KR20210041524A - Coating method for stent, and Stent prepared therefrom - Google Patents

Abstract

Provided are a stent coating method and a stent manufactured by the same. The method comprises: a step of providing a stent substrate; a step of arranging a first coating layer on one or more surfaces in the inside and the outside of the stent substrate by supplying at least one among a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, and an aromatic ring compound containing an unsaturated functional group and a polar functional group; and a step of arranging a second coating layer containing a prylene-based polymer on the first coating layer by supplying a prylene-based radical induced from a prylene-based precursor on the first coating layer.

Description

The stent coating method, and the stent manufactured thereby {Coating method for stent, and Stent prepared therefrom}

It relates to a stent coating method, and a stent obtained thereby.

A stent is an endoprosthesis implanted into conduits such as blood vessels in the body. The stent is transported into the body, for example in a compressed shape, then placed at a target location in the conduit and then expanded to its final shape.

Stents are used in the treatment of many body ducts, such as vascular, gallbladder, gastrointestinal, respiratory and other organ ducts. For example, stents are used to treat the stenosis layer.

Since the stent is inserted into the body and used, durability for a biological component and compatibility with a living body are required. A coating layer is introduced to impart durability and biocompatibility to the stent substrate.

In order to introduce a coating layer on the surface of a metal or non-metallic substrate, a wet method such as spin coating is generally used. Spin coating includes a solvent.

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

In order to introduce a coating layer on the surface of the stent substrate, a dry method such as iCVD may be considered. In iCVD, the initiator is thermally decomposed into radicals by hot filament, and the radicals undergo polymerization reaction of monomers to introduce a polymer coating layer on the substrate.

In iCVD, radicals are generated only in adjacent regions of hot filaments arranged in a straight line. Therefore, it is difficult to apply to a stent substrate having a three-dimensional porous structure that does not have a certain distance from the hot filament.

Therefore, there is a need for a method of introducing a uniform and robust coating layer on the surface of a stent substrate.

One aspect of the present invention is to provide a new coating method for introducing a coating layer on the surface of a stent substrate.

Another aspect of the present invention is to provide a stent coated with the coating method.

According to one side

Providing a stent substrate;

A first coating layer is disposed by supplying at least one of a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, and an aromatic ring compound containing an unsaturated functional group and a polar functional group on one or more surfaces of the inside and outside of the stent substrate. The step of doing; And

A stent coating method comprising: disposing a second coating layer including a parylene-based polymer on the first coating layer by supplying a parylene-based radical derived from a parylene-based precursor on the first coating layer.

According to the other side,

A stent substrate for transporting fluid;

A first coating layer disposed on one or more surfaces of the inside and outside of the stent substrate; And

Includes; a second coating layer disposed on the first coating layer,

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

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

According to one aspect, by disposing an intermediate layer derived from a non-fluorine-based acrylic compound or an aromatic heterocyclic compound between the stent substrate and the coating layer containing the parylene-based polymer, the adhesion of the coating layer to the stent substrate is improved, including such a coating layer. The durability and biocompatibility of the stent is improved.

Fig. 1 is a schematic diagram of a method of disposing a first coating layer and a second coating layer according to an exemplary embodiment.
2 is a perspective view showing a stent into which a coating layer is introduced according to an embodiment.
3 is a partial cross-sectional schematic view of a stent to which a coating layer is introduced according to an exemplary embodiment, taken along the line Ib-Ib of FIG. 1.
4 is a partial cross-sectional schematic view of a stent to which a coating layer is introduced according to an exemplary embodiment, taken along line Ib-Ib of FIG. 1.
5 is a partial cross-sectional schematic view of a substrate to which a coating layer is introduced according to an exemplary embodiment, taken along the line Ib-Ib of FIG. 1.
6 is a partial cross-sectional schematic view of a substrate to which a coating layer is introduced according to an exemplary embodiment, taken along the line Ib-Ib of FIG. 1.
Fig. 7 is a schematic cross-sectional view of a coating device according to an exemplary embodiment.
8A is an XPS analysis result of the first coating layer of Example 1-1.
8B is an XPS analysis result of the first coating layer of Example 1-4.
8C is a result of measuring a contact angle with respect to the first coating layer of Example 1-1.
8D is a result of measuring a contact angle for the first coating layer of Example 1-4.
8e is a result of measuring the contact angle with respect to the first coating layer of Comparative Example 1-1.
8F is a test result of adhesion to the coating layer of Example 1-1.
8G is a test result of adhesion to the coating layer of Example 1-6.
8H is an adhesion test result for the coating layer of Example 1-11.
8i is a test result of adhesion to the coating layer of Comparative Example 1-1.
8J is an ATR-FTIR measurement result of the first coating layer of Example 1-1.
8K is an ATR-FTIR measurement result of the first coating layer of Example 1-4.
8L is an ATR-FTIR measurement result of the second coating layer of Example 1-1.
8M is an ATR-FTIR measurement result of the second coating layer of Example 1-3.
<Explanation of symbols for major parts of drawings>
10: stent substrate 20: second coating layer
30: drug-containing polymer layer 50: stent
100: first carburetor 110: first transfer pipe
120: first heat source 200: first flow controller
250: first valve 300: pyrolyzer
310: second transfer pipe 320; Second heat source
400: deposition chamber 500: cooling trap
600: vacuum pump 700: second vaporizer
710: third transfer pipe 800: second flow controller
850: second valve 1000: coating device

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

The terms used below are only used to describe specific embodiments, and are not intended to limit the present inventive idea. Singular expressions include plural expressions unless the context clearly indicates otherwise. Hereinafter, terms such as "include" or "have" are intended to indicate the presence of features, numbers, steps, actions, components, parts, components, materials, or a combination thereof described in the specification. It is to be understood that the above other features, or the possibility of the presence or addition of numbers, steps, actions, components, parts, components, materials, or combinations thereof, are not excluded in advance. "/" used below may be interpreted as "and" or "or" depending on the situation.

In the drawings, the thickness is enlarged or reduced in order to clearly express various layers and regions. Like reference numerals are attached to similar parts throughout the specification. Throughout the specification, when a part such as a layer, film, region, or plate is said to be "on" or "on" another part, this includes not only the case directly above the other part, but also the case where there is another part in the middle. . Throughout the specification, terms such as first and second may be used to describe various constituent elements, but constituent elements should not be limited by terms. The terms are used only to distinguish one component from another. In the present specification and drawings, elements having substantially the same functional configuration are referred to by the same reference numerals, and redundant descriptions are omitted.

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

In the present specification, "three-dimensional structure" refers to a structure in which three dimensions (eg, x, y, z dimensions) are similar in size to each other. For example, a sphere, a cube, a tetrahedron, etc. have a three-dimensional structure. It is also possible to have a three-dimensional structure introduced into a part of the surface of the two-dimensional structure. For example, a printed circuit board on which a three-dimensional circuit including an uneven structure is printed on a two-dimensional substrate also has a three-dimensional structure.

