WO2022235080A1 - Substrate surface-modified with unsaturated acyclic amine compound and method for surface-modifying same - Google Patents

Substrate surface-modified with unsaturated acyclic amine compound and method for surface-modifying same Download PDF

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WO2022235080A1
WO2022235080A1 PCT/KR2022/006417 KR2022006417W WO2022235080A1 WO 2022235080 A1 WO2022235080 A1 WO 2022235080A1 KR 2022006417 W KR2022006417 W KR 2022006417W WO 2022235080 A1 WO2022235080 A1 WO 2022235080A1
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Prior art keywords
substrate
formula
hydrogen
alkyl
amine compound
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PCT/KR2022/006417
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French (fr)
Korean (ko)
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이경훈
에스.알트하우스 존
박형진
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하이드로메이트 코팅스, 인크.
이경훈
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Publication of WO2022235080A1 publication Critical patent/WO2022235080A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/02—Polyamines

Definitions

  • the present invention relates to a substrate surface-modified with an unsaturated acyclic amine compound or an oligomer or (co)polymer thereof, and a method for modifying the same.
  • the technology for chemically modifying the surface of a substrate is an important technology required in various fields of study and applied technology.
  • Basic methods for such chemical modification include surface treatment reactions and other physicochemical treatment techniques, which can impart desired chemical and/or physical properties onto a substrate surface with little or no activity.
  • most of the compounds used for chemical modification through the surface treatment reaction have chemical functional groups at both ends. It provides functionality.
  • polymer materials widely used throughout industrial fields have light weight, flexibility, processability, insulation and transparency as inherent properties of the polymer material itself. If the polymer surface can be modified to a surface having properties suitable for each application field without changing these intrinsic properties, not only the field of application of the polymer becomes wider, but also the polymer material can be used more effectively.
  • the main reason that polymer materials sometimes have unsuitable surface properties is that the surface tension is low and there is little reactivity. may result in loss.
  • the hydrophilicity of polymeric materials is an important property directly related to the adhesion, biocompatibility, colorability, printability, dyeability and antistatic effect of polymeric materials. . Conversely, if the hydrophobicity of the surface of the polymer material is further increased, water repellency and stain resistance may be improved.
  • Korean Patent Laid-Open Publication No. 10-2003-0009732 describes an organic polymer substrate coated with multiple aminoethyl molecular layers. Specifically, the physicochemical properties of the substrate surface are determined by reacting a substrate composed of various organic polymers or oligomers containing a nucleophilic functional group with aziridine or a derivative thereof to form multiple aminoethyl molecular layers composed of a high-density polymer on the surface of the substrate. Disclosed are a modified organic polymer substrate and a method for preparing the same. However, since the surface modification method through the nucleophilic reaction is adopted, it has a fundamental limitation that a nucleophilic functional group must exist in the substrate.
  • Mussels can adhere to virtually any type of inorganic or organic substrate, and the mussel adhesive protein secreted from the mussel's mussel ends is a representative substrate-independent natural adhesive.
  • Techniques for mimicking the adhesion mechanism of the mussel adhesion protein have been studied and developed, for example, using dopamine or a similar compound containing both catechol and amine groups in an alkaline solution state.
  • U.S. Patent Publication Nos. US8,541,060 and US8,999,452 are directed to a multifunctional coating capable of surface modification independent of a substrate and application examples thereof, using dopamine or a compound similar to dopamine as a surface modifier to react with a substrate in an alkaline solution.
  • a method for modifying the substrate surface by contacting is presented.
  • the surface modification method can be carried out only under alkaline conditions.
  • Most of the experiments are performed in a tris [tris (hydroxymethyl) aminomethane] buffer solution, 10 mM pH 8.5, which is close to the pKa (dissociation constant) value of dopamine, which is about pH 9, so it is difficult to control the reactivity as needed.
  • dopamine or its analog compound has two different reactive groups such as at least two hydroxyl groups and one amino group, so it is difficult to uniformly control the functionality of the modified surface.
  • a large number of amino groups cannot be present, thus limiting the performance of subsequent applications based on the modification of the amine structure.
  • Korean Patent Publication No. 1831613 discloses a polymer on which an aromatic amine-based compound is surface-coated independently of a substrate and a method for coating the surface thereof.
  • the coating method according to the above patent is based on an oxidation-reduction reaction, and thus requires the addition of a compound for the oxidation-reduction reaction, that is, the oxidation of the aromatic amine-based compound, and a basic pH condition for the subsequent reduction reaction. Therefore, there is still a need for a surface modifying compound capable of effectively modifying the surface of a substrate even under milder conditions because it does not require the addition of such a compound and has excellent reactivity.
  • Patent Document 1 Republic of Korea Patent Publication No. 10-2003-0009732
  • Patent Document 2 US Patent Publication No. 8,541,060
  • Patent Document 3 US Patent Publication No. 8,999,452
  • Patent Document 4 Korean Patent Publication No. 1831613
  • an object of the present invention is to provide a substrate modified with an unsaturated acyclic amine compound or an oligomer or (co)polymer thereof.
  • Another object of the present invention is to provide a modification method capable of chemically modifying the surface of a solid substrate independently of the substrate using an unsaturated acyclic amine compound.
  • the present invention reacts an unsaturated acyclic amine compound of the following formula (I) to at least a part of the surface of a substrate with a surface modifier to form a substrate surface-modified with the compound or an oligomer or (co)polymer thereof. to provide.
  • R 1 is hydrogen, C 1 -C 6 alkyl, or —CN
  • R 2 and R 3 are each independently hydrogen, C 1 -C 6 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or a substituent selected from the group consisting of C 1 -C 6 alkyl.
  • X is -NH 2
  • R 1 is hydrogen, C 1 -C 3 alkyl, or —CN
  • R 2 and R 3 are each independently hydrogen, C 1 -C 3 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or C 1 -C 3 alkyl).
  • X is -NH 2
  • R 1 is hydrogen, methyl, or —CN
  • R 2 and R 3 are each independently hydrogen, methyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 , wherein R 4 and R 5 is a substituent selected from the group consisting of hydrogen or methyl.
  • the compound of formula (I) is, for example, methyl 3-aminocrotonic acid, ethyl 3-aminocrotonic acid, N-vinylformamide, 3-aminocrotonitrile, N[(2E)-3- Nitrosobut-2-en-2yl]hydroxyamine, diaminomaleonitrile, 4-aminopent-3-en-2-one.
  • the present inventors have disclosed that in Korean Patent Application Nos. 10-2020-0008102, 10-2020-0008103, 10-2020-0008109 and 10-2020-0008115, respectively, amino unsaturated heterocyclic compounds having specific structures, vinyl hetero
  • a method for modifying the surface of a substrate with a cyclic compound, an amino cycloalkene compound, and a vinyl amino non-aromatic cyclic compound and the invention for the surface-modified substrate have been disclosed.
  • the entire contents of the specification of the above applications are incorporated herein by reference.
  • the unsaturated acyclic amine compound of the present invention does not belong to the formula defined in the preceding applications, and can be used alone as well as in combination with the compounds mentioned in the preceding applications for surface modification.
  • the unsaturated acyclic amine compound is expected to undergo a chain polymerization reaction between the unsaturated acyclic amine compounds at the same time or before or after the nucleophilic reaction by the nucleophile on the substrate surface (refer to Schemes 1 to 3 below) .
  • these predicted reaction pathways are only intended to aid the understanding of the present invention, and the scope of the present invention is not limited or particularly limited by the reaction pathway itself.
  • the present invention comprises the steps of preparing an aqueous solution of an unsaturated acyclic amine compound of formula (I), contacting the aqueous solution with at least a portion of the surface of a substrate, washing and drying the substrate It provides a method for modifying the substrate, characterized in that.
  • R 1 is hydrogen, C 1 -C 6 alkyl, or —CN
  • R 2 and R 3 are each independently hydrogen, C 1 -C 6 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or a substituent selected from the group consisting of C 1 -C 6 alkyl.
  • X is -NH 2
  • R 1 is hydrogen, C 1 -C 3 alkyl, or —CN
  • R 2 and R 3 are each independently hydrogen, C 1 -C 3 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or C 1 -C 3 alkyl).
  • X is -NH 2
  • R 1 is hydrogen, methyl, or —CN
  • R 2 and R 3 are each independently hydrogen, methyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 , wherein R 4 and R 5 is a substituent selected from the group consisting of hydrogen or methyl.
  • the compound of formula (I) is, for example, methyl 3-aminocrotonic acid, ethyl 3-aminocrotonic acid, N-vinylformamide, 3-aminocrotonitrile, N[(2E)-3- Nitrosobut-2-en-2yl]hydroxyamine, diaminomaleonitrile, 4-aminopent-3-en-2-one.
  • the surface of a substrate can be chemically modified independently of the substrate by using an unsaturated acyclic amine compound, and it can be carried out in a simple process without using a special device or treatment means.
  • the unsaturated acyclic amine compound used as a surface modifier has better reactivity than the aromatic amine compound, which is a surface modifier disclosed in the prior invention, so that the surface of the substrate can be effectively modified, and the present inventors first completed the invention.
  • the aromatic amine compound which is a surface modifier disclosed in the prior invention
  • the present inventors first completed the invention.
  • amino unsaturated heterocycle compounds, vinyl heterocycle compounds, amino cycloalkene compounds and vinyl amino non-aromatic cyclic compounds it is advantageous in terms of cost, and can be advantageously applied to applications where toxicity is sensitive, such as food packaging. The advantage exists.
  • oligomer refers to a polymer consisting of a relatively small number of repeating units, approximately 100 or less repeating units.
  • the repeating unit may be composed of the same molecules or may be composed of different molecules.
  • (co)polymer refers to both “polymer” and “copolymer”, and refers to a polymer composed of a larger number of repeating units than an oligomer, and is produced by bonding between different molecules. These are specifically referred to as "copolymers".
  • the form of the copolymer may be in various forms, such as an alternating copolymer, a random copolymer, a block copolymer, and a graft copolymer.
