placed in an oven at 70°C for 3 hours, after which it was washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 70°C for 5 minutes. The glass slide was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 70°C for 5 minutes.

[0342] Example 17b: Copolymer of furfurylamine and methyl 3-aminocrotonate modified on glass slides in a weakly basic solution at room temperature Furfurylamine and methyl 3-aminocrotonate were added to a borate buffer (50 mM) at pH 9.0 to prepare solutions with concentrations of 1 mg / 1 mL and 1.7 mg / 1 mL for the two solutes, respectively. The subsequent steps were carried out in the same manner as in Example 1a to prepare the modified sample.

[0343] Comparative Example 17 A glass slide of the same specifications as used in Example 17 was immersed in a pH 9.0 borate buffer (50 mM) at room temperature for 20 hours. The glass slide was removed and placed in an oven at 70°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 70°C for 5 minutes. The glass slide was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 70°C for 5 minutes.

[0344] Example 18a: Furfurylamine modification on glass slides in a strongly basic solution at room temperature Furfurylamine was added to an 8% aqueous solution of dimethylethanolamine at pH 13 to prepare a solution with a concentration of 1 mg / 1 mL. A glass slide was immersed in the solution at room temperature for 12 hours. The glass slide was then removed and placed in an oven at 70°C for 3 hours, after which it was washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 70°C for 5 minutes. The glass slide was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 70°C for 5 minutes.

[0345] Example 18b: Copolymer of furfurylamine and methyl 3-aminocrotonate modified on glass slides in a strongly basic solution at room temperature Furfurylamine and methyl 3-aminocrotonate were added to an 8% aqueous solution of dimethylethanolamine at pH 13 to prepare solutions with concentrations of 1 mg / 1 mL and 1.7 mg / 1 mL for the two solutes, respectively. The subsequent steps were carried out in the same manner as in Example 18a to prepare the modified sample.

[0346] Comparative Example 18 A glass slide of the same specifications as used in Example 18 was immersed in a pH 9.0 borate buffer (50 mM) at room temperature for 12 hours. The glass slide was removed and placed in an oven at 70°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 70°C for 5 minutes. The glass slide was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 70°C for 5 minutes.

[0347] Example 19a: Furfurylamine modification on polyimide film in a weakly basic solution at room temperature A surface-modified film was prepared in the same manner as in Example 17a, except that a polyimide (PI) film was used.

[0348] Example 19b: Furfurylamine and methyl 3-aminocrotonate copolymer modification on polyimide film in a weakly basic solution at room temperature A surface-modified film was prepared in the same manner as in Example 17b, except that a polyimide (PI) film was used.

[0349] Comparative Example 19 A sample was prepared in the same manner as in Comparative Example 17, except that a polyimide (PI) film was used.

[0350] Example 20: Furfurylamine modification on polyimide film in a weakly basic solution at 50°C Furfurylamine was added to a pH 9.0 borate buffer (50 mM) to prepare a solution with a concentration of 1 mg / 1 mL. A polyimide (PI) film was immersed in the solution and incubated at 50°C for 3 hours. The PI film was removed and placed in an oven at 70°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 70°C for 5 minutes. The glass slide was then washed with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 70°C for 5 minutes.

[0351] Comparative Example 20 A PI film of the same specifications as used in Example 20a was immersed in a borate buffer (50 mM) at pH 9.0 and incubated at 50°C for 3 hours. The PI film was removed and placed in an oven at 70°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 70°C for 5 minutes. The PI film was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 70°C for 5 minutes.

[0352] Example 21: Furfurylamine modification on polyimide film in a weakly basic solution at 70°C Furfurylamine was added to a borate buffer (50 mM) at pH 9.0 to prepare a solution with a concentration of 1 mg / 1 mL. A polyimide (PI) film was immersed in the solution and incubated at 70°C for 20 hours. The subsequent steps were the same as in Example 20 to prepare a modified sample.