In the present specification, "conformal coating layer" refers to a coating layer disposed on the surface of a substrate so as to conform to the phase according to the topology of the substrate.

In the present specification, the "stent substrate" is a tubular structure substrate made of metal or non-metal. The stent serves to secure the conduit of the conduit by having a radial force to expand in the direction of the outer surface.

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

A stent coating method according to an embodiment includes the steps of providing a stent substrate for transporting a fluid; Disposing a first coating layer by supplying at least one of a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, and an aromatic ring compound containing an unsaturated functional group and a polar functional group on the surface of the stent substrate; And disposing a second coating layer including a parylene-based polymer on the first coating layer by supplying a parylene-based radical derived from a parylene-based precursor on the first coating layer.

In the stent coating method, disposing a first coating layer by supplying at least one of a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, and an aromatic ring compound containing an unsaturated functional group and a polar functional group on the surface of the stent substrate. By including, the adhesion between the stent substrate and the second coating layer disposed on the first coating layer is improved. Accordingly, the adhesion between the stent substrate and the second coating layer is improved, and the second coating layer provides corrosion resistance, oxidation resistance, water resistance, and chemical resistance to the stent substrate. Therefore, the corrosion resistance, oxidation resistance, water resistance, and chemical resistance of the stent substrate including the first coating layer and the second coating layer are improved, and the second coating layer coated on the stent substrate is not easily separated from the stent substrate. It can be reliably protected for a long time in the duct of the body, and the occurrence of side effects in the body is prevented. The above-described first coating layer may be referred to by various names such as a modified layer, an intermediate layer, and an adhesive layer. The second coating layer described above may be otherwise referred to by various names such as a protective layer, a sealing layer, a blocking layer, and an insulating layer.

In the step of providing a stent substrate for transporting fluid, the stent substrate may have a porous three-dimensional structure, for example, as shown in FIG. 2.

Conventionally, a silane-based compound, for example, an alkoxysilane compound represented by the following formula, has been used in order to improve the bonding strength between a base material such as metal, metal oxide, glass, ceramic, etc. and a polymer coating layer. In the following formula, R ₄ is a general organic functional group.

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

Compared to the conventional method of forming the first coating layer by wet coating a composition containing a silane-based compound, the coating method of the present invention does not require an additional curing process such as plasma pretreatment and/or heat treatment of the stent substrate. It's simple and efficient. In addition, no additional equipment is required for plasma treatment and/or heat treatment. In addition, since it is a dry method in which the coating solution is not applied on the stent substrate, additional steps such as removal of the solvent after coating are not required, so the time required for the overall process is shortened and the process is simplified. In addition, there is no problem of environmental pollution due to a volatilized solvent. In addition, since the first coating layer and the second coating layer can be continuously deposited in the same chamber by the same dry method, manufacturing efficiency is improved.

In the step of disposing the first coating layer by supplying at least one of a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, and an aromatic ring compound containing an unsaturated functional group and a polar functional group on the surface of the stent substrate, the unsaturated functional group The containing aromatic heterocyclic compound and the aromatic ring compound containing an unsaturated functional group and a polar functional group are, for example, a 5-membered ring or a 6-membered ring, and the aromatic heterocyclic compound is nitrogen, oxygen, and sulfur. It contains at least one hetero atom selected from among, the aromatic heterocyclic compound contains 1 to 4 heteroatoms, the aromatic ring compound does not contain a hetero atom, and the unsaturated functional group is a functional group including a double bond or a triple bond, The polar functional group may be a functional group containing an oxygen or sulfur atom.

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

The heterocyclic compound containing an unsaturated functional group is, for example, a compound represented by the following formulas 1 to 9, and the aromatic ring compound containing an unsaturated functional group and a polar functional group may be a compound represented by the following formulas 10 to 11:

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

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

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

<Formula 10> <Formula 11>

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

The aromatic heterocyclic compound containing an unsaturated functional group may be, for example, an azole compound having a vinyl group, a pyridine compound having a vinyl group, or the like. The aromatic heterocyclic compound containing an unsaturated functional group is, for example, 4-vinylpyridine, 2-vinylpyridine, 3-allylpyridine, and 1-vinylimida. It may be a sol (1-vinylimidazole), 2-methyl-1-vinylimidazole (2-methyl-1-vinylimidazole).

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

The non-fluorine-based acrylic compound may be, for example, a compound represented by the following formula (20):

<Formula 20>

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

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

The first coating layer may be a self-assembled layer of a non-fluorine-based acrylic compound chemically adsorbed on the stent substrate, a heterocyclic compound containing an unsaturated functional group, and/or an aromatic ring compound containing an unsaturated functional group and a polar functional group. have. A non-fluorine-based acrylic compound, a heterocyclic compound containing an unsaturated functional group, and/or an aromatic ring compound containing an unsaturated functional group and a polar functional group are adsorbed and/or condensed on the stent substrate to form a chemical bond with the stent substrate to form a chemical bond. ) Can be. For example, as shown in FIG. 1, the nitrogen atom of 1-vinylimidazole may be chemically adsorbed by forming a chemical bond on the surface of the metal stent substrate. In addition, a heterocyclic compound containing an unsaturated functional group and/or an aromatic ring compound containing an unsaturated functional group and a polar functional group may be self-assembled on the stent substrate to form a monomolecular layer. It is also possible to form a plurality of layers of a non-fluorine-based acrylic compound, a heterocyclic compound containing an unsaturated functional group, and/or an aromatic ring compound containing an unsaturated functional group and a polar functional group. The first coating layer, for example, does not contain a polymer and may be made of a monomolecular compound. The first coating layer may be obtained, for example, by chemical vapor deposition (CVD).

In the step of disposing a second coating layer including a parylene-based polymer on the first coating layer by supplying a parylene-based radical derived from a parylene-based precursor on the first coating layer, the second coating layer is an unsaturated functional group included in the first coating layer. It may include a parylene-based polymer grafted on. For example, referring to FIG. 1, a parylene-based polymer is graphed with an unsaturated functional group included in the first coating layer by reacting a radical derived from a parylene-based precursor with an unsaturated functional group included in the heterocyclic compound forming the first coating layer. May be formed to form a second coating layer. Since the unsaturated functional group included in the first coating layer reacts with the radical derived from the parylene-based precursor to form a parylene-based polymer, a separate catalyst or initiator for the graft reaction may not be used. Therefore, the formation of the second coating layer can be performed more simply. Since the first coating layer chemically adsorbed on the stent substrate is disposed, bonding of the second coating layer and the first coating layer may be more easily and strongly formed. As a result, the second coating layer may be more strongly bonded to the stent substrate. The second coating layer can be obtained, for example, by chemical vapor deposition (CVD). The first coating layer and the second coating layer may be, for example, a conformal coating layer. Accordingly, the first coating layer and the second coating layer can form a uniform coating layer even on a 3D stent substrate having a complex structure.