  • modification refers to an unsaturated acyclic amine compound of formula (I) acting as a surface modifier so that the compound, its oligomer or (co)polymer is chemically bonded to the surface of a substrate. means to be attached through
  • a method for modifying a substrate according to the present invention comprises the steps of preparing an aqueous solution of an unsaturated acyclic amine compound of formula (I), contacting the aqueous solution with at least a portion of the substrate surface, washing and drying the substrate characterized in that
  • R 1 is hydrogen, C 1 -C 6 alkyl, or —CN
  • R 2 and R 3 are each independently hydrogen, C 1 -C 6 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or a substituent selected from the group consisting of C 1 -C 6 alkyl.
  • X is -NH 2
  • R 1 is hydrogen, C 1 -C 3 alkyl, or —CN
  • R 2 and R 3 are each independently hydrogen, C 1 -C 3 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or C 1 -C 3 alkyl).
  • X is -NH 2
  • R 1 is hydrogen, methyl, or —CN
  • R 2 and R 3 are each independently hydrogen, methyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 , wherein R 4 and R 5 is a substituent selected from the group consisting of hydrogen or methyl.
  • the compound of formula (I) is, for example, methyl 3-aminocrotonic acid, ethyl 3-aminocrotonic acid, N-vinylformamide, 3-aminocrotonitrile, N[(2E)-3- Nitrosobut-2-en-2yl]hydroxyamine, diaminomaleonitrile, 4-aminopent-3-en-2-one.
  • the aqueous solution of the unsaturated acyclic amine compound of formula (I) may be acidic, neutral or basic.
  • acidic, neutral or basic For example, pure water, buffer (weak acid, neutral or basic), NaOH solution (0.01 M, 0.1 M or 1 M), or 15-20% DMEA (N,N-dimethylamine: CAS 598-56) -1; salt free, pH 13-14), etc. can be used as a solvent, and are not particularly limited thereto.
  • An aqueous solution is prepared by adding the compound of formula (I) to these solvents.
  • the concentration of the solution is not particularly limited, and can be appropriately adjusted depending on the solute and solvent used and other reaction conditions.
  • the concentration of the solution may be 0.1 to 10 mg/mL.
  • the solution prepared as described above is filled in a container having a volume sufficient to accommodate the substrate to be modified, and then the substrate to be modified is immersed in the aqueous solution.
  • any method other than immersing the substrate in the aqueous solution is possible.
  • it is possible to contact the aqueous solution with the substrate by spraying the aqueous solution on the surface of the substrate or using a method used in various coating processes so that the surface of the substrate can sufficiently contact the aqueous solution.
  • Modification according to the present invention can be performed only by incubation treatment in which the substrate and the aqueous solution are left in contact for a certain period of time.
  • the aqueous solution of the compound of formula (I) may be stirred or heated to activate the binding reaction with the substrate.
  • a catalyst when a catalyst can be used, a catalyst for accelerating the reaction may be added, but it is not necessary.
  • the reaction time and reaction temperature are not particularly limited, and a person skilled in the art may appropriately select and adjust it according to the type of the specific compound used and the type of the substrate.
  • the reaction temperature may be 50° C. to 100° C.
  • the reaction time may be 6 to 48 hours, but is not limited thereto.
  • the substrate After incubation for a period of time, the substrate is washed to remove bound or unpolymerized compounds of formula (I) or impurities. After washing, it is dried at room temperature or elevated temperature to obtain a surface-modified substrate.
  • the substrate may be glass, wood, stone, metal, ceramic, natural or synthetic polymer, and the like, and is not particularly limited.
  • Metal substrates include, but are not particularly limited to, iron, copper, aluminum, zinc, tin, silver, gold, titanium, tungsten, nickel, molybdenum, cobalt, magnesium, and alloys thereof.
  • Ceramics are inorganic compounds of metals, nonmetals or metalloids, for example, zinc oxide, zirconium oxide, titanium oxide, aluminum borate, iron oxide, calcium carbonate, barium carbonate, lead oxide, tin oxide, cerium oxide, lithium oxide, calcium oxide, Magnesium oxide, trimanganese tetraoxide, niobium oxide, tantalum oxide, tungsten oxide, antimony oxide, aluminum phosphate, calcium silicate, zirconium silicate, ITO (indium oxide with tin), titanium silicate, barium titanate, strontium titanate, calcium titanate, montmorillonite, sandpaper Nit, vermiclite, hydrotalcite, kaolinite, kanemite, margadiite, kenyite, silica, alumina, zeolite, lithium nitride, lithium silicate, lithium borate, lithium aluminate, lithium phosphate, lithium phosphorus oxynite Lithium, lithium silicon s
  • Natural polymers include, for example, starch, cellulose, chitosan, chitin, gelatin, pectin, carrageenan, dextran, collagen, hyaluronic acid, alginate, gluten, fibrin, agarose, and the like, but are not particularly limited thereto.
  • Synthetic polymers include all general-purpose thermoplastic polymers, thermosetting polymers, engineering polymers, elastomers, etc., for example, polyolefins including polyethylene, polypropylene, polymethylpentene, polybutene-1, etc., polyisobutylene, ethylene-propylene rubber , polyolefin elastomers including ethylene-propylene-diene rubber (EPDM), etc., halogenated polyolefins including polyvinyl chloride, polyvinylidene chloride, polychlorotrifluoroethylene, polyvinylidene fluoride, polytetrafluoroethylene, etc.
  • polyolefins including polyethylene, polypropylene, polymethylpentene, polybutene-1, etc.
  • polyisobutylene ethylene-propylene rubber
  • polyolefin elastomers including ethylene-propylene-diene rubber (EPDM), etc.
  • halogenated polyolefins
  • Polyester including polystyrene, polyvinyl alcohol, polyacetal, polyvinyl acetate, polyacrylonitrile, polybutadiene, polyisoprene, phenol resin, epoxy resin, polyamide, polyethylene terephthalate and polybutylene terephthalate; Polyimide, polyamideimide, polyetherimide, polyacrylate, polyurethane, polysiloxane, polynaphthalene, polythiophene, polyaniline, polyparaphenylene sulfide, polychloroprene, styrene-butadiene rubber, nitrile rubber, silicone rubber and these of copolymers, and the like, and are not particularly limited thereto.
  • the shape of the substrate may also be a powder, a bead, a plate, a rod, a tube, or any three-dimensional shape, and is not particularly limited. It is also possible, if necessary, to modify only a part of the substrate by contacting only part of the substrate with an aqueous solution of the compound of formula (I).
  • Example 1 Modification of 3-aminocrotonic acid methyl on glass slides in weakly basic solution at room temperature
  • Methyl 3-aminocrotonic acid was added to borate buffer (50 mM) of pH 9.0 to prepare a solution having a concentration of 1 mg/1mL. Glass slides were immersed in the solution at room temperature for 20 hours. The glass slides were taken out and placed in an oven at 70° C. for 3 hours and then washed with NaOH solution for 20 seconds. Then, it was washed with a sufficient amount of water and dried at 70° C. for 5 minutes. Again, the glass slide was washed with HCl solution for 20 seconds, washed with a sufficient amount of water, and then dried at 70° C. for 5 minutes.
  • Glass slides having the same specifications as those used in Example 1 were immersed in borate buffer (50 mM) of pH 9.0 at room temperature for 20 hours. The glass slides were taken out and placed in an oven at 70° C. for 3 hours and then washed with NaOH solution for 20 seconds. Then, it was washed with a sufficient amount of water and dried at 70° C. for 5 minutes. Again, the glass slide was washed with HCl solution for 20 seconds, washed with a sufficient amount of water, and then dried at 70° C. for 5 minutes.
  • borate buffer 50 mM
  • Example 2 Modification of 3-aminocrotonic acid methyl on glass slides in strong basic solution at room temperature
  • Methyl 3-aminocrotonic acid was added to an 8% aqueous solution of dimethylethanolamine having a pH of 13 to prepare a solution having a concentration of 1 mg/1 mL.
  • Glass slides were immersed in the solution at room temperature for 12 hours. The glass slides were taken out and placed in an oven at 70° C. for 3 hours and then washed with NaOH solution for 20 seconds. Then, it was washed with a sufficient amount of water and dried at 70° C. for 5 minutes. Again, the glass slide was washed with HCl solution for 20 seconds, washed with a sufficient amount of water, and then dried at 70° C. for 5 minutes.
  • Glass slides having the same specifications as those used in Example 2 were immersed in borate buffer (50 mM) of pH 9.0 at room temperature for 12 hours. The glass slides were taken out and placed in an oven at 70° C. for 3 hours and then washed with NaOH solution for 20 seconds. Then, it was washed with a sufficient amount of water and dried at 70° C. for 5 minutes. Again, the glass slide was washed with HCl solution for 20 seconds, washed with a sufficient amount of water, and then dried at 70° C. for 5 minutes.
  • borate buffer 50 mM
  • Example 3 Modification of 3-aminocrotonic acid methyl on polyimide film in weakly basic solution at room temperature
  • a surface-modified film was prepared in the same manner as in Example 1, except that a polyimide (PI) film was used.
  • PI polyimide
  • a sample was prepared in the same manner as in Comparative Example 1, except that a polyimide (PI) film was used.
  • PI polyimide
  • Example 4 Modification of 3-aminocrotonic acid methyl on polyimide film in strong basic solution at room temperature
  • a surface-modified film was prepared in the same manner as in Example 2, except that a polyimide (PI) film was used.
  • PI polyimide
  • a sample was prepared in the same manner as in Comparative Example 2, except that a polyimide (PI) film was used.
  • PI polyimide
  • Example 5 Modification of 3-aminocrotonic acid methyl on polyethylene film in weakly basic solution at room temperature
  • a surface-modified film was prepared in the same manner as in Example 1, except that a polyethylene (PE) film for food packaging (a composite film in which a printing film and an aluminum film are present between the polyethylene films on both sides) was used.
  • PE polyethylene
  • a sample was prepared in the same manner as in Comparative Example 1, except that a polyethylene (PE) film for food packaging was used.
  • PE polyethylene
  • Example 6 Modification of 3-aminocrotonic acid methyl on polyethylene film in strong basic solution at room temperature
  • a surface-modified film was prepared in the same manner as in Example 2, except that a polyethylene (PE) film for food packaging was used.