[0353] Comparative Example 21 A PI film of the same specifications as that used in Example 21 was immersed in a borate buffer (50 mM) at pH 9.0 and was incubated at 70°C for 20 hours. The subsequent steps were the same as in Comparative Example 20 to prepare a modified sample.

[0354] Example 22a: Furfurylamine modification on polyimide film in a strongly basic solution at room temperature A surface-modified film was prepared in the same manner as in Example 18a, except that a polyimide (PI) film was used.

[0355] Example 22b: Furfurylamine and methyl 3-aminocrotonate copolymer modification on polyimide film in a strongly basic solution at room temperature A surface-modified film was prepared in the same manner as in Example 18b, except that a polyimide (PI) film was used.

[0356] Comparative Example 22 A sample was prepared in the same manner as in Comparative Example 18, except that a polyimide (PI) film was used.

[0357] Example 23: Furfurylamine modification on polyimide film in a strong basic solution at 70°C Furfurylamine was added to an 8% aqueous solution of dimethylethanolamine at pH 13 to prepare a solution with a concentration of 1 mg / 1 mL. A polyimide (PI) film was immersed in the solution and incubated at 70°C for 20 hours. The PI film was removed and placed in an oven at 70°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then rinsed with a sufficient amount of water and dried at 70°C for 5 minutes. The glass slide was then rinsed with HCl solution for 20 seconds, rinsed with a sufficient amount of water, and dried at 70°C for 5 minutes.

[0358] Comparative Example 23 A PI film of the same specifications as used in Example 7 was immersed in an 8% dimethylethanolamine aqueous solution with a pH of 13 and incubated at 70°C for 20 hours. The glass slide was removed and placed in an oven at 70°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then rinsed with a sufficient amount of water and dried at 70°C for 5 minutes. The glass slide was then rinsed again with HCl solution for 20 seconds, rinsed with a sufficient amount of water, and dried at 70°C for 5 minutes.

[0359] Example 24a: Furfurylamine modification on polyethylene film in a weakly basic solution at room temperature A surface-modified film was prepared in the same manner as in Example 17a, except that a polyethylene (PE) film for food packaging (a composite film having a printed surface film and an aluminum film between two polyethylene films on both sides) was used.

[0360] Example 24b: Furfurylamine and methyl 3-aminocrotonate copolymer modification on polyethylene film in a weakly basic solution at room temperature A surface-modified film was prepared in the same manner as in Example 17b, except that a polyethylene (PE) film for food packaging was used.

[0361] Comparative Example 24 A sample was prepared in the same manner as in Comparative Example 17, except that a polyethylene (PE) film for food packaging was used.

[0362] Example 25a: Furfurylamine modification on polyethylene film in a strongly basic solution at room temperature A surface-modified film was prepared in the same manner as in Example 18a, except that a polyethylene (PE) film for food packaging was used.

[0363] Example 25b: Furfurylamine and methyl 3-aminocrotonate copolymer modification on polyethylene film in a strongly basic solution at room temperature A surface-modified film was prepared in the same manner as in Example 18b, except that a polyethylene (PE) film for food packaging was used.

[0364] Comparative Example 25 A sample was prepared in the same manner as in Comparative Example 18, except that a polyethylene (PE) film for food packaging was used.

[0365] The contact angles of the sample films of Examples 17-25 and Comparative Examples 17-25 were measured using the above method, and the results are shown in Tables 18 to 26. "Dropping liquid" refers to the sample liquid used in the contact angle measurement. [Table 18] [Table 19] [Table 20] [Table 21] [Table 22] [Table 23] [Table 24] [Table 25] [Table 26]

[0366] These results confirm that furfurylamine, whether used alone or together with methyl 3-aminocrotonate, provides a hydrophobic coating for the surface modification of various substrates. The properties of the modified surface can vary depending on the specific substrate and surface modification conditions, and it was confirmed that a more hydrophobic coating tends to be obtained when the two compounds, furfurylamine and methyl 3-aminocrotonate, are used together. From these experimental results, those skilled in the art should be able to optimize the appropriate compound and surface modification conditions to obtain a substrate surface with the desired properties.