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

The second coating layer containing a parylene-based polymer is obtained, for example, by forming a polymer-type thin film from a parylene-based dimer powder represented by the following formulas 12 to 19 by chemical vapor deposition (CVD). Lose. In the second coating layer containing a parylene-based polymer, a parylene-based dimer in a powder state is evaporated by heat, and the evaporated parylene-based dimer is thermally decomposed while passing through the pyrolysis unit of the coating device to be converted into a parylene-based monomer, and a parylene-based monomer Is cooled before being diffused into the vacuum chamber, and the cooled monomer is polymerized in the vacuum chamber to form a polymer layer in the form of a film on the surface of the substrate. Since the polymerization reaction of the parylene-based monomer proceeds at a very low pressure and at room temperature of 30° C. or less, thermal stress is not generated on the surface of the stent substrate. In addition, since the coating using the parylene-based monomer is a dry coating, unlike wet coating, the coating is uniformly made even in the fine gaps on the stent substrate, regardless of the shape of the stent substrate such as sharp needles, holes, corners, corners, and fine holes. It is possible to form a uniform conformal coating film on the stent substrate. Since the second coating layer including the parylene-based polymer has biocompatibility, the biocompatibility of the coated stent is improved. In addition, since pinholes and/or pores do not occur in the second coating layer containing the parylene-based polymer, excellent protective film properties can be provided on a stent substrate made of an inorganic compound in addition to the organic compound substrate. In addition, the second coating layer including the parylene-based polymer can completely seal the stent substrate and has little absorption of moisture and/or oxygen, and thus has excellent water resistance. Therefore, the water resistance of the stent coated with the second coating layer containing the parylene-based polymer is improved. In addition, since the second coating layer including the parylene-based polymer is hardly affected by most chemicals such as acids, alkalis or solvents, it has excellent chemical resistance. In addition, the second coating layer containing a parylene-based polymer has excellent light transmittance, so it is not suitable for coating. There is no change in the appearance of the surface of the stent substrate after. In addition, the surface lubricity of the stent substrate coated by the second coating layer containing the parylene-based polymer is improved. Therefore, there is little adsorption of fine dust or viscous oil components on the coated substrate.

The parylene precursor may include, for example, one or more selected from dimers represented by the following Chemical Formulas 12 to 19:

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

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

The parylene-based polymer included in the second coating layer is Parylene N, Parylene C, Parylene D, Parylene AF-4, Parylene HT, Parylene VT-4, Parylene CF, Parylene A, Parylene AM, It may include at least one selected from parylene H, parylene SR, parylene HR, and parylene NR. When the parylene-based polymer includes such a parylene-based compound, water resistance may be improved. The parylene-based polymer may include parylene N, for example.

In order to supply a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group and/or an aromatic ring compound containing an unsaturated functional group and a polar functional group, on the surface of the stent substrate, a heterocyclic compound containing an unsaturated functional group and/or The vaporization temperature of the aromatic ring compound containing an unsaturated functional group and a polar functional group may be, for example, 25 to 150°C, 30 to 140°C, 40 to 130°C, 50 to 120°C, 60 to 110°C, or 70 to 100°C. However, it is not necessarily limited to this range and may be adjusted according to the boiling point of the compound to be vaporized.

In order to supply a parylene-based radical derived from a parylene-based precursor on the first coating layer, the vaporization temperature of the parylene-based precursor is, for example, 100 to 200°C, 110 to 190°C, 120 to 180°C, or 130 to 170°C. , The thermal decomposition temperature of the parylene precursor may be, for example, 500 to 750°C, 550 to 750°C, 550 to 700°C, 600 to 700°C, 650 to 700°C, 660 to 700°C, or 670 to 690°C. During the introduction of the first coating layer and the second coating layer, the temperature of the stent substrate may be 20 to 40°C, 20 to 35°C, or 20 to 30°C. By having a vaporization temperature, pyrolysis temperature and/or stent substrate temperature in such a range, biocompatibility, water resistance, and adhesion of the coating layer are improved, and a more uniform coating layer can be introduced.

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

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

3 to 6, the material of the stent substrate 10 may be a metal or a non-metal.

As the material of the stent substrate 10, a general known material may be used without any particular limitation. For example, stainless steel, nickel titanium (Ni-Ti) alloy, copper aluminum manganese (Cu-Al-Mn) alloy, tantalum, cobalt chromium (Co-Cr) alloy, iridium, iridium oxide or niobium, etc. The formed metal tube can be cut with a laser so as to form a stent design, and then electropolished can be used. In addition, it may be formed using a method of etching a metal tube, a method of welding the flat metal after laser cutting, or a method of weaving a metal wire. Materials for the stent base are, for example, copper (Cu), aluminum (Al), stainless steel, nickel (Ni), zinc (Zn), iron (Ti), titanium (Ti), lead (Pb), cobalt (Co). , Chromium (Cr), tungsten (W), magnesium (Mg), gold (Au), silver (Ag), platinum (Pt), it may be an alloy of two or more selected from. The material of the stent base may be, for example, a Co-Cr-W-Ni-Mg alloy.

In addition, the material of the stent substrate 10 is not limited to a metal material, but is polyolefin, polyolefin elastomer, polyamide, polyamide elastomer, polyurethane, polyurethane elastomer, polyester, polyester elastomer, It may be formed using a polymer material such as polyimide, polyamideimide, or polyetheretherketone, or an inorganic material such as ceramic or hydroxyapatite. The method of stent processing a polymer material or an inorganic material does not affect the effect of the present invention, and a processing method suitable for each material can be arbitrarily selected.

A coating method according to an embodiment will be described in more detail with reference to FIG. 7.

First, a coating device is prepared.

The coating device 1000 includes a first vaporizer 100 for receiving and vaporizing a parylene precursor powder therein, a first flow controller 200 in communication with the first vaporizer 100, and a first flow controller 200. The connected pyrolyzer 300, the deposition chamber 400 in which the parylene free radicals passed through the pyrolyzer 300 are deposited on the substrate, a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group and/or an unsaturated functional group, and Cooling to discharge and cool the gas generated during deposition, the second vaporizer 700 that accommodates and vaporizes the aromatic ring compound containing the polar functional group inside the second vaporizer 700, the second flow controller 800 in communication with the second vaporizer 700, etc. It includes a trap 500, and a vacuum pump 600 for maintaining the inside of the deposition chamber 400 in a vacuum state. A first valve 250 is disposed between the first flow controller 200 and the pyrolyzer 300, and a second valve 850 that can be opened and closed between the second flow controller 800 and the deposition chamber 300 Is placed.