  • PE polyethylene
  • a sample was prepared in the same manner as in Comparative Example 2, except that a polyethylene (PE) film for food packaging was used.
  • PE polyethylene
  • a goniometer (model 300) from Ramehart Instruments, New Jersey, USA was used. A droplet of 2 ⁇ l of the sample solution (15% aqueous solution of dimethylethanolamine or distilled shoe) was placed on the surface of the sample on the goniometer sample stage using a micro-injector. After taking a side picture that shows the contact state between the droplet of the sample solution placed on the sample stage of the goniometer and the sample surface, the quantitative information of the contact angle is obtained using the DROPImage software of the goniometer. The contact angle was measured in this way.
  • Tables 1 to 6 show the results of measuring the contact angles for all of the sample films of Examples and each of the sample films of Comparative Examples in the same manner as above.
  • "Drip solution” means a sample solution used for measuring the contact angle.
  • Example 3 Sample and Comparative Example 3 Contact Angle Measurement Results Drops: water
  • Example 3 Comparative Example 3 One 66.2 ⁇ 73.0 ⁇ 2 69.8 ⁇ 70.6 ⁇ 3 65.8 ⁇ 65.4 ⁇ 4 67.5 ⁇ 73.0 ⁇ 5 80.4 ⁇ 67.6 ⁇ Average 69.9 ⁇ 69.9 ⁇
  • Example 4 Sample and Comparative Example 4 Contact Angle Measurement Results Drops: water Drops: 15% DMEA aqueous solution
  • Example 4 Comparative Example 4 Example 4 Comparative Example 4 One 78.0 ⁇ ⁇ 10 ⁇ 31.9 ⁇ - 2 68.8 ⁇ ⁇ 10 ⁇ 30.0 ⁇ 21.8 ⁇ 3 66.6 ⁇ ⁇ 15 ⁇ 23.9 ⁇ 25.8 ⁇ 4 61.2 ⁇ - 36.6 ⁇ 28.3 ⁇ 5 69.0 ⁇ - 37.3 ⁇ 33.0 ⁇ Average 68.7 ⁇ ⁇ 15 ⁇ 31.9 ⁇ 27.2 ⁇
  • the hydrophobic coating was provided when the unsaturated acyclic amine compound was used for surface modification of various substrates. It was confirmed that the properties of the modified surface can vary depending on a specific substrate and surface modification conditions, and it is possible to adjust the properties of the modified surface by appropriately selecting the unsaturated acyclic amine compound used for surface modification. A person skilled in the art will be able to optimize suitable compounds and surface modification conditions to obtain a substrate surface having desired properties from the above experimental results.
  • the present invention relates to a substrate in which an unsaturated acyclic amine compound or an oligomer or (co)polymer thereof is surface-modified independently of a substrate and a method for modifying the same, and can be used for chemical surface modification of various substrates.
  • it is possible to impart suitable hydrophobicity to the surface of the material used in applications where hydrophobicity is required, and vice versa.
  • it is possible to improve the separation yield and reliability of biochemicals by modifying the chemical properties of one interface to improve the adhesion between the interfaces, or by using a modified compound appropriately selected to match the properties of the biochemical to be fixed and/or separated.
  • the industrial fields in which the present invention can be used are limitless.

Abstract

The present invention relates to: a substrate of which the surface is at least partially modified with an unsaturated acyclic amine compound or an oligomer or (co)polymer thereof; and a method for surface-modifying same. The present invention also provides a method for surface-treating the substrate, the method comprising the steps of: providing an aqueous solution of an unsaturated acyclic amine compound; bringing the aqueous solution into contact with at least a portion of the surface of the substrate; and washing and drying the substrate.

Description

불포화 비고리 아민 화합물로 표면 개질된 기질 및 그의 표면 개질 방법Substrate surface-modified with unsaturated acyclic amine compound and method for surface modification thereof
본 발명은 불포화 비고리 아민 화합물 또는 그의 올리고머 또는 (공)중합체로 표면 개질된 기질 및 그 개질 방법에 관한 것이다.The present invention relates to a substrate surface-modified with an unsaturated acyclic amine compound or an oligomer or (co)polymer thereof, and a method for modifying the same.
기질의 표면을 화학적으로 개질시키는 기술은 다양한 학문 및 응용기술 분야에서 요구되는 중요한 기술이다. 그러한 화학적 개질에 대한 기본적인 방법은 표면 처리 반응과 기타 물리화학적 처리 기술들을 포함하는데, 이러한 방법에 의해 활성이 거의 없거나 전혀 없는 기질 표면상에 원하는 화학적 및/또는 물리적 특성들을 부여할 수 있다. 특히 표면 처리 반응을 통한 화학적 개질에 사용되는 화합물들은 대부분 양 말단에 화학적 작용기를 가지는데, 한쪽 말단의 작용기는 화학 반응을 통해 기질에 부착되고, 다른 쪽 말단의 작용기는 그 자체로 기질 표면에 화학적 기능성을 부여하는 역할을 한다.The technology for chemically modifying the surface of a substrate is an important technology required in various fields of study and applied technology. Basic methods for such chemical modification include surface treatment reactions and other physicochemical treatment techniques, which can impart desired chemical and/or physical properties onto a substrate surface with little or no activity. In particular, most of the compounds used for chemical modification through the surface treatment reaction have chemical functional groups at both ends. It provides functionality.
다양한 기질 중 특히 전반적인 산업분야에 걸쳐 널리 사용되는 고분자 재료의 경우 고분자 재료 자체의 고유 성질로 경량성, 유연성, 가공성, 절연성 및 투명성 등을 갖는다. 이러한 고유 성질은 변화시키지 않으면서 각각의 응용분야에 적합한 성질을 갖는 표면으로 고분자 표면을 개질시킬 수 있다면 고분자의 활용 분야가 더욱 넓어질 뿐만 아니라, 고분자 재료를 더욱 효과적으로 사용할 수 있다. 고분자 재료가 때때로 부적합한 표면 성질을 갖게 되는 주된 이유는 표면 장력이 낮고 반응성이 거의 없기 때문이므로, 고분자 재료의 표면 장력을 높이거나 반응성을 갖는 작용기의 분포를 늘릴 수 있다면 고분자 재료의 활용 분야가 매우 넓어지는 결과를 가져올 수 있다. 특히, 고분자 재료의 친수성(hydrophilicity)은 고분자 재료의 접착력, 생체 적합성, 착색성, 인쇄성, 염색성 및 정전기 방지 효과와 직접 관련되는 중요한 성질이므로 친수성이 보다 강한 표면을 만들고자 다양한 표면 개질 기술이 개발되고 있다. 반대로 고분자 재료 표면의 소수성(hydrophobicity)을 더욱 증대시키면 발수성, 내오염성 등을 향상시키는 결과를 가져올 수 있다.Among various substrates, polymer materials widely used throughout industrial fields, in particular, have light weight, flexibility, processability, insulation and transparency as inherent properties of the polymer material itself. If the polymer surface can be modified to a surface having properties suitable for each application field without changing these intrinsic properties, not only the field of application of the polymer becomes wider, but also the polymer material can be used more effectively. The main reason that polymer materials sometimes have unsuitable surface properties is that the surface tension is low and there is little reactivity. may result in loss. In particular, the hydrophilicity of polymeric materials is an important property directly related to the adhesion, biocompatibility, colorability, printability, dyeability and antistatic effect of polymeric materials. . Conversely, if the hydrophobicity of the surface of the polymer material is further increased, water repellency and stain resistance may be improved.
그런데 기질의 표면을 개질하기 위해 화학적 처리를 하는 경우 기질 자체의 성질에 의해 제한되는 경우가 많다. 예컨대 친핵성 반응을 통해 기질 표면을 개질하고자 하는 경우, 기질 자체에 친핵성 반응기가 존재하지 않거나 매우 낮은 농도로 존재하면 효과적인 개질이 이루어지기 어려우므로 기질내에 친핵성 반응기를 미리 도입하는 단계가 필요하다. 이러한 추가 단계는 시간과 비용적인 면에서 결코 바람직하지 않으며, 기질내에 도입된 친핵성 반응기를 갖는 물질들이 시간이 경과함에 따라 기질 표면으로 이동하는 현상에 의해 개질된 표면의 성질이 변화하는 문제점도 갖고 있다. 따라서 기질에 의존하지 않는 표면개질 방법의 요구가 절실하다.However, in the case of chemical treatment to modify the surface of the substrate, it is often limited by the nature of the substrate itself. For example, in the case of modifying the surface of a substrate through a nucleophilic reaction, if there is no nucleophilic reactive group in the substrate itself or is present at a very low concentration, effective modification is difficult, so a step of introducing a nucleophilic reactive group into the substrate in advance is required. . Such an additional step is not preferable in terms of time and cost, and there is also a problem in that the properties of the modified surface are changed by the phenomenon that materials having a nucleophilic reactive group introduced into the substrate migrate to the substrate surface over time. have. Therefore, there is an urgent need for a surface modification method that does not depend on a substrate.
대한민국 공개특허공보 제10-2003-0009732호는 다중 아미노에틸 분자층으로 표면을 코팅한 유기고분자기질에 대해 기술하고 있다. 구체적으로, 친핵성 작용기를 함유한 다양한 유기 고분자 또는 올리고머로 이루어진 기질을 아지리딘 혹은 그 유도체와 반응시켜 기질의 표면상에 고밀도 중합체로 이루어진 다중 아미노에틸 분자층을 형성함으로써 기질 표면의 이화학적 특성을 변화시킨 유기 고분자 기질 및 그 제조방법을 개시하고 있다. 그러나 친핵성 반응을 통한 표면 개질방법을 채택하고 있어서 기질내에 친핵성 작용기가 존재해야 하는 근본적인 제약을 가지고 있다.Korean Patent Laid-Open Publication No. 10-2003-0009732 describes an organic polymer substrate coated with multiple aminoethyl molecular layers. Specifically, the physicochemical properties of the substrate surface are determined by reacting a substrate composed of various organic polymers or oligomers containing a nucleophilic functional group with aziridine or a derivative thereof to form multiple aminoethyl molecular layers composed of a high-density polymer on the surface of the substrate. Disclosed are a modified organic polymer substrate and a method for preparing the same. However, since the surface modification method through the nucleophilic reaction is adopted, it has a fundamental limitation that a nucleophilic functional group must exist in the substrate.