[0367] Example 26: Methyl 3-aminocrotonate modification on glass slides in a weakly basic solution at room temperature Methyl 3-aminocrotonate was added to a pH 9.0 borate buffer (50 mM) to prepare a solution with a concentration of 1 mg / 1 mL. A glass slide was immersed in the solution at room temperature for 20 hours. The glass slide was then removed and placed in a 70°C oven for 3 hours, after which it was washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 70°C for 5 minutes. The glass slide was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 70°C for 5 minutes.

[0368] Comparative Example 26 A glass slide of the same specifications as used in Example 26 was immersed in a pH 9.0 borate buffer (50 mM) at room temperature for 20 hours. The glass slide was removed and placed in an oven at 70°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 70°C for 5 minutes. The glass slide was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 70°C for 5 minutes.

[0369] Example 27: Methyl 3-aminocrotonate modification on glass slides in a strongly basic solution at room temperature Methyl 3-aminocrotonate was added to an 8% aqueous solution of dimethylethanolamine at pH 13 to prepare a solution with a concentration of 1 mg / 1 mL. A glass slide was immersed in the solution at room temperature for 12 hours. The glass slide was then removed and placed in an oven at 70°C for 3 hours, after which it was washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 70°C for 5 minutes. The glass slide was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 70°C for 5 minutes.

[0370] Comparative Example 27 A glass slide of the same specifications as used in Example 28 was immersed in a pH 9.0 borate buffer (50 mM) at room temperature for 12 hours. The glass slide was removed and placed in an oven at 70°C for 3 hours, then washed with NaOH solution for 20 seconds. It was then washed with a sufficient amount of water and dried at 70°C for 5 minutes. The glass slide was then washed again with HCl solution for 20 seconds, washed with a sufficient amount of water, and dried at 70°C for 5 minutes.

[0371] Example 28: Methyl 3-aminocrotonate modification on polyimide film in a weakly basic solution at room temperature A surface-modified film was prepared in the same manner as in Example 27, except that a polyimide (PI) film was used.

[0372] Comparative Example 28 A sample was prepared in the same manner as in Comparative Example 27, except that a polyimide (PI) film was used.

[0373] Example 29: Methyl 3-aminocrotonate modification on polyimide film in a strongly basic solution at room temperature A surface-modified film was prepared in the same manner as in Example 28, except that a polyimide (PI) film was used.

[0374] Comparative Example 29 A sample was prepared in the same manner as in Comparative Example 28, except that a polyimide (PI) film was used.

[0375] Example 30: Methyl 3-aminocrotonate modification on polyethylene film in a weakly basic solution at room temperature A surface-modified film was prepared in the same manner as in Example 27, except that a polyethylene (PE) film for food packaging (a composite film having a printed surface film and an aluminum film between two polyethylene films on both sides) was used.

[0376] Comparative Example 30 A sample was prepared in the same manner as in Comparative Example 27, except that a polyethylene (PE) film for food packaging was used.

[0377] Example 31: Methyl 3-aminocrotonate modification on polyethylene film in a strongly basic solution at room temperature A surface-modified film was prepared in the same manner as in Example 28, except that a polyethylene (PE) film for food packaging was used.

[0378] Comparative Example 31 A sample was prepared in the same manner as in Comparative Example 28, except that a polyethylene (PE) film for food packaging was used. [Table 27] [Table 28] [Table 29] [Table 30] [Table 31] [Table 32]

[0379] From the above results, it was confirmed that when an unsaturated acyclic amine compound is used for surface modification of various substrates, a hydrophobic coating is provided. The properties of the modified surface can vary depending on the specific substrate and surface modification conditions, and it was also confirmed that the properties of the modified surface can be adjusted by appropriately selecting the unsaturated acyclic amine compound used for surface modification. From the above experimental results, those skilled in the art should be able to optimize the appropriate compound and surface modification conditions to obtain a substrate surface with desired properties.