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

The first vaporizer 100 generates a vaporized parylene precursor by heating the parylene precursor powder supplied therein. A container (not shown) containing parylene powder may be disposed in the first vaporizer 100. Alternatively, it is possible to introduce the parylene precursor powder into the first vaporizer 100 in a predetermined space connected to the first vaporizer 100. The first vaporizer 100 is provided with a first transfer pipe 110 having a cylindrical inner space that is long left and right, and a first heat source 120 is disposed on the outer surface of the space to vaporize the parylene powder contained therein. Make it possible to move along the interior space. The heat source 120 on the outer surface of the first vaporizer 100 may use a heating coil or the like. The parylene precursor powder is heated in the first vaporizer 100 to a temperature of about 100 to 200° C. and moves toward the pyrolyzer 300 along the first transfer pipe 110 in the form of a vaporized parylene precursor.

The pyrolyzer 300 is in communication with the first vaporizer 100 and includes a second transfer pipe 310 through which the vaporized parylene precursor generated in the first vaporizer 100 moves, and contains the vaporized parylene precursor. It includes a second heat source 320 that generates parylene free radicals by heating and thermal decomposition. The pyrolyzer 300 thermally decomposes the vaporized parylene precursor supplied from the first vaporizer 100 to generate a parylene free radical, that is, a parylene monomer. The internal temperature of the pyrolyzer 300 is about 500 ~ 750 ℃. The shape of the pyrolyzer 300 is, for example, a shape of a furnace through which the second transfer pipe 310 made of quartz passes. In order to minimize heat loss of the first vaporizer 100 and the pyrolyzer 300, an insulating layer may be disposed outside them.

The deposition chamber 400 communicates with the pyrolyzer 300 and includes a space formed therein. A stent substrate is disposed in the inner space of the deposition chamber 400.

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

Subsequently, a parylene-based radical derived from a parylene precursor generated in the pyrolyzer 300 is supplied onto the first coating layer. The parylene free radical generated in the pyrolysis unit 300 proceeds to a graft polymerization reaction to the unsaturated functional groups of the non-fluorine-based acrylic compound, aromatic heterocyclic compound, and/or aromatic ring compound on the surface of the first coating layer. A second coating layer containing a parylene-based polymer is formed. The inside of the deposition chamber 400 is a low temperature environment of about 20 to 40° C. adjacent to room temperature. The second coating layer comprising a parylene-based polymer is formed by graft polymerization of a vaporized parylene free radical and an unsaturated functional group of a non-fluorine-based acrylic compound/aromatic heterocyclic compound/aromatic ring compound. It is carried out at a low temperature of 20 to 40°C. Accordingly, the stent substrate may be a material having poor heat resistance at high temperatures, such as a thermoplastic polymer film or a thermoplastic plastic, in addition to heat-resistant materials such as metal, semimetal, semiconductor, and glass. Since the deposition is substantially performed at room temperature, thermal denaturation of the stent substrate and deterioration due to heat can be prevented. Therefore, it is applicable to substantially all types of stent substrates. Referring to FIGS. 3 to 6, a conformal coating layer having a predetermined thickness is formed in accordance with the surface contour of the stent substrate 10. The pressure inside the deposition chamber 400 may be maintained at 1.5 to 10 times as compared to before the parylene free radicals are supplied. In this pressure range, the second coating layer may be deposited more efficiently. The rate at which parylene free radicals are supplied into the deposition chamber 400 may be controlled within a range in which the pressure inside the deposition chamber 400 is maintained.

The first vaporizer 100, the second vaporizer 700, the pyrolyzer 300, and the deposition chamber 400 all maintain an internal vacuum state during the coating process. To this end, a cooling trap 500 and a vacuum pump 600 are connected to the deposition chamber 400. The cooling trap 500 is a device that collects and cools gas generated during coating, and the vacuum pump 600 communicated with the cooling trap 500 is a first vaporizer 100 and a second vaporizer 700 during the coating process. ), the inside of the pyrolyzer 300 and the deposition chamber 400 is made into a vacuum and the vacuum state thereof is maintained.

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

A first valve 250 capable of opening and closing is disposed between the first flow controller 200 and the pyrolyzer 300. The first valve 250 may be closed when a next step is prepared after the coating layer forming step is completed, or when it is necessary to fill the parylene precursor powder during the coating layer forming step. The first valve 250 is, for example, a vacuum ball valve.

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

A second valve 850 capable of opening and closing is disposed between the second flow rate controller 700 and the deposition chamber 400. The second valve 850 prepares the next step after the coating layer formation step is completed, or in the coating layer formation step, a non-fluorine-based acrylic compound, an aromatic heterocyclic compound having an unsaturated functional group, and/or an aromatic ring compound including an unsaturated functional group and a polar functional group Can be locked if it needs to be charged. The second valve 850 is, for example, a vacuum ball valve.

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

2 to 6, in the stent 50 according to an embodiment, conformal coating layers 20 and 30 are disposed on the stent substrate 10. The conformal coating layers 20 and 30 have substantially the same shape as the stent substrate 10. By disposing the conformal coating layers 20 and 30 on the stent substrate 10, the corrosion resistance, oxidation resistance, water resistance, and chemical resistance of the stent 50 are improved, and as a result, the durability of the stent 50 is improved. In addition, the biocompatibility of the stent 50 is improved.

2 and 3, the stent 50 according to an embodiment, the stent substrate 10; And a first coating layer (not shown) disposed on the surface of the stent substrate, wherein the first coating layer is a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, an aromatic ring compound containing an unsaturated functional group and a polar functional group , And at least one selected from derivatives thereof, a second coating layer 20 disposed on the surface of the first coating layer (not shown); including, and the second coating layer 20 is a parylene derived from a parylene precursor. It contains a rene-based polymer. Since the stent 50 includes a first coating layer (not shown) and a second coating layer 20, which are conformal coating layers introduced on the surface of the stent substrate 10, corrosion resistance, oxidation resistance, water resistance, Chemical resistance and the like may be improved. In addition, the biocompatibility of the stent 50 is improved.

2 and 4 to 6, the stent 50 according to an embodiment further includes a polymer layer 30 disposed on the second coating layer 20.

The polymer layer 30 is formed by fixing a polymer to the surface of the second coating layer 20. The polymer fixed to the surface of the second coating layer 20 is fixed to the surface of the second coating layer 20, contains a drug, and may have an ability to release the drug at a constant rate. In addition, it may be a polymer that is difficult to adhere to platelets and does not exhibit irritation to tissues.