홍합은 실질적으로 모든 유형의 무기 또는 유기 기질에 접착할 수 있는데, 홍합의 족사(足絲) 말단에서 분비되는 홍합 접착 단백질은 대표적인 기질 비의존적인 천연 접착제이다. 이러한 홍합 접착 단백질의 접착 메카니즘을 연구하여 이를 모방하는 기술들도 개발되고 있는데, 예컨대 카테콜과 아민기 모두를 함유하는 도파민 또는 이와 유사한 화합물을 알칼리 용액 상태로 사용하는 것이다. 미국 특허공보 US8,541,060호 및 US8,999,452호는 기질에 비의존적으로 표면 개질할 수 있는 다기능 코팅 및 그 적용예에 대한 것으로서, 도파민 또는 도파민과 유사한 화합물을 표면 개질제로 이용하여 알칼리 용액에서 기질과 접촉시켜 기질 표면을 개질하는 방법을 제시하고 있다. 그러나 도파민 또는 도파민 유사체를 이용하는 기초한 기술에는 여러가지 기술적 제한들이 존재한다. 우선 상기 특허공보에도 기재되어 있듯이 상기 표면 개질 방법은 알칼리 조건 하에서만 실행될 수 있다. 대다수의 실험들이 트리스[tris(hydroxymethyl)aminomethane] 완충용액 10 mM pH 8.5에서 수행되는데, 상기 값은 대략 pH 9정도인 도파민의 pKa(해리상수) 값에 가까우므로, 필요에 따른 반응도를 제어하기 어려운 문제점이 있다. 또한, 도파민 또는 그의 유사체 화합물은 적어도 2개의 히드록실기와 1개의 아미노기와 같은 두 종류의 다른 반응기들을 가지고 있어, 개질된 표면의 기능성을 일정하게 제어하기 어렵다. 마지막으로, 상기 방법에 사용한 화합물의 화학 구조상 아미노기가 다수 존재할 수 없고, 그에 따라 아민 구조의 개질을 기초로 하는 후속 적용예들의 성능이 제한된다.Mussels can adhere to virtually any type of inorganic or organic substrate, and the mussel adhesive protein secreted from the mussel's mussel ends is a representative substrate-independent natural adhesive. Techniques for mimicking the adhesion mechanism of the mussel adhesion protein have been studied and developed, for example, using dopamine or a similar compound containing both catechol and amine groups in an alkaline solution state. U.S. Patent Publication Nos. US8,541,060 and US8,999,452 are directed to a multifunctional coating capable of surface modification independent of a substrate and application examples thereof, using dopamine or a compound similar to dopamine as a surface modifier to react with a substrate in an alkaline solution. A method for modifying the substrate surface by contacting is presented. However, there are several technical limitations to the technology based on dopamine or dopamine analogs. First, as described in the above patent publication, the surface modification method can be carried out only under alkaline conditions. Most of the experiments are performed in a tris [tris (hydroxymethyl) aminomethane] buffer solution, 10 mM pH 8.5, which is close to the pKa (dissociation constant) value of dopamine, which is about pH 9, so it is difficult to control the reactivity as needed. There is a problem. In addition, dopamine or its analog compound has two different reactive groups such as at least two hydroxyl groups and one amino group, so it is difficult to uniformly control the functionality of the modified surface. Finally, in the chemical structure of the compound used in the above method, a large number of amino groups cannot be present, thus limiting the performance of subsequent applications based on the modification of the amine structure.
대한민국 특허공보 제1831613호는 방향족 아민계 화합물이 기질 독립적으로 표면 코팅된 폴리머 및 그 표면 코팅방법을 개시하고 있다. 상기 특허에 따른 코팅방법은 산화-환원 반응에 기초한 것이어서 산화-환원 반응을 일으키기 위한 화합물의 추가, 즉 방향족 아민계 화합물의 산화를 촉진하고 이후의 환원반응을 위한 염기성 pH 조건을 필요로 한다. 따라서 이러한 화합물의 추가가 필요치 않으며 반응성이 우수하여 보다 온화한 조건하에서도 기질의 표면을 효과적으로 개질할 수 있는 표면개질 화합물의 요구가 여전히 존재한다.Korean Patent Publication No. 1831613 discloses a polymer on which an aromatic amine-based compound is surface-coated independently of a substrate and a method for coating the surface thereof. The coating method according to the above patent is based on an oxidation-reduction reaction, and thus requires the addition of a compound for the oxidation-reduction reaction, that is, the oxidation of the aromatic amine-based compound, and a basic pH condition for the subsequent reduction reaction. Therefore, there is still a need for a surface modifying compound capable of effectively modifying the surface of a substrate even under milder conditions because it does not require the addition of such a compound and has excellent reactivity.
[선행기술문헌][Prior art literature]
[특허문헌][Patent Literature]
(특허문헌 1) 대한민국 공개특허공보 제10-2003-0009732호(Patent Document 1) Republic of Korea Patent Publication No. 10-2003-0009732
(특허문헌 2) 미국 특허공보 US 8,541,060호(Patent Document 2) US Patent Publication No. 8,541,060
(특허문헌 3) 미국 특허공보 US 8,999,452호(Patent Document 3) US Patent Publication No. 8,999,452
(특허문헌 4) 대한민국 특허공보 제1831613호(Patent Document 4) Korean Patent Publication No. 1831613
상기와 같은 문제점을 해결하기 위해, 본 발명은 불포화 비고리 아민 화합물 또는 그의 올리고머 또는 (공)중합체로 개질된 기질을 제공하는 것을 목적으로 한다.In order to solve the above problems, an object of the present invention is to provide a substrate modified with an unsaturated acyclic amine compound or an oligomer or (co)polymer thereof.
또한, 본 발명은 불포화 비고리 아민 화합물을 사용하여 기질에 비의존적으로 고형 기질의 표면을 화학적으로 개질할 수 있는 개질방법을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide a modification method capable of chemically modifying the surface of a solid substrate independently of the substrate using an unsaturated acyclic amine compound.
상기의 목적을 달성하기 위해 본 발명은 기질 표면의 적어도 일부에 하기 화학식 (I)의 불포화 비고리 아민 화합물을 표면개질제로 반응시켜, 상기 화합물 또는 그의 올리고머 또는 (공)중합체로 표면개질된 기질을 제공한다.In order to achieve the above object, the present invention reacts an unsaturated acyclic amine compound of the following formula (I) to at least a part of the surface of a substrate with a surface modifier to form a substrate surface-modified with the compound or an oligomer or (co)polymer thereof. to provide.
<화학식 (I)><Formula (I)>
Figure PCTKR2022006417-appb-I000001
Figure PCTKR2022006417-appb-I000001
상기 식에서,In the above formula,
X는 -NH2, -N=CH-OH, 또는 -N=O이고,X is -NH 2 , -N=CH-OH, or -N=O,
R1은 수소, C1-C6 알킬, 또는 -CN이며,R 1 is hydrogen, C 1 -C 6 alkyl, or —CN,
R2 및 R3은 각각 독립적으로 수소, C1-C6알킬, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 C1-C6알킬임)로 이루어진 군에서 선택되는 치환기이다. R 2 and R 3 are each independently hydrogen, C 1 -C 6 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or a substituent selected from the group consisting of C 1 -C 6 alkyl.
바람직하게는, 상기 화학식 (I)에서,Preferably, in the formula (I),
X는 -NH2이고,X is -NH 2 ,
R1은 수소, C1-C3 알킬, 또는 -CN이며R 1 is hydrogen, C 1 -C 3 alkyl, or —CN
R2 및 R3은 각각 독립적으로 수소, C1-C3알킬, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 C1-C3알킬임)로 이루어진 군에서 선택되는 치환기이다. R 2 and R 3 are each independently hydrogen, C 1 -C 3 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or C 1 -C 3 alkyl).
더욱 바람직하게는, 상기 화학식 (I)에서,More preferably, in the formula (I),
X는 -NH2이고,X is -NH 2 ,
R1은 수소, 메틸, 또는 -CN이며R 1 is hydrogen, methyl, or —CN
R2 및 R3은 각각 독립적으로 수소, 메틸, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 메틸임)로 이루어진 군에서 선택되는 치환기이다. R 2 and R 3 are each independently hydrogen, methyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 , wherein R 4 and R 5 is a substituent selected from the group consisting of hydrogen or methyl.
가장 바람직하게는, 상기 화학식 (I)의 화합물은 예컨대, 3-아미노크로톤산 메틸, 3-아미노크로톤산 에틸, N-비닐포름아미드, 3-아미노크로토니트릴, N[(2E)-3-니트로소부트-2-엔-2일]하이드록시아민, 디아미노말레오니트릴, 4-아미노펜트-3-엔-2-온으로 이루어진 군으로부터 선택되는 화합물이다.Most preferably, the compound of formula (I) is, for example, methyl 3-aminocrotonic acid, ethyl 3-aminocrotonic acid, N-vinylformamide, 3-aminocrotonitrile, N[(2E)-3- Nitrosobut-2-en-2yl]hydroxyamine, diaminomaleonitrile, 4-aminopent-3-en-2-one.