[0380] Experimental Example - Monomer Solution Preparation Experiment 32 Prepare a monomer solution with a concentration of 1 mg / 1 mL by adding compound No. 1 from Table 1 to a pH 9.0 borate buffer (50 mM).

[0381] Experiment 33-256 Monomer solutions were prepared in the same manner as in Experiment 32, except that Compounds Nos. 2 to 225 in Table 1 were added instead of Compound No. 1, respectively.

[0382] Experiment 257 Prepare a monomer solution with a concentration of 0.5 mg / 1 mL by adding compound No. 1 from Table 1 to a pH 9.0 borate buffer (50 mM).

[0383] Experiments 258-481 Monomer solutions were prepared in the same manner as in Experiment 257, except that Compound Nos. 2 to 225 in Table 1 were added instead of Compound No. 1, respectively.

[0384] Experiment 482 Prepare a monomer solution with a concentration of 5 mg / 1 mL by adding compound No. 1 from Table 1 to a pH 9.0 borate buffer (50 mM).

[0385] Experiments 483-706 Monomer solutions were prepared in the same manner as in Experiment 482, except that compound Nos. 2 to 225 in Table 1 were added instead of compound No. 1, respectively.

[0386] Experiment 707 Compound No. 1 in Table 1 was added to an 8% aqueous solution of dimethylethanolamine at pH 13 to prepare a monomer solution with a concentration of 1 mg / 1 mL.

[0387] Experiments 708-931 Monomer solutions were prepared in the same manner as in Experiment 707, except that compound Nos. 2 to 225 in Table 1 were added instead of compound No. 1, respectively.

[0388] Experiment 932 Add compound No. 1 from Table 1 to a 0.1 M NaOH aqueous solution to prepare a monomer solution with a concentration of 1 mg / 1 mL.

[0389] Experiment 933-1156 Monomer solutions were prepared in the same manner as in Experiment 932, except that compound Nos. 2 to 225 in Table 1 were added instead of compound No. 1, respectively.

[0390] Experimental Example - Polymer Layer Formation Experiment 1157 An aluminum foil is immersed in the monomer solution prepared in Experiments 32 to 1156. After maintaining it at 60°C for 12 hours, the aluminum foil is removed from the monomer solution and placed in a 90°C oven. After leaving it in the 90°C oven for 3 hours, it is removed, washed, and dried. It is confirmed whether a polymer layer has formed on the surface of the dried aluminum foil.

[0391] Experiment 1158 An aluminum foil is immersed in the monomer solution prepared in Experiments 32 to 1156. After maintaining it at 60°C for 24 hours, the aluminum foil is removed from the monomer solution and placed in a 90°C oven. After leaving it in the 90°C oven for 3 hours, it is removed, washed, and dried. It is confirmed whether a polymer layer has formed on the surface of the dried aluminum foil.

[0392] Experiment 1159 An aluminum foil is immersed in the monomer solution prepared in Experiments 32 to 1156. After maintaining it at 60°C for 48 hours, the aluminum foil is removed from the monomer solution and placed in a 90°C oven. After leaving it in the 90°C oven for 3 hours, it is removed, washed, and dried. It is confirmed whether a polymer layer has formed on the surface of the dried aluminum foil.

[0393] Experiment 1160 An aluminum foil is immersed in the monomer solution prepared in Experiments 32 to 1156. After maintaining it at 90°C for 12 hours, the aluminum foil is removed from the monomer solution and placed in a 90°C oven. After leaving it in the 90°C oven for 3 hours, it is removed, washed, and dried. It is confirmed whether a polymer layer has formed on the surface of the dried aluminum foil.

[0394] Experiment 1161 Immerse an aluminum foil in the monomer solution prepared in Experiments 32 to 1156. After maintaining it at 90°C for 24 hours, remove the aluminum foil from the monomer solution and place it in a 90°C oven. Leave it in the 90°C oven for 3 hours, then remove it, wash it, and dry it. Check to see if a polymer layer has formed on the surface of the dried aluminum foil.