The polymer included in the polymer layer 30 is, for example, polyglycolic acid, a copolymer of lactic acid and glycolic acid, poly-DL-lactic acid (DL-PLA), poly-L-lactic acid (L-PLA), and lactide. , Polycaprolactone (PCL), collagen, gelatin, chitin, chitosan, hyaluronic acid, polyamino acids such as poly-L-glutamic acid and poly-L-ridine, starch, poly-ε-caprolactone, polyethylene succinate, or poly It may be a biodegradable polymer such as -β hydroxylalkanoate. Further, for example, a polar functional group may be introduced into the terminal of polylactic acid, polyglycolic acid, or a copolymer of polylactic acid and polyglycolic acid. In addition, as long as it is decomposed enzymatically or non-enzymatically in a living body, the decomposition product does not show toxicity, and the drug can be released, all are possible. Further, a plasticizer may be added in order to promote decomposition by the living body and to efficiently release the drug. The plasticizer may be, for example, an ester plasticizer of tartaric acid, malic acid or citric acid, or other plasticizers that have been confirmed to be safe for living organisms. In addition, non-degradable polymers having biocompatibility can be used. For example, polycarbonates such as parylene, parillast, polyethylene, polyethylene terephthalate, ethylene vinyl acetate, silicone, polyethylene oxide (PEO), polybutylmethyl acrylate, polyacrylamide, polyethylene carbonate or polypropylene carbonate, Polyurethane, such as segmented polyurethane, or a mixture of polyether-type polyurethane and dimethyl silicone, or a synthetic polymer such as a block copolymer may be used. In addition, natural polymers such as fibrin can be used. In addition, a functional group may be introduced to fix the polymer to the second coating layer 20.

The drug contained in the polymer layer 30 may be, for example, a drug having an effect of preventing restenosis of blood vessels. For example, antiplatelet agents, anticoagulants, antifibrin, antithrombin, thrombolytic agents, antiproliferative agents, anticancer agents, immunosuppressants, antibiotics and anti-inflammatory agents.

Antiplatelet agents, anticoagulants, antifibrin, and antithrombin include sodium heparin, low molecular weight heparin, hirudin, argatroban, forskolin, sarpogrelate hydrochloride, vapiprost, prostacyclin. ), prostacycline homolog, dextran, D-phe-pro-arg-chloromethylketone (synthetic antithrombin), dipyridamole, glycosyl Protein IIb/IIIa platelet receptor antagonist, vitronectin receptor antagonist, anti-thrombin, and the like.

The thrombolytic agent may be, for example, a tissue plasminogen activating factor, streptokinase and urokinase.

Antiproliferative agents include angiotensin converting enzyme inhibitors such as angiopeptin, captopril, silazapril and lisinopril, calcium channel blockers, colchicine ( colchicine), fibroblast growth factor (FGF) antagonist, fish oil (omega3-fatty acid), hetamine antagonist, lovastatin (HMG0CoA reductase inhibitor), methotrexate, nitropurside, phospho Diesterase inhibitor, prostaglandin inhibitor, ceramine (PDGF antagonist), serotonin inhibitor, steroid, thioprotease inhibitor, triazolopyrimidine (PDGF antagonist), nitric oxide, ol Trans retinoic acid (all-trans retinoic acid), 13-cisretinoic acid (13-cisretinoic acid) and 9-cis retinoic acid (retinoind;-9 -alitretinoin) and the like. In addition, nitrogen mustard (including mechloretamine, cyclophosphamide and its analogs, melphalan and chlorambucil, etc.), ethyleneimine, methylmelamine (including hexamethylmelamine and thiotepa), sulfonic acid Antiproliferative antimitotic alkylation drugs such as alkyl-busulfan complex, nitrosourea (including carmustine (BCNU), BCNU analog and sotreptozosin) and trazenes-dacarbazine (DTIC) complex Etc.

In addition, pyrimidine analogs (such as fluorouracil, phloxuridine and cytarabine), purine analogs (such as mercaptopurine, thioguanine, pentostatin, and 2-chlorodioxyadenosine) and other inhibitors may be used. Even antiproliferative mitotic metabolic antagonists such as platinum coordination complexes (cisplatinum, carboplatin), procarbazine, hydroxyurea, mitotane, aminoglutethymide, or hormones (containing estrogen, etc.) do. In addition, it may be an enzyme such as L-asparaginase that metabolizes L-asparagine systemically and takes away various cells that do not have a function of magnetically synthesizing asparagine.

Anticancer drugs include alkaloids such as Taxol, Taxotere, Topotesine, antibiotics such as adreacin and Breo, metabolic antagonists such as 5-FU, and vinca alkaloids (vinblastine, vincristine and vinorelbine), etc. It may be a natural product of.

The immunosuppressant may be cyclospoline, tacrolimus (FK-506), sirolimus (rapamycin), azathioprine, and mofetil mycophenolate. Examples of antibiotics include dactinomycin (actinomycin D), daunorubicin, doxorubicin, and idarubicin, anthracycline, mitoxantrone, breomycin, pricamycin (citramycin), and mitomycin. .

Anti-inflammatory drugs include aspirin, dipyridamole, ticlopidine, clopidogrel, absiximab, antimigratory, antisecretory drug (brleveldin), adrenocorticosteroids (cortisol, cortisone, fludro). Cortisone (fludrocortisone), prednisone, 6α-methylprednisolone, triamcinolone, betamethazone, and dexamethazone), nonsteroidal drugs (salicylic acid derivatives, i.e. aspirin, paraaminophenol derivatives, i.e. acetminophene), indole Acetic acid and indenic acid (indomethacin, sulindac, etodalac, etc.), heteroarylacetic acid (tolmethine, diclofenac, ketorolac, etc.), arylpropionic acid (ibuprofen and its derivatives), antoranilic acid (mefenamic acid, meclofe Namic acid), enoleic acid (piroxicam, tenoxycam, phenylbutazone and oxypentatrazone), nabumetone and gold compounds (oranopine, gold thioglucose and gold thiosaperate sodium), and the like. In addition, alpha interferon, angiogenesis agent, vascular endothelial cell growth factor (VEGF), angiotensin receptor blocker, nitric oxide donor, antisense oligonucleotides and combinations thereof, cell cycle inhibitory factor, mTOR inhibitory factor, growth factor Signaling kinase inhibitors, retenoids, cyclin/CDK inhibitors, HMG coenzyme retactase inhibitors (statins), and protease inhibitors.

The above-described drugs can be used alone or in combination. In addition, it is possible to use epithelial cells whose genes have been altered to secrete various drugs by genetic engineering, rather than the drug itself.

The above-described drugs can be placed in the polymer by a known method. For example, it can be placed in the polymer by mixing the polymer and the drug in a gel state. In this case, the drug is placed in the polymer by physical interaction or ionic interaction or the like. In addition, depending on the type of polymer, drugs may be incorporated into the three-dimensional structure of the polymer. When a solution of a polymer and a drug is used, or the like, is fixed to the first coating layer 20 of the polymer, the disposition of the drug by the polymer and the fixation of the polymer to the second coating layer 20 can be simultaneously performed.