본 발명자들은 대한민국 특허출원 제10-2020-0008102호, 제10-2020-0008103호, 제10-2020-0008109호 및 10-2020-0008115호에서 각각 특정 구조를 갖는 아미노 불포화 헤테로사이클 화합물, 비닐 헤테로사이클 화합물, 아미노 사이클로알켄 화합물 및 비닐 아미노 비방향족고리 화합물로 기질의 표면을 개질하는 방법 및 표면개질된 기질에 대한 발명을 개시한 바 있다. 상기 출원들의 명세서 전체 기재 내용은 본 출원에 참고로 인용한다. 본 발명의 불포화 비고리 아민 화합물은 상기 선행출원들에 정의된 화학식에 속하지 않으며, 단독으로는 물론 상기 선행출원들에 언급된 화합물들과 함께 표면 개질에 사용될 수 있다.The present inventors have disclosed that in Korean Patent Application Nos. 10-2020-0008102, 10-2020-0008103, 10-2020-0008109 and 10-2020-0008115, respectively, amino unsaturated heterocyclic compounds having specific structures, vinyl hetero A method for modifying the surface of a substrate with a cyclic compound, an amino cycloalkene compound, and a vinyl amino non-aromatic cyclic compound and the invention for the surface-modified substrate have been disclosed. The entire contents of the specification of the above applications are incorporated herein by reference. The unsaturated acyclic amine compound of the present invention does not belong to the formula defined in the preceding applications, and can be used alone as well as in combination with the compounds mentioned in the preceding applications for surface modification.
본 발명에 따르면, 불포화 비고리 아민 화합물은 기질 표면의 친핵체에 의한 친핵성 반응과 동시에, 또는 그 전후에 불포화 비고리 아민 화합물들간의 연쇄 중합 반응이 일어나는 것으로 예상된다(하기 반응식 1 내지 3 참조). 그러나, 이러한 예상 반응 경로는 본 발명의 이해를 돕기 위한 것일 뿐, 본 발명의 범위가 이러한 반응 경로 자체에 의해 구속되거나 특별히 한정되지는 않는다.According to the present invention, the unsaturated acyclic amine compound is expected to undergo a chain polymerization reaction between the unsaturated acyclic amine compounds at the same time or before or after the nucleophilic reaction by the nucleophile on the substrate surface (refer to Schemes 1 to 3 below) . However, these predicted reaction pathways are only intended to aid the understanding of the present invention, and the scope of the present invention is not limited or particularly limited by the reaction pathway itself.
<반응식 1><Scheme 1>
Figure PCTKR2022006417-appb-I000002
Figure PCTKR2022006417-appb-I000002
<반응식 2><Scheme 2>
Figure PCTKR2022006417-appb-I000003
Figure PCTKR2022006417-appb-I000003
<반응식 3><Scheme 3>
Figure PCTKR2022006417-appb-I000004
Figure PCTKR2022006417-appb-I000004
본 발명의 또 다른 일면에 따라, 하기 화학식 (I)의 불포화 비고리 아민 화합물의 수용액을 제조하는 단계, 상기 수용액을 기질 표면의 적어도 일부에 접촉시키는 단계, 상기 기질을 세척 및 건조하는 단계를 포함하는 것을 특징으로 하는 기질의 개질방법을 제공한다.According to another aspect of the present invention, it comprises the steps of preparing an aqueous solution of an unsaturated acyclic amine compound of formula (I), contacting the aqueous solution with at least a portion of the surface of a substrate, washing and drying the substrate It provides a method for modifying the substrate, characterized in that.
<화학식 (I)><Formula (I)>
Figure PCTKR2022006417-appb-I000005
Figure PCTKR2022006417-appb-I000005
상기 식에서,In the above formula,
X는 -NH2, -N=CH-OH, 또는 -N=O이고,X is -NH 2 , -N=CH-OH, or -N=O,
R1은 수소, C1-C6 알킬, 또는 -CN이며,R 1 is hydrogen, C 1 -C 6 alkyl, or —CN,
R2 및 R3은 각각 독립적으로 수소, C1-C6알킬, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 C1-C6알킬임)로 이루어진 군에서 선택되는 치환기이다. R 2 and R 3 are each independently hydrogen, C 1 -C 6 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or a substituent selected from the group consisting of C 1 -C 6 alkyl.
바람직하게는, 상기 화학식 (I)에서,Preferably, in the formula (I),
X는 -NH2이고,X is -NH 2 ,
R1은 수소, C1-C3 알킬, 또는 -CN이며R 1 is hydrogen, C 1 -C 3 alkyl, or —CN
R2 및 R3은 각각 독립적으로 수소, C1-C3알킬, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 C1-C3알킬임)로 이루어진 군에서 선택되는 치환기이다. R 2 and R 3 are each independently hydrogen, C 1 -C 3 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or C 1 -C 3 alkyl).
더욱 바람직하게는, 상기 화학식 (I)에서,More preferably, in the formula (I),
X는 -NH2이고,X is -NH 2 ,
R1은 수소, 메틸, 또는 -CN이며R 1 is hydrogen, methyl, or —CN
R2 및 R3은 각각 독립적으로 수소, 메틸, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 메틸임)로 이루어진 군에서 선택되는 치환기이다. R 2 and R 3 are each independently hydrogen, methyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 , wherein R 4 and R 5 is a substituent selected from the group consisting of hydrogen or methyl.
가장 바람직하게는, 상기 화학식 (I)의 화합물은 예컨대, 3-아미노크로톤산 메틸, 3-아미노크로톤산 에틸, N-비닐포름아미드, 3-아미노크로토니트릴, N[(2E)-3-니트로소부트-2-엔-2일]하이드록시아민, 디아미노말레오니트릴, 4-아미노펜트-3-엔-2-온으로 이루어진 군으로부터 선택되는 화합물이다.Most preferably, the compound of formula (I) is, for example, methyl 3-aminocrotonic acid, ethyl 3-aminocrotonic acid, N-vinylformamide, 3-aminocrotonitrile, N[(2E)-3- Nitrosobut-2-en-2yl]hydroxyamine, diaminomaleonitrile, 4-aminopent-3-en-2-one.
본 발명에 따르면 불포화 비고리 아민 화합물을 사용하여 기질에 비의존적으로 기질의 표면을 화학적으로 개질할 수 있으며, 특별한 장치나 처리수단을 사용하지 않고도 간단한 공정으로 수행할 수 있다.According to the present invention, the surface of a substrate can be chemically modified independently of the substrate by using an unsaturated acyclic amine compound, and it can be carried out in a simple process without using a special device or treatment means.
또한, 본 발명은 표면 개질제로 사용하는 불포화 비고리 아민 화합물은 선행 발명에 개시된 표면 개질제인 방향족 아민계 화합물에 비해 반응성이 보다 우수하여 기질의 표면을 효과적으로 개질할 수 있고, 본 발명자들이 먼저 완성한 발명인 아미노 불포화 헤테로사이클 화합물, 비닐 헤테로사이클 화합물, 아미노 사이클로알켄 화합물 및 비닐 아미노 비방향족고리 화합물과 대비하여 비용적인 측면에서 유리하고, 예컨대 식품 포장재와 같이 독성 문제가 민감한 적용분야에 유리하게 적용할 수 있는 이점이 존재한다.In addition, in the present invention, the unsaturated acyclic amine compound used as a surface modifier has better reactivity than the aromatic amine compound, which is a surface modifier disclosed in the prior invention, so that the surface of the substrate can be effectively modified, and the present inventors first completed the invention. Compared to amino unsaturated heterocycle compounds, vinyl heterocycle compounds, amino cycloalkene compounds and vinyl amino non-aromatic cyclic compounds, it is advantageous in terms of cost, and can be advantageously applied to applications where toxicity is sensitive, such as food packaging. The advantage exists.
본 명세서에 사용된 "올리고머"라는 용어는 비교적 적은 수의 반복단위, 대략 100 이하의 반복단위로 이루어진 중합체를 의미한다. 이때 반복단위는 동일한 분자들로 이루어질 수 있거나 서로 상이한 분자들로 이루어질 수도 있다. As used herein, the term "oligomer" refers to a polymer consisting of a relatively small number of repeating units, approximately 100 or less repeating units. In this case, the repeating unit may be composed of the same molecules or may be composed of different molecules.
본 명세서에 사용된 "(공)중합체"라는 용어는 "중합체"와 "공중합체"를 함께 일컫는 용어로서, 올리고머보다 많은 수의 반복단위로 이루어진 중합체를 의미하며, 상이한 분자들간의 결합에 의해 생성된 것을 특히 "공중합체"라 지칭한다. 공중합체의 형태는 교호 공중합체(alternating copolymer), 랜덤 공중합체(random copolymer), 블록 공중합체(block copolymer), 그래프트 공중합체(graft copolymer) 등 다양한 형태가 가능하다.As used herein, the term “(co)polymer” refers to both “polymer” and “copolymer”, and refers to a polymer composed of a larger number of repeating units than an oligomer, and is produced by bonding between different molecules. These are specifically referred to as "copolymers". The form of the copolymer may be in various forms, such as an alternating copolymer, a random copolymer, a block copolymer, and a graft copolymer.
본 명세서에 사용된 "개질" 또는 "표면개질"이라는 용어는 화학식 (I)의 불포화 비고리 아민 화합물을 표면 개질제로 작용시켜 기질의 표면에 상기 화합물, 그의 올리고머 또는 (공)중합체가 화학적 결합을 통해 부착되는 것을 의미한다.As used herein, the term "modification" or "surface modification" refers to an unsaturated acyclic amine compound of formula (I) acting as a surface modifier so that the compound, its oligomer or (co)polymer is chemically bonded to the surface of a substrate. means to be attached through
본 발명에 따른 기질의 개질방법은 화학식 (I)의 불포화 비고리 아민 화합물의 수용액을 제조하는 단계, 상기 수용액을 기질 표면의 적어도 일부에 접촉시키는 단계, 상기 기질을 세척 및 건조하는 단계를 포함하는 것을 특징으로 한다.A method for modifying a substrate according to the present invention comprises the steps of preparing an aqueous solution of an unsaturated acyclic amine compound of formula (I), contacting the aqueous solution with at least a portion of the substrate surface, washing and drying the substrate characterized in that
<화학식 (I)><Formula (I)>
Figure PCTKR2022006417-appb-I000006
Figure PCTKR2022006417-appb-I000006
상기 식에서,In the above formula,
X는 -NH2, -N=CH-OH, 또는 -N=O이고,X is -NH 2 , -N=CH-OH, or -N=O,
R1은 수소, C1-C6 알킬, 또는 -CN이며,R 1 is hydrogen, C 1 -C 6 alkyl, or —CN,
R2 및 R3은 각각 독립적으로 수소, C1-C6알킬, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 C1-C6알킬임)로 이루어진 군에서 선택되는 치환기이다. R 2 and R 3 are each independently hydrogen, C 1 -C 6 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or a substituent selected from the group consisting of C 1 -C 6 alkyl.