[0395] Experiment 1162 An aluminum foil is immersed in the monomer solution prepared in Experiments 32 to 1156. After maintaining it at 90°C for 48 hours, the aluminum foil is removed from the monomer solution and placed in a 90°C oven. After leaving it in the 90°C oven for 3 hours, it is removed, washed, and dried. It is confirmed whether a polymer layer has formed on the surface of the dried aluminum foil.

[0396] Experiment 1163 An aluminum foil is immersed in the monomer solution prepared in Experiments 32 to 1156. After maintaining it at 60°C for 24 hours, the aluminum foil is removed from the monomer solution and placed in a 90°C oven. After leaving it in the 90°C oven for 6 hours, it is removed, washed, and dried. It is confirmed whether a polymer layer has formed on the surface of the dried aluminum foil.

[0397] Experiment 1164 An aluminum foil is immersed in the monomer solution prepared in Experiments 32 to 1156. After maintaining it at 60°C for 24 hours, the aluminum foil is removed from the monomer solution and placed in a 120°C oven. After leaving it in the 120°C oven for 3 hours, it is removed, washed, and dried. It is confirmed whether a polymer layer has formed on the surface of the dried aluminum foil.

[0398] Experiment 1165 An aluminum foil is immersed in the monomer solution prepared in Experiments 32 to 1156. After maintaining it at 60°C for 24 hours, the aluminum foil is removed from the monomer solution and placed in a 120°C oven. After leaving it in the 120°C oven for 6 hours, it is removed, washed, and dried. It is confirmed whether a polymer layer has formed on the surface of the dried aluminum foil.

[0399] Experiments 1166 through 1174 The same experiment as Experiments 1157 to 1165 was carried out except that a polyethylene (PE) film was used instead of the aluminum thin film, to confirm whether a polymer layer was formed.

[0400] Experiments 1175 through 1183 The same experiment as Experiments 1157 to 1165 was carried out except that a polypropylene (PP) film was used instead of the aluminum thin film, to confirm whether a polymer layer was formed.

[0401] Experiments 1184 through 1192 The same experiment as Experiments 1157 to 1165 was carried out except that a polyimide (PI) film was used instead of an aluminum thin film, to confirm whether a polymer layer was formed.

[0402] Experiments 1193 through 1201 The same experiment as Experiments 1157 to 1165 was carried out except that PET nonwoven fabric was used instead of the aluminum thin film, to confirm whether a polymer layer was formed.

[0403] Experimental example - Moisture permeability of aluminum foil Experiment 1202 The moisture permeability of an aluminum foil sample with a thickness of 63 μm and an area of ​​10 cm × 10 cm is measured. The moisture permeability is 1 × 10 -2 〜1×10 -1 g / m 2 It is confirmed to have a value of / day.

[0404] Experiment 1203 A polymer layer was formed on an aluminum foil of the same size as in Experiment 1202 in the same manner as in Experiments 632 to 639, and the moisture permeability was measured. -4 〜1×10 -3 g / m 2 It is confirmed as / day.

[0405] Experimental example - OLED panel sealing structure Experiment 672 Prepare an aluminum foil laminate by bonding approximately 63 μm thick aluminum foil and a polyethylene terephthalate (PET) film with adhesive and crimping them together. Check for defects in the aluminum foil and measure the moisture permeability of the prepared aluminum foil laminate.

[0406] Experiments 673 through 680 The same experiment as Experiments 632 to 639 was conducted to confirm whether a polymer layer was formed on the surface of the aluminum foil, except that the aluminum foil laminate of Experiment 672 was used instead of the thin aluminum film. After confirming that the defects in the aluminum foil identified in Experiment 672 had been filled with the polymer layer, the moisture permeability was measured.