The fixing of the polymer layer 30 on the surface of the second coating layer 20 is a method of immersing the stent body 10 in which the second coating layer 20 is disposed in a polymer solution, and the stent body in which the second coating layer 20 is disposed. In (10), a method of spraying or dropping a polymer solution may be used. The solvent and the concentration of the polymer in the polymer solution used for immersion or spraying are not particularly limited, and may be determined in consideration of the required drug content and release rate. The thickness of the polymer layer 30 may be thick in terms of thickness uniformity, but if it is too thick, cracks may occur when the stent is used. The thickness of the polymer layer 30 may be, for example, 0.1 μm to 200 μm or 1 μm to 100 μm. The polymer layer 30 may be a single layer or a multilayer. Some or all of the polymer layer 30 may contain a drug.

2 and 4, the stent 50 according to an embodiment, for example, the stent substrate 10; A first coating layer (not shown) comprising at least one selected from a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, and a derivative thereof; A second coating layer 20 comprising a parylene-based polymer derived from a parylene precursor; And a polymer layer 30 containing a drug. When the coating layer includes such a three-layer structure, the biocompatibility, corrosion resistance, oxidation resistance, water resistance, and chemical resistance of the stent 50 may be further improved. In addition, since the drug is continuously released from the stent 50, for example, blood vessel stenosis can be more effectively prevented.

2 and 5, the stent 50 according to an embodiment includes, for example, a stent substrate 10; A first coating layer (not shown) comprising at least one selected from a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, and a derivative thereof; A second coating layer 20 comprising a parylene-based polymer derived from a parylene precursor; A polymer layer 30 containing a drug; And a second coating layer 20 including a parylene-based polymer derived from a parylene precursor. When the coating layer includes such a four-layer structure, biocompatibility, corrosion resistance, oxidation resistance, water resistance, chemical resistance, and the like of the stent 50 may be further improved. In addition, since the drug is continuously released from the stent 50, for example, blood vessel stenosis can be more effectively prevented.

2 and 6, the stent 50 according to an embodiment includes, for example, a stent substrate 10; A first coating layer (not shown) comprising at least one selected from a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, and a derivative thereof; A second coating layer 20 comprising a parylene-based polymer derived from a parylene precursor; A polymer layer 30 containing a drug; A second coating layer 20 comprising a parylene-based polymer derived from a parylene precursor; And a polymer layer 30 containing a drug. When the coating layer includes such a five-layer structure, biocompatibility, corrosion resistance, oxidation resistance, water resistance, chemical resistance, and the like of the stent 50 may be further improved. In addition, since the drug is continuously released from the stent 50, for example, blood vessel stenosis can be more effectively prevented.

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

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

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

The aromatic bicyclic heterocyclic compound includes, for example, indole, isoindole, indazole, purine, quinoline, isoquinoline, and the like.

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

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

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

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

In the present specification, "alkyl group" refers to a group of fully saturated branched or unbranched (or straight or linear) hydrocarbons.

Non-limiting examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, iso-amyl, n-hexyl , 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, and the like.

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

(Manufacture of coated articles)

Example 1: Coating of the first coating layer (1-vinylimidazole) and the second coating layer (parylene N)

A chamber in which the first vaporizer, the second vaporizer, and the pyrolysis device are connected was prepared.

One sheet of an aluminum foil (100 μm thick) having a size of 300 mm×300 mm was mounted in a vacuum chamber having a diameter of 700 mm and a height of 800 mm in a vertical direction.

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

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

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

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

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

Example 2: Coating of the first coating layer (4-vinylpyrine) and the second coating layer (parylene N)

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

Example 3: Coating of the first coating layer (1-vinylimidazole) and the second coating layer (parylene C)

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

Example 1-4

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

Example 1-5

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

Examples 1-6 to 1-10

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

Examples 1-11 to 1-15

A coating layer was deposited in the same manner as in Examples 1-1 to 1-5, except that the time for supplying the compound for forming the first coating layer in the chamber was changed from 20 minutes to 60 minutes.

Comparative Example 1-1: Parylene N alone coating

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

Comparative Example 1-2: Parylene C alone coating

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

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

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

Evaluation Example 1-1: XPS analysis of Al substrate into which the first coating layer was introduced

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

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

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

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

It was determined that the peaks of zinc (Zn) and lead (Pb) contained impurities contained in aluminum metal.

Evaluation Example 1-2: Water (H ₂ O) Contact angle measurement

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

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

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

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

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

Evaluation Example 1-3: Adhesion Test

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

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at 1 mm intervals, cut into a grid, and then a scotch tape was attached to the grid-shaped coating layer and the area of the coating layer removed by peeling was evaluated. .

The evaluation criteria are as follows.

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

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

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

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

As shown in Table 2 and FIGS. 8F to 8I, the adhesive strength of the coating layer of the example was mostly 4B or more, and the adhesion of the coating layers of Comparative Examples 1-1 to 1-3 was all 0B, which was poor.

8F is a coating layer of Example 1-1, FIG. 8G is a coating layer of Example 1-6, FIG. 8H is a coating layer of Example 1-11, and FIG. 8I is an adhesion test result of the coating layer of Comparative Example 1-1. The coating layer was transparent. Therefore, the surface of the substrate was seen as it was.

In FIGS. 8F to 8H, the coating layer was hardly removed.

On the other hand, in FIG. 8I, most of the coating layer is detached and the coating layer is partially detached in the part where the coating layer is not partially detached, so that the coating layer appears opaque due to the empty space generated between the substrate and the coating layer.

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

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

Evaluation Example 1-4: ATR-FTIR analysis of an Al substrate into which the first coating layer and the second coating layer were introduced

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

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

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

Fig on, Al substrate, as shown in the 8k (hydroxyethyl) after the coating ^{methacrylate, 3100-3500 cm -1 (OH Stretching)} , 1716 cm -1 (C = O stretching), 1607 cm - ^{In 1} (C=C stretching), 1161 cm ^-1 (ester OC-OC stretching), a characteristic peak due to (hydroxyethyl) methacrylate was confirmed. Therefore, it was confirmed that (hydroxyethyl) methacrylate was coated. The OH stretching vibration (hydrogen bonds) of ATR-FTIR of pure (hydroxyethyl) methacrylate in solution is confirmed as a broad peak in the region of ^{3100-3600 cm -1, but on the Al substrate (hydroxyethyl)} When the methacrylate was coated, it was found to be split into 4 peaks in ^{the 3100-3500 cm -1 area.}

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

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

(Cu description)

Example 2-1

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

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

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

Evaluation Example 2-1: XPS analysis of Cu substrate into which the first coating layer was introduced

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

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

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

Evaluation Example 2-2: Water (H ₂ O) Contact angle measurement

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

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

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

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

Evaluation Example 2-3: Adhesion Test

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

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at 1 mm intervals, cut into a grid, and then a scotch tape was attached to the grid-shaped coating layer and the area of the coating layer removed by peeling was evaluated. .