바람직하게는, 상기 화학식 (I)에서,Preferably, in the formula (I),
X는 -NH2이고,X is -NH 2 ,
R1은 수소, C1-C3 알킬, 또는 -CN이며R 1 is hydrogen, C 1 -C 3 alkyl, or —CN
R2 및 R3은 각각 독립적으로 수소, C1-C3알킬, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 C1-C3알킬임)로 이루어진 군에서 선택되는 치환기이다. R 2 and R 3 are each independently hydrogen, C 1 -C 3 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or C 1 -C 3 alkyl).
더욱 바람직하게는, 상기 화학식 (I)에서,More preferably, in the formula (I),
X는 -NH2이고,X is -NH 2 ,
R1은 수소, 메틸, 또는 -CN이며R 1 is hydrogen, methyl, or —CN
R2 및 R3은 각각 독립적으로 수소, 메틸, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 메틸임)로 이루어진 군에서 선택되는 치환기이다. R 2 and R 3 are each independently hydrogen, methyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 , wherein R 4 and R 5 is a substituent selected from the group consisting of hydrogen or methyl.
가장 바람직하게는, 상기 화학식 (I)의 화합물은 예컨대, 3-아미노크로톤산 메틸, 3-아미노크로톤산 에틸, N-비닐포름아미드, 3-아미노크로토니트릴, N[(2E)-3-니트로소부트-2-엔-2일]하이드록시아민, 디아미노말레오니트릴, 4-아미노펜트-3-엔-2-온으로 이루어진 군으로부터 선택되는 화합물이다.Most preferably, the compound of formula (I) is, for example, methyl 3-aminocrotonic acid, ethyl 3-aminocrotonic acid, N-vinylformamide, 3-aminocrotonitrile, N[(2E)-3- Nitrosobut-2-en-2yl]hydroxyamine, diaminomaleonitrile, 4-aminopent-3-en-2-one.
본 발명에 따른 기질의 개질방법에서 화학식 (I)의 불포화 비고리 아민 화합물의 수용액은 산성, 중성 또는 염기성일 수 있다. 예컨대, 순수(pure water), 완충액(buffer: 약산성, 중성 또는 염기성), NaOH 용액 (0.01 M, 0.1 M 또는 1 M), 또는 15~20% DMEA(N,N-디메틸아민: CAS 598-56-1; salt free, pH 13~14) 등을 용매로 사용할 수 있으며, 이들로 특별히 제한되지는 않는다. 이들 용매에 화학식 (I)의 화합물을 가하여 수용액을 제조한다. 용액의 농도는 특별히 한정되지 않으며, 사용하는 용질과 용매, 기타 반응 조건에 따라 적절히 조절 가능하다. 예컨대 용액의 농도는 0.1 ~ 10 mg/mL일 수 있다.In the method for modifying a substrate according to the present invention, the aqueous solution of the unsaturated acyclic amine compound of formula (I) may be acidic, neutral or basic. For example, pure water, buffer (weak acid, neutral or basic), NaOH solution (0.01 M, 0.1 M or 1 M), or 15-20% DMEA (N,N-dimethylamine: CAS 598-56) -1; salt free, pH 13-14), etc. can be used as a solvent, and are not particularly limited thereto. An aqueous solution is prepared by adding the compound of formula (I) to these solvents. The concentration of the solution is not particularly limited, and can be appropriately adjusted depending on the solute and solvent used and other reaction conditions. For example, the concentration of the solution may be 0.1 to 10 mg/mL.
개질하고자 하는 기질을 충분히 수용할 수 있는 용적의 용기에 상기한 바와 같이 준비한 용액을 채운 다음, 개질하고자 하는 기질을 상기 수용액에 담근다. 다만, 개질하고자 하는 기질의 표면이 화학식 (I)의 화합물의 수용액과 일정 시간 동안 충분히 접촉할 수만 있다면 기질을 수용액에 담그는 방식 이외에 어떠한 방식으로도 가능하다. 예컨대, 기질의 표면이 상기 수용액과 충분히 접촉할 수 있도록 기질의 표면에 상기 수용액을 뿌려 주거나 다양한 코팅 프로세스에서 사용하는 방법에 의해 기질과 상기 수용액을 접촉시키는 것이 가능하다.The solution prepared as described above is filled in a container having a volume sufficient to accommodate the substrate to be modified, and then the substrate to be modified is immersed in the aqueous solution. However, as long as the surface of the substrate to be modified can sufficiently contact the aqueous solution of the compound of formula (I) for a predetermined time, any method other than immersing the substrate in the aqueous solution is possible. For example, it is possible to contact the aqueous solution with the substrate by spraying the aqueous solution on the surface of the substrate or using a method used in various coating processes so that the surface of the substrate can sufficiently contact the aqueous solution.
기질과 상기 수용액이 접촉한 상태로 일정 시간 방치하는 항온처리만으로 본 발명에 따른 개질이 수행될 수 있다. 기질과의 결합반응을 활성화하기 위해 가열하거나 화학식 (I) 화합물의 수용액을 교반할 수 있다. 또한 촉매를 사용할 수 있는 경우에는 반응을 촉진시키기 위한 촉매를 투입할 수도 있으나, 반드시 필요한 것은 아니다. 반응시간 및 반응온도는 특별히 제한되지는 않으며, 사용하는 구체적인 화합물의 종류 및 기질의 종류에 따라 통상의 기술자가 적절히 선택 및 조절할 수 있다. 예컨대 반응온도는 50℃ 내지 100℃일 수 있고, 반응시간은 6 내지 48시간일 수 있으나, 이로 한정되지는 않는다.Modification according to the present invention can be performed only by incubation treatment in which the substrate and the aqueous solution are left in contact for a certain period of time. The aqueous solution of the compound of formula (I) may be stirred or heated to activate the binding reaction with the substrate. In addition, when a catalyst can be used, a catalyst for accelerating the reaction may be added, but it is not necessary. The reaction time and reaction temperature are not particularly limited, and a person skilled in the art may appropriately select and adjust it according to the type of the specific compound used and the type of the substrate. For example, the reaction temperature may be 50° C. to 100° C., and the reaction time may be 6 to 48 hours, but is not limited thereto.
일정시간의 항온처리 후 기질을 세척하여 결합 또는 중합되지 않은 화학식 (I) 화합물이나 불순물을 제거한다. 세척 후 상온 또는 승온하에서 건조하여 표면개질된 기질을 얻는다.After incubation for a period of time, the substrate is washed to remove bound or unpolymerized compounds of formula (I) or impurities. After washing, it is dried at room temperature or elevated temperature to obtain a surface-modified substrate.
다른 표면 개질제와 함께 사용하는 경우에는 본 발명의 불포화 비고리 아민 화합물과 다른 표면 개질제 화합물을 모두 포함하는 수용액을 제조하여 상기한 제조방법에 그대로 적용하는 것만으로 충분하다.When used together with other surface modifiers, it is sufficient to prepare an aqueous solution containing both the unsaturated acyclic amine compound of the present invention and another surface modifier compound and apply it as it is to the above-described manufacturing method.
본 발명에서 기질은 유리, 목재, 석재, 금속, 세라믹, 천연 및 합성 고분자 등일 수 있고 특별히 한정되지 않는다.In the present invention, the substrate may be glass, wood, stone, metal, ceramic, natural or synthetic polymer, and the like, and is not particularly limited.
금속 기질로는 예컨대, 철, 구리, 알루미늄, 아연, 주석, 은, 금, 티탄, 텅스텐, 니켈, 몰리브덴, 코발트, 마그네슘 및 이들의 합금류가 있으며 이들로 특별히 제한되지는 않는다.Metal substrates include, but are not particularly limited to, iron, copper, aluminum, zinc, tin, silver, gold, titanium, tungsten, nickel, molybdenum, cobalt, magnesium, and alloys thereof.
세라믹은 금속, 비금속 또는 준금속의 무기 화합물로서, 예컨대, 산화아연, 산화지르코늄, 산화티탄, 붕산 알루미늄, 산화철, 탄산칼슘, 탄산바륨, 산화납, 산화주석, 산화세륨, 산화리튬, 산화칼슘, 산화마그네슘, 사산화삼망간, 산화니오브, 산화탄탈, 산화텅스텐, 산화안티몬, 인산알루미늄, 칼슘실리케이트, 지르코늄실리케이트, ITO(주석 함유 산화 인듐), 티탄실리케이트, 티탄산바륨, 티탄산스트론튬, 티탄산칼슘, 몬모릴로나이트, 사포나이트, 버미클라이트, 하이드로탈사이트, 카올리나이트, 카네마이트, 마가디아이트, 케니아이트, 실리카, 알루미나, 제올라이트, 리튬나이트라이드, 리튬실리케이트, 리튬보레이트, 리튬알루미네이트, 리튬포스페이트, 리튬 인 옥시나이트라이드, 리튬 실리콘설파이드, 리튬 란탄 옥사이드, 리튬 티타늄 옥사이드, 리튬 보로설파이드, 리튬 알루미노설파이드, 리튬 포스포설파이드, 알루미늄 티타늄 옥사이드 등이 있으며 이들로 특별히 제한되지는 않는다.Ceramics are inorganic compounds of metals, nonmetals or metalloids, for example, zinc oxide, zirconium oxide, titanium oxide, aluminum borate, iron oxide, calcium carbonate, barium carbonate, lead oxide, tin oxide, cerium oxide, lithium oxide, calcium oxide, Magnesium oxide, trimanganese tetraoxide, niobium oxide, tantalum oxide, tungsten oxide, antimony oxide, aluminum phosphate, calcium silicate, zirconium silicate, ITO (indium oxide with tin), titanium silicate, barium titanate, strontium titanate, calcium titanate, montmorillonite, sandpaper Nit, vermiclite, hydrotalcite, kaolinite, kanemite, margadiite, kenyite, silica, alumina, zeolite, lithium nitride, lithium silicate, lithium borate, lithium aluminate, lithium phosphate, lithium phosphorus oxynite Lithium, lithium silicon sulfide, lithium lanthanum oxide, lithium titanium oxide, lithium borosulfide, lithium aluminosulfide, lithium phosphosulfide, aluminum titanium oxide, and the like, but is not particularly limited thereto.