[0407] Experimental example - Food packaging material Experiment 681 A polypropylene (PP) film approximately 50 μm thick is placed in a vapor deposition chamber and aluminum is vapor-deposited onto it to prepare an aluminum-deposited polypropylene laminate. The aluminum layer of the prepared aluminum-deposited polypropylene laminate is checked for defects and its moisture permeability is measured.

[0408] Experiments 682 through 689 Experiments 632 to 639 were conducted in the same manner as Experiments 632 to 639, except that the aluminum-coated polypropylene laminate used in Experiment 681 was used instead of the thin aluminum film, to confirm whether a polymer layer was formed on the surface of the aluminum layer. After confirming that the defects in the aluminum layer confirmed in Experiment 632 had been filled with the polymer layer, the moisture permeability was measured.

[0409] Experimental example - Coated separation membrane Experiment 690 A porous polypropylene (PP) separation membrane with a thickness of approximately 30 μm is prepared and its ionic conductivity is confirmed.

[0410] Experiment 691 The same experiments as in Experiments 632 to 639 were conducted, except that the porous polypropylene (PP) separator used in Experiment 690 was used instead of the aluminum thin film, to confirm whether a polymer layer was formed on the surface of the porous polypropylene (PP) layer. The ionic conductivity of the coated separator with the polymer layer formed was confirmed.

Claims

1. providing an intermediate structure comprising a plastic film and a metal layer formed thereon; 1. A method for manufacturing a metal laminate structure, comprising: forming a polymer layer by polymerizing a metal layer on the intermediate structure; The metal laminate structure includes a plastic film, a metal layer formed on the plastic film, and a polymer layer formed on the metal layer; the composition of the polymerization reaction is binder-free, so that the polymer layer formed by the polymerization reaction is binder-free; The polymer layer contains a polymer obtained using at least one of the compounds belonging to chemical formulas 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11, and the compounds of compound numbers 204-248, as a monomer.

2. the metal layer comprises a metal foil having a thickness ranging from about 1 μm to about 200 μm, and the intermediate structure has an adhesive layer sandwiched between the metal layer and a plastic film; A method for manufacturing the metal laminate structure of claim 1.

3. providing the intermediate structure comprises: providing a plastic film and a metal layer; 10. A method for manufacturing a metal laminate structure according to claim 1, including the step of applying an adhesive between the plastic film and the metal layer and laminating them to provide an adhesive layer interposed between the plastic film and the metal layer.

4. 10. The method for manufacturing a metal laminate structure according to claim 1, wherein the metal layer comprises a metal deposit formed on a plastic film, the thickness of the metal layer is from about 1 nm to about 50 nm, and there is no separate layer interposed between the metal layer and the plastic film.

5. providing the intermediate structure comprises: providing a plastic film; 10. The method of claim 1, further comprising the step of vapor depositing a metal to form a metal layer on a plastic film.

6. providing the intermediate structure comprises: The method further includes a step of plasma treating the surface of the plastic film before performing the metal deposition; 6. The method for manufacturing a metal laminate structure according to claim 5, wherein the metal is vapor-deposited on the surface of the plastic film.

7. 7. The method of claim 1, wherein the step of inducing a polymerization reaction comprises contacting the metal layer of the intermediate structure with a polymerization reaction composition.

8. 7. The method for producing a metal laminate structure according to claim 1, wherein the polymer layer formed as a result of the polymerization reaction on the metal layer contains a substantial amount of one or more compounds selected from the group consisting of oligomers, tetramers, trimers, and dimers derived from the at least one monomer, the substantial amount being such that commercially available polymer compositions having a specific molecular weight range do not contain significant amounts of oligomers, tetramers, trimers, and dimers.

9. 7. The method for producing a metal laminate structure according to any one of claims 1 to 6, wherein one or more compounds selected from the group consisting of oligomers, tetramers, trimers, and dimers are chemically bonded to the metal layer in the polymer layer formed as a result of the polymerization reaction on the metal layer, and such chemical bonding of oligomers, tetramers, trimers, and dimers to the metal layer is of a nature that cannot occur when a pre-polymerized polymer is coated on the metal layer.