The evaluation criteria are as follows.

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

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

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

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

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

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

Evaluation Example 2-4: ATR-FTIR analysis of Cu substrate into which the first coating layer and the second coating layer were introduced

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

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

(Fe description)

Example 3-1

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

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

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

Evaluation Example 3-1: XPS analysis of Fe substrate into which the first coating layer was introduced

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

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

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

Evaluation Example 3-2: Water (H ₂ O) Contact angle measurement

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

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

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

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

Evaluation Example 3-3: Adhesion Test

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

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at 1 mm intervals, cut into a grid, and then a scotch tape was attached to the grid-shaped coating layer and the area of the coating layer removed by peeling was evaluated. .

The evaluation criteria are as follows.

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

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

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

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

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

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

Evaluation Example 3-4: ATR-FTIR analysis of the Fe substrate into which the first coating layer and the second coating layer were introduced

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

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

(Ti description)

Example 4-1

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

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

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

Evaluation Example 4-1: XPS analysis of Ti substrate into which the first coating layer was introduced

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

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

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

Evaluation Example 4-2: Water (H ₂ O) Contact angle measurement

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

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

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

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

Evaluation Example 4-3: Adhesion Test

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

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at 1 mm intervals, cut into a grid, and then a scotch tape was attached to the grid-shaped coating layer and the area of the coating layer removed by peeling was evaluated. .

The evaluation criteria are as follows.

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

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

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

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

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

Examples 4-5, 4-10, 4-14, and 4-15 in which (hydroxy) methacrylate were used had overall improved adhesion compared to Comparative Examples 4-1 to 4-3, but 1-vinyl imida. Compared to the sol, the adhesion was poor.

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

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

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

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

(Pb description)

Example 5-1

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

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

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

Evaluation Example 5-1: XPS analysis of the Pb substrate into which the first coating layer was introduced

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

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

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

Evaluation Example 5-2: Water (H ₂ O) Contact angle measurement

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

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

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

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

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

Evaluation Example 5-3: Adhesion Test

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

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at 1 mm intervals, cut into a grid, and then a scotch tape was attached to the grid-shaped coating layer and the area of the coating layer removed by peeling was evaluated. .

The evaluation criteria are as follows.

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

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

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

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

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

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

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

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

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

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

(SUS description)

Example 6-1

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

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

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

Evaluation Example 6-1: XPS analysis of the SUS substrate to which the first coating layer was introduced

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

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

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

Evaluation Example 6-2: Water (H ₂ O) Contact angle measurement

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

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

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

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

Evaluation Example 6-3: Adhesion Test

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

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at 1 mm intervals, cut into a grid, and then a scotch tape was attached to the grid-shaped coating layer and the area of the coating layer removed by peeling was evaluated. .

The evaluation criteria are as follows.

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

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

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

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

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

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

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

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

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

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

(Glass base material)

Example 7-1

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

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

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

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

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

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

In Example 7-4, after (hydroxyethyl) methacrylate was coated on the glass substrate, a peak for an oxygen atom and a peak for a carbon atom were confirmed on the surface of the substrate. Therefore, it was confirmed that (hydroxyethyl) methacrylate was coated. The peak for the carbon atom decreased significantly compared to the oxygen atom.

Evaluation Example 7-2: Water (H ₂ O) Contact angle measurement

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

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

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

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

Evaluation Example 7-3: Adhesion Test

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

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at 1 mm intervals, cut into a grid, and then a scotch tape was attached to the grid-shaped coating layer and the area of the coating layer removed by peeling was evaluated. .

The evaluation criteria are as follows.

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

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

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

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

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

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

Evaluation Example 7-4: ATR-FTIR analysis of a glass substrate into which the first coating layer and the second coating layer were introduced

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

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

(Ni description)

Example 8-1

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

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

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

Evaluation Example 8-1: XPS analysis of the Ni substrate into which the first coating layer was introduced

In the manufacturing process of the substrates coated in Examples 8-1 to 8-15 and Comparative Examples 8-1 to 8-3, XPS (X-ray Photoelectron Spectroscopy) analysis was performed on the surface of the substrate after the first coating layer was introduced. Thus, it was confirmed whether the first coating layer was introduced.

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

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

Evaluation Example 8-2: Water (H ₂ O) Contact angle measurement

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

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

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

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

Evaluation Example 8-3: Adhesion Test

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

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at 1 mm intervals, cut into a grid, and then a scotch tape was attached to the grid-shaped coating layer and the area of the coating layer removed by peeling was evaluated. .

The evaluation criteria are as follows.

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

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

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

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

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

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

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

Evaluation Example 8-4: ATR-FTIR analysis of the Ni substrate into which the first coating layer and the second coating layer were introduced

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

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

(Zn description)

Example 9-1

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

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

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

Evaluation Example 9-1: XPS analysis of the Zn substrate into which the first coating layer was introduced

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

In Example 9-1, after 1-vinylimidazole was coated on a Zn substrate, a peak for an oxygen atom, a peak for a nitrogen atom, and a peak for a carbon atom were observed on the surface of the substrate. Therefore, it was confirmed that 1-vinylimidazole was coated. The peak for the oxygen atom was determined to be due to a hydrophilic functional group such as a hydroxy group present on the Zn substrate. The peak for the nitrogen atom was insignificant.

In Example 9-4, after (hydroxyethyl) methacrylate was coated on the Zn substrate, a peak for an oxygen atom and a peak for a carbon atom were confirmed on the surface of the substrate. Therefore, it was confirmed that (hydroxyethyl) methacrylate was coated.

Evaluation Example 9-2: Water (H ₂ O) Contact angle measurement

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

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

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

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

Evaluation Example 9-3: Adhesion Test

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

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at 1 mm intervals, cut into a grid, and then a scotch tape was attached to the grid-shaped coating layer and the area of the coating layer removed by peeling was evaluated. .

The evaluation criteria are as follows.

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

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

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

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

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

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

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

Evaluation Example 9-4: ATR-FTIR analysis of the Zn substrate into which the first coating layer and the second coating layer were introduced

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

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

(Alloy description)

Example 10-1

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

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

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

Example 10-16: stent substrate coating

In place of the aluminum foil, a coating layer was deposited in the same manner as in Example 10-1, except that a tube-shaped Co-Cr alloy stent substrate having a length of 20 mm, a diameter of 2 mm, and a thickness of 60 μm was used.

It was confirmed that a conformal coating layer was formed on the inner and outer surfaces of the stent substrate.