천연 고분자로는 예컨대 전분, 셀룰로스, 키토산, 키틴, 젤라틴, 펙틴, 카라기난, 덱스트란, 콜라겐, 히알루론산, 알지네이트, 글루텐, 피브린, 아가로스 등이 있으며 이들로 특별히 제한되지는 않는다. Natural polymers include, for example, starch, cellulose, chitosan, chitin, gelatin, pectin, carrageenan, dextran, collagen, hyaluronic acid, alginate, gluten, fibrin, agarose, and the like, but are not particularly limited thereto.
합성 고분자로는 모든 범용 열가소성 고분자, 열경화성 고분자, 엔지니어링 고분자, 엘라스토머 등이 포함되며, 예컨대 폴리에틸렌, 폴리프로필렌, 폴리메틸펜텐, 폴리부텐-1 등을 포함하는 폴리올레핀, 폴리이소부틸렌, 에틸렌-프로필렌 고무, 에틸렌-프로필렌-디엔 고무(EPDM) 등을 포함하는 폴리올레핀 엘라스토머, 폴리비닐클로라이드, 폴리비닐리덴클로라이드, 폴리클로로트리플루오로에틸렌, 폴리비닐리덴플루오라이드, 폴리테트라플루오로에틸렌 등을 포함하는 할로겐화폴리올레핀, 폴리스티렌, 폴리비닐알코올, 폴리아세탈, 폴리비닐아세테이트, 폴리아크릴로니트릴, 폴리부타디엔, 폴리이소프렌, 페놀수지, 에폭시수지, 폴리아미드, 폴리에틸렌테레프탈레이트 및 폴리부틸렌테레프탈레이트 등을 포함하는 폴리에스테르, 폴리이미드, 폴리아미드이미드, 폴리에테르이미드, 폴리아크릴레이트, 폴리우레탄, 폴리실록산, 폴리나프탈렌, 폴리티오펜, 폴리아닐린, 폴리파라페닐렌설파이드, 폴리클로로프렌, 스티렌-부타디엔 고무, 니트릴고무, 실리콘고무 및 이들의 공중합체 등이 있으며 이들로 특별히 제한되지는 않는다.Synthetic polymers include all general-purpose thermoplastic polymers, thermosetting polymers, engineering polymers, elastomers, etc., for example, polyolefins including polyethylene, polypropylene, polymethylpentene, polybutene-1, etc., polyisobutylene, ethylene-propylene rubber , polyolefin elastomers including ethylene-propylene-diene rubber (EPDM), etc., halogenated polyolefins including polyvinyl chloride, polyvinylidene chloride, polychlorotrifluoroethylene, polyvinylidene fluoride, polytetrafluoroethylene, etc. Polyester, including polystyrene, polyvinyl alcohol, polyacetal, polyvinyl acetate, polyacrylonitrile, polybutadiene, polyisoprene, phenol resin, epoxy resin, polyamide, polyethylene terephthalate and polybutylene terephthalate; Polyimide, polyamideimide, polyetherimide, polyacrylate, polyurethane, polysiloxane, polynaphthalene, polythiophene, polyaniline, polyparaphenylene sulfide, polychloroprene, styrene-butadiene rubber, nitrile rubber, silicone rubber and these of copolymers, and the like, and are not particularly limited thereto.
기질의 형상도 분말(powder), 비드(bead), 평판(plate), 막대(rod), 튜브(tube) 또는 임의의 3차원 형상일 수 있고 특별히 한정되지 않는다. 또한 필요에 따라 기질의 일부분만을 화학식 (I) 화합물의 수용액과 접촉시킴으로써 기질의 일부분만을 개질하는 것도 가능하다.The shape of the substrate may also be a powder, a bead, a plate, a rod, a tube, or any three-dimensional shape, and is not particularly limited. It is also possible, if necessary, to modify only a part of the substrate by contacting only part of the substrate with an aqueous solution of the compound of formula (I).
<실시예><Example>
이하에서는 실시예에 의거하여 본 발명의 다양한 실시 형태들을 더욱 상세히 설명하고자 하나, 본 발명의 보호범위는 결코 후술하는 실시예에 의해 제한되지 않는다. 통상의 기술자는 실시예에 예시된 화합물과 기질, 실시 기법들은 본 발명을 실시하는데 있어서 대표적인 예들을 나타내는 것임을 잘 알 수 있다. 또한, 통상의 기술자는 개시된 내용을 바탕으로 기재된 구체적인 실시 형태들을 여러가지로 변경시킬 수 있으며 본 발명의 기술사상과 보호 범위를 벗어나지 않는 유사한 결과를 얻을 수 있을 것이다.Hereinafter, various embodiments of the present invention will be described in more detail based on examples, but the protection scope of the present invention is by no means limited by the examples described below. Those of ordinary skill in the art can understand that the compounds, substrates, and techniques exemplified in the Examples represent representative examples for practicing the present invention. In addition, those skilled in the art can make various changes to the specific embodiments described based on the disclosed contents, and similar results can be obtained without departing from the spirit and protection scope of the present invention.
실시예 1: 실온의 약염기성 용액에서 유리 슬라이드 상에 3-아미노크로톤산 메틸 개질 Example 1: Modification of 3-aminocrotonic acid methyl on glass slides in weakly basic solution at room temperature
pH 9.0의 보레이트 버퍼(50 mM)에 3-아미노크로톤산 메틸을 가하여 1 mg/1mL 농도의 용액을 제조하였다. 상기 용액에 유리 슬라이드를 실온에서 20시간 동안 담가두었다. 유리 슬라이드를 꺼내 70℃ 오븐에 3시간 동안 두었다가 NaOH 용액으로 20초간 세척하였다. 그 다음 충분한 양의 물로 세척하고 70℃에서 5분간 건조시켰다. 다시 유리 슬라이드를 HCl 용액으로 20초간 세척하고 충분한 양의 물로 세척한 다음 70℃에서 5분간 건조시켰다.Methyl 3-aminocrotonic acid was added to borate buffer (50 mM) of pH 9.0 to prepare a solution having a concentration of 1 mg/1mL. Glass slides were immersed in the solution at room temperature for 20 hours. The glass slides were taken out and placed in an oven at 70° C. for 3 hours and then washed with NaOH solution for 20 seconds. Then, it was washed with a sufficient amount of water and dried at 70° C. for 5 minutes. Again, the glass slide was washed with HCl solution for 20 seconds, washed with a sufficient amount of water, and then dried at 70° C. for 5 minutes.
비교예 1Comparative Example 1
pH 9.0의 보레이트 버퍼(50 mM)에 실시예 1에서 사용한 것과 동일한 규격의 유리 슬라이드를 실온에서 20시간 동안 담가 두었다. 유리 슬라이드를 꺼내 70℃ 오븐에 3시간 동안 두었다가 NaOH 용액으로 20초간 세척하였다. 그 다음 충분한 양의 물로 세척하고 70℃에서 5분간 건조시켰다. 다시 유리 슬라이드를 HCl용액으로 20초간 세척하고 충분한 양의 물로 세척한 다음 70℃에서 5분간 건조시켰다.Glass slides having the same specifications as those used in Example 1 were immersed in borate buffer (50 mM) of pH 9.0 at room temperature for 20 hours. The glass slides were taken out and placed in an oven at 70° C. for 3 hours and then washed with NaOH solution for 20 seconds. Then, it was washed with a sufficient amount of water and dried at 70° C. for 5 minutes. Again, the glass slide was washed with HCl solution for 20 seconds, washed with a sufficient amount of water, and then dried at 70° C. for 5 minutes.
실시예 2: 실온의 강염기성 용액에서 유리 슬라이드 상에 3-아미노크로톤산 메틸 개질 Example 2: Modification of 3-aminocrotonic acid methyl on glass slides in strong basic solution at room temperature
pH 13의 디메틸에탄올아민 8% 수용액에 3-아미노크로톤산 메틸을 가하여 1mg/1mL 농도의 용액을 제조하였다. 상기 용액에 유리 슬라이드를 실온에서 12시간 동안 담가 두었다. 유리 슬라이드를 꺼내 70℃ 오븐에 3시간 동안 두었다가 NaOH 용액으로 20초간 세척하였다. 그 다음 충분한 양의 물로 세척하고 70℃에서 5분간 건조시켰다. 다시 유리 슬라이드를 HCl 용액으로 20초간 세척하고 충분한 양의 물로 세척한 다음 70℃에서 5분간 건조시켰다.Methyl 3-aminocrotonic acid was added to an 8% aqueous solution of dimethylethanolamine having a pH of 13 to prepare a solution having a concentration of 1 mg/1 mL. Glass slides were immersed in the solution at room temperature for 12 hours. The glass slides were taken out and placed in an oven at 70° C. for 3 hours and then washed with NaOH solution for 20 seconds. Then, it was washed with a sufficient amount of water and dried at 70° C. for 5 minutes. Again, the glass slide was washed with HCl solution for 20 seconds, washed with a sufficient amount of water, and then dried at 70° C. for 5 minutes.
비교예 2Comparative Example 2
pH 9.0의 보레이트 버퍼(50 mM)에 실시예 2에서 사용한 것과 동일한 규격의 유리 슬라이드를 실온에서 12시간 동안 담가 두었다. 유리 슬라이드를 꺼내 70℃ 오븐에 3시간 동안 두었다가 NaOH 용액으로 20초간 세척하였다. 그 다음 충분한 양의 물로 세척하고 70℃에서 5분간 건조시켰다. 다시 유리 슬라이드를 HCl용액으로 20초간 세척하고 충분한 양의 물로 세척한 다음 70℃에서 5분간 건조시켰다.Glass slides having the same specifications as those used in Example 2 were immersed in borate buffer (50 mM) of pH 9.0 at room temperature for 12 hours. The glass slides were taken out and placed in an oven at 70° C. for 3 hours and then washed with NaOH solution for 20 seconds. Then, it was washed with a sufficient amount of water and dried at 70° C. for 5 minutes. Again, the glass slide was washed with HCl solution for 20 seconds, washed with a sufficient amount of water, and then dried at 70° C. for 5 minutes.