10. 7. A method for producing a metal laminate structure according to any one of claims 1 to 6, wherein the metal layer has pinholes extending through the thickness of the metal layer, and at least one of an oligomer and a polymer is chemically bonded to the inner surface of the pinhole while occupying at least a portion of the pinhole space, and such chemical bonding of the oligomer, polymer, or inner surface of the pinhole is of a nature that would not occur when a prepolymerized polymer is coated onto the metal layer.

11. 7. A method for producing a metal laminate structure according to any one of claims 1 to 6, wherein the polymer layer is not obtained by coating a metal layer with a prepolymerized polymer, but is a commercially available polymer composition having a molecular weight within a specific range, and does not contain a polymerization inhibitor contained to inhibit polymerization reactions or crosslinking reactions.

12. 7. The method for producing a metal laminate structure according to claim 1, wherein when a prepolymerized polymer is coated to form a polymer layer, the polymer layer does not contain a surfactant that can be used to uniformly coat the prepolymerized polymer on the metal surface.

13. The polymer layer is referred to as a first polymer layer, and the method for manufacturing the metal laminate structure includes: The method further includes contacting the plastic film of the intermediate structure with a polymerization reaction composition for the polymerization reaction to form a second polymer layer under the plastic film, so that the plastic film is interposed between the metal layer and the second polymer layer; The second polymer layer is not a coating of a pre-polymerized polymer composition, but comprises a polymer formed by polymerizing at least one monomer on the plastic film, but does not comprise a binder for adhering the second polymer layer to the plastic film. A method for manufacturing a metal laminate structure according to any one of claims 1 to 6.

14. 14. The method for manufacturing a metal laminate structure according to claim 13, wherein the first polymer layer and the second polymer layer each have a thickness ranging from about 1 μm to about 20 μm.

15. 14. The method for producing a metal laminate structure according to claim 13, wherein the second polymer layer formed as a result of the polymerization reaction on the plastic film contains a substantial amount of one or more compounds selected from the group consisting of oligomers, tetramers, trimers, and dimers derived from the at least one monomer, the substantial amount being such that commercially available polymer compositions having a specific molecular weight range do not contain significant amounts of oligomers, tetramers, trimers, and dimers.

16. The method for manufacturing a metal laminate structure according to claim 13, wherein the second polymer layer formed as a result of the polymerization reaction on the plastic film includes one or more selected from the group consisting of oligomers, tetramers, trimers, and dimers chemically bonded to the plastic film, and such chemical bonding of oligomers, tetramers, trimers, and dimers to the plastic film is of a nature that cannot occur when a pre-polymerized polymer is coated on a plastic film.

17. 14. The method for manufacturing a metal laminate structure according to claim 13, wherein the plastic film comprises an engineering polymer layer having pores, and at least one of the oligomer and the polymer is present in at least one of the pores and chemically bonded to the inner surface of the pores, and such chemical bonding of the oligomer and the polymer to the inner surface of the pores is of a nature that cannot occur when a prepolymerized polymer is coated onto a plastic film.

18. 14. The method for manufacturing a metal laminate structure according to claim 13, wherein the second polymer layer has a large number of polymer molecules chemically bonded to the plastic film, such that the second polymer layer is attached to the plastic film without the need for a binder.

19. The method for manufacturing a metal laminate structure according to claim 13, wherein the second polymer layer is not obtained by coating a prepolymerized polymer composition on the surface of a plastic film, but is a commercially available polymer composition having a molecular weight within a specific range and does not contain a polymerization inhibitor contained to inhibit polymerization or crosslinking reactions.

20. 14. The method for producing a metal laminate structure according to claim 13, wherein the polymerization reaction composition does not contain any of a surfactant, a polymerization initiator, and a polymerization inhibitor, and the polymer layer formed as a result of the polymerization reaction does not contain any of a surfactant, a polymerization initiator, and a polymerization inhibitor.

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