Evaluation Example 10-1: XPS analysis of the alloy substrate into which the first coating layer was introduced

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

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

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

Evaluation Example 10-2: Water (H ₂ O) Contact angle measurement

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

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

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

As shown in Table 19, the contact angle was reduced by the introduction of the first coating layer on the alloy substrate. Therefore, it was confirmed that the first coating layer was introduced on the alloy substrate.

Evaluation Example 10-3: Adhesion Test (I)

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

The coating layer was cut into 11 straight lines in the horizontal and vertical directions at 1 mm intervals, cut into a grid, and then a scotch tape was attached to the grid-shaped coating layer and the area of the coating layer removed by peeling was evaluated. .

The evaluation criteria are as follows.

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

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

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

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

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

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

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

Evaluation Example 10-4: Adhesion Test (II)

The outer surface of the stent prepared in Examples 10-16 was observed under a microscope at 400 times magnification.

No defects such as cracks and peeling were found on the outer surface of the stent prepared in Example 10-16.

The stent prepared in Examples 10-16 was mounted on a balloon catheter, and the diameter of the stent was expanded to 3.5 mm by pressing the balloon.

The maximum distortion rate of the extended stent was 45% at the maximum. After expansion, the catheter was removed and the outer surface of the stent was observed.

In the stent prepared in Example 10-16, there was no crack in the coating layer, and no peeling of the coating layer from the stent substrate was observed.

Therefore, the first coating layer improves the binding force between the stent substrate and the second coating layer, the first coating layer is firmly fixed on the stent substrate by covalent bonding, and the second coating layer is again covalently bonded to the first coating layer. It is firmly fixed.

Therefore, there was no cracking or peeling of the coating layer even when the stent was deformed.

Evaluation Example 10-5: ATR-FTIR analysis of the alloy substrate into which the first coating layer and the second coating layer were introduced

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

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

Claims (11)

Providing a stent substrate;
A first coating layer is disposed by supplying at least one of a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, and an aromatic ring compound containing an unsaturated functional group and a polar functional group on one or more surfaces of the inside and outside of the stent substrate The step of doing; And
A stent coating method comprising: supplying a parylene-based radical derived from a parylene-based precursor on the first coating layer and disposing a second coating layer including a parylene-based polymer on the first coating layer. The method of claim 1, wherein the terminal substituent connected to the oxygen atom of the non-fluorine-based acrylic compound contains 5 or less carbon atoms,
The aromatic heterocyclic compound containing an unsaturated functional group and the aromatic ring compound containing an unsaturated functional group and a polar functional group are a 5-membered ring or a 6-membered ring,
The aromatic heterocyclic compound contains at least one hetero atom selected from nitrogen, oxygen, and sulfur,
The aromatic heterocyclic compound contains 1 to 4 heteroatoms,
The aromatic ring compound is a hetero atom free,
The unsaturated functional group is a functional group including a double bond or a triple bond,
The polar functional group is a functional group containing an oxygen or sulfur atom, the stent coating method. The method of claim 1, wherein the aromatic heterocyclic compound containing an unsaturated functional group is a compound represented by the following formulas 1 to 9,
The aromatic ring compound containing the unsaturated functional group and the polar functional group is a compound represented by the following formulas 10 to 11, stent coating method:
<Formula 1><Formula2><Formula3>

<Formula 4><Formula5><Formula7>

<Formula 7><Formula8><Formula9>

<Formula 10><Formula11>

In the above equations,
R ₁ to R ₁₄ are each independently selected from hydrogen, an alkyl group having 1 to 5 carbon atoms, a vinyl group, an allyl group, or a propargyl group,
At least one of R ₁ to R ₄ is a vinyl group, an allyl group, or a propalyl group,
At least one of R ₆ , R ₇ and R ₉ is a vinyl group, an allyl group, or a propalyl group,
At least one of R ₁₀ to R ₁₄ is a vinyl group, an allyl group, or a propalyl group.
R ₁₅ to R ₂₅ are each independently selected from hydrogen, an alkyl group having 1 to 5 carbon atoms, a hydroxy group, a thiol group, a vinyl group, an allyl group, or a propargyl group,
At least one of R ₁₅ to R ₂₀ is a vinyl group, an allyl group, or a propalyl group, and at least the other is a hydroxy group or a thiol group,
At least one of R ₂₁ to R ₂₆ is a vinyl group, an allyl group, or a propalyl group, and at least the other is a hydroxy group or a thiol group. The method of claim 1, wherein the non-fluorine-based acrylic compound is a compound represented by the following formula (20):
<Formula 20>

In the above formula,
R ₂₇ is hydrogen, methyl group, ethyl group, propyl group, butyl group, hydroxymethyl group, or 2-hydroxyethyl group,
R ₂₈ is hydrogen or a methyl group. The self-assembly of one or more of a non-fluorine-based acrylic compound chemically adsorbed on the stent substrate, an aromatic heterocyclic compound containing an unsaturated functional group, and an aromatic ring compound containing an unsaturated functional group and a polar functional group. It includes a self-assembled layer,
The second coating layer includes a parylene-based polymer grafted to an unsaturated functional group included in the first coating layer,
In the step of disposing the second coating layer, a separate catalyst or initiator other than the parylene-based bulb is not used,
The first coating layer and the second coating layer is a conformal coating layer (conformal coating layer), the stent coating method. The stent coating method according to claim 1, wherein the parylene precursor comprises at least one selected from dimers represented by the following Chemical Formulas 12 to 19:
<Formula 12><Formula13><Formula14><Formula15>

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

The method of claim 1, wherein the parylene-based polymer is Parylene N, Parylene C, Parylene D, Parylene AF-4, Parylene HT, Parylene VT-4, Parylene CF, Parylene A, Parylene AM. , Parylene H, parylene SR, parylene HR, and stent coating method comprising at least one selected from parylene NR. The method of claim 1,
At least one of the non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, and an aromatic ring compound containing an unsaturated functional group and a polar functional group is 25 to 150° C.,
The vaporization temperature of the parylene precursor is 100 to 200 °C, the thermal decomposition temperature of the parylene precursor is 500 to 750 °C,
The temperature of the stent substrate is 20 to 40 ℃, stent coating method. The method of claim 1, wherein the thickness of the first coating layer is 100 nm or less, and the thickness of the second coating layer is 100 nm to 500 μm,
The stent substrate is a metal or non-metallic, stent coating method. Stent substrate;
A first coating layer disposed on at least one of the inside and outside of the stent substrate; And
Includes; a second coating layer disposed on the first coating layer,
The first coating layer comprises at least one selected from a non-fluorine-based acrylic compound, an aromatic heterocyclic compound containing an unsaturated functional group, an aromatic ring compound containing an unsaturated functional group and a polar functional group, and derivatives thereof,
The stent, wherein the second coating layer comprises a parylene-based polymer. The stent according to claim 10, further comprising a polymer layer disposed between or on the second coating layer and the first coating layer and the second coaching layer, wherein the polymer layer contains a drug.

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