실시예 3: 실온의 약염기성 용액에서 폴리이미드 필름 상에 3-아미노크로톤산 메틸 개질 Example 3: Modification of 3-aminocrotonic acid methyl on polyimide film in weakly basic solution at room temperature
폴리이미드(PI) 필름을 사용한 점만 제외하고 실시예 1에서와 동일한 방법으로 표면개질 필름을 제조하였다.A surface-modified film was prepared in the same manner as in Example 1, except that a polyimide (PI) film was used.
비교예 3Comparative Example 3
폴리이미드(PI) 필름을 사용한 점만 제외하고 비교예 1에서와 동일한 방법으로 시료를 준비하였다.A sample was prepared in the same manner as in Comparative Example 1, except that a polyimide (PI) film was used.
실시예 4: 실온의 강염기성 용액에서 폴리이미드 필름 상에 3-아미노크로톤산 메틸 개질 Example 4: Modification of 3-aminocrotonic acid methyl on polyimide film in strong basic solution at room temperature
폴리이미드(PI) 필름을 사용한 점만 제외하고 실시예 2에서와 동일한 방법으로 표면개질 필름을 제조하였다.A surface-modified film was prepared in the same manner as in Example 2, except that a polyimide (PI) film was used.
비교예 4Comparative Example 4
폴리이미드(PI) 필름을 사용한 점만 제외하고 비교예 2에서와 동일한 방법으로 시료를 준비하였다.A sample was prepared in the same manner as in Comparative Example 2, except that a polyimide (PI) film was used.
실시예 5: 실온의 약염기성 용액에서 폴리에틸렌 필름 상에 3-아미노크로톤산 메틸 개질 Example 5: Modification of 3-aminocrotonic acid methyl on polyethylene film in weakly basic solution at room temperature
식품포장재용 폴리에틸렌 (PE) 필름(양면의 폴리에틸렌 필름 사이에 인쇄면 필름 및 알루미늄 필름이 존재하는 복합 필름)을 사용한 점만 제외하고 실시예 1에서와 동일한 방법으로 표면개질 필름을 제조하였다.A surface-modified film was prepared in the same manner as in Example 1, except that a polyethylene (PE) film for food packaging (a composite film in which a printing film and an aluminum film are present between the polyethylene films on both sides) was used.
비교예 5Comparative Example 5
식품포장재용 폴리에틸렌 (PE) 필름을 사용한 점만 제외하고 비교예 1에서와 동일한 방법으로 시료를 준비하였다.A sample was prepared in the same manner as in Comparative Example 1, except that a polyethylene (PE) film for food packaging was used.
실시예 6: 실온의 강염기성 용액에서 폴리에틸렌 필름 상에 3-아미노크로톤산 메틸 개질 Example 6: Modification of 3-aminocrotonic acid methyl on polyethylene film in strong basic solution at room temperature
식품포장재용 폴리에틸렌 (PE) 필름을 사용한 점만 제외하고 실시예 2에서와 동일한 방법으로 표면개질 필름을 제조하였다.A surface-modified film was prepared in the same manner as in Example 2, except that a polyethylene (PE) film for food packaging was used.
비교예 6Comparative Example 6
식품포장재용 폴리에틸렌 (PE) 필름을 사용한 점만 제외하고 비교예 2에서와 동일한 방법으로 시료를 준비하였다.A sample was prepared in the same manner as in Comparative Example 2, except that a polyethylene (PE) film for food packaging was used.
<접촉각의 측정><Measurement of contact angle>
접촉각을 측정하기 위하여 미국 뉴저지주 소재 라메하트 인스트루먼트사의 고니오미터(모델 300)를 사용하였다. 미량주사기를 사용하여 시료액(디메틸에탄올 아민 15% 수용액 또는 증류슈) 2 ㎕의 액체방울을 고니오미터 샘플스테이지 상의 시료 표면에 올려놓았다. 고니오미터의 샘플스테이지에 올려 놓은 시료액 방울과 시료 표면과의 접촉상태를 알 수 있는 측면사진을 찍은 후에, 고니오미터의 드롭이미지(DROPImage) 소프트웨어를 사용하여 접촉각의 정량적인 정보를 알아내는 방식으로 접촉각을 측정하였다.To measure the contact angle, a goniometer (model 300) from Ramehart Instruments, New Jersey, USA was used. A droplet of 2 μl of the sample solution (15% aqueous solution of dimethylethanolamine or distilled shoe) was placed on the surface of the sample on the goniometer sample stage using a micro-injector. After taking a side picture that shows the contact state between the droplet of the sample solution placed on the sample stage of the goniometer and the sample surface, the quantitative information of the contact angle is obtained using the DROPImage software of the goniometer. The contact angle was measured in this way.
위와 같은 방법으로 모든 실시예 시료 필름과 각각의 비교예 시료 필름에 대해 접촉각을 측정한 결과를 표 1 내지 표 6에 나타내었다. "점적액"이란 접촉각 측정에 사용한 시료액을 의미한다.Tables 1 to 6 show the results of measuring the contact angles for all of the sample films of Examples and each of the sample films of Comparative Examples in the same manner as above. "Drip solution" means a sample solution used for measuring the contact angle.
실시예 1 시료와 비교예 1 시료의 접촉각 측정 결과Contact angle measurement result of the sample of Example 1 and the sample of Comparative Example 1
실시예 1Example 1 비교예 1Comparative Example 1
1One 60.2˚60.2˚ 48.2˚48.2˚
22 56.6˚56.6˚ 52.5˚52.5˚
33 58.4˚58.4˚ 53.2˚53.2˚
44 61.4˚61.4˚ 51.0˚51.0˚
55 52.6˚52.6˚ 54.0˚54.0˚
평균Average 57.8˚57.8˚ 51.8˚51.8˚
실시예 2 시료와 비교예 2 시료의 접촉각 측정 결과Contact angle measurement result of the sample of Example 2 and the sample of Comparative Example 2
점적액: 물Drops: water
실시예 2Example 2 비교예 2Comparative Example 2
1One 56.2˚56.2˚ 32.9˚32.9˚
22 33.2˚33.2˚ 35.6˚35.6˚
33 28.4˚28.4˚ 27.9˚27.9˚
44 33.6˚33.6˚ 30.6˚30.6˚
55 45.2˚45.2˚ 28.2˚28.2˚
평균Average 39.3˚39.3˚ 31.0˚31.0˚
실시예 3 시료와 비교예 3 시료의 접촉각 측정 결과Example 3 Sample and Comparative Example 3 Contact Angle Measurement Results
점적액: 물Drops: water
실시예 3Example 3 비교예 3Comparative Example 3
1One 66.2˚66.2˚ 73.0˚73.0˚
22 69.8˚69.8˚ 70.6˚70.6˚
33 65.8˚65.8˚ 65.4˚65.4˚
44 67.5˚67.5˚ 73.0˚73.0˚
55 80.4˚80.4˚ 67.6˚67.6˚
평균Average 69.9˚69.9˚ 69.9˚69.9˚
실시예 4 시료와 비교예 4 시료의 접촉각 측정 결과Example 4 Sample and Comparative Example 4 Contact Angle Measurement Results
점적액: 물Drops: water 점적액: 15% DMEA 수용액Drops: 15% DMEA aqueous solution
실시예 4Example 4 비교예 4Comparative Example 4 실시예 4Example 4 비교예 4Comparative Example 4
1One 78.0˚78.0˚ < 10˚< 10˚ 31.9˚31.9˚ --
22 68.8˚68.8˚ < 10˚< 10˚ 30.0˚30.0˚ 21.8˚21.8˚
33 66.6˚66.6˚ < 15˚< 15˚ 23.9˚23.9˚ 25.8˚25.8˚
44 61.2˚61.2˚ -- 36.6˚36.6˚ 28.3˚28.3˚
55 69.0˚69.0˚ -- 37.3˚37.3˚ 33.0˚33.0˚
평균Average 68.7˚68.7˚ < 15˚< 15˚ 31.9˚31.9˚ 27.2˚27.2˚
실시예 5 시료와 비교예 5 시료의 접촉각 측정 결과Contact angle measurement result of the sample of Example 5 and the sample of Comparative Example 5
점적액: 물Drops: water 점적액: 15% DMEA 수용액Drops: 15% DMEA aqueous solution
실시예 5Example 5 비교예 5Comparative Example 5 실시예 5Example 5 비교예 5Comparative Example 5
1One 104.2˚104.2˚ 95.8˚95.8˚ 97.0˚97.0˚ 85.9˚85.9˚
22 106.6˚106.6˚ 91.2˚91.2˚ 88.5˚88.5˚ 77.2˚77.2˚
33 96.9˚96.9˚ 87.9˚87.9˚ 93.0˚93.0˚ 64.6˚64.6˚
44 109.2˚109.2˚ 93.4˚93.4˚ 97.4˚97.4˚ 90.1˚90.1˚
55 107.4˚107.4˚ 90.6˚90.6˚ 83.1˚83.1˚ 86.6˚86.6˚
평균Average 104.9˚104.9˚ 91.8˚91.8˚ 91.8˚91.8˚ 80.1˚80.1˚
실시예 6 시료와 비교예 6 시료의 접촉각 측정 결과Contact angle measurement result of the sample of Example 6 and the sample of Comparative Example 6
점적액: 15% DMEA 수용액Drops: 15% DMEA aqueous solution
실시예 6Example 6 비교예 6Comparative Example 6
1One 91.2˚91.2˚ 74.7˚74.7˚
22 94.0˚94.0˚ 76.3˚76.3˚
33 81.0˚81.0˚ 74.1˚74.1˚
44 78.6˚78.6˚ 86.3˚86.3˚
55 73.3˚73.3˚ 76.0˚76.0˚
평균Average 83.6˚83.6˚ 77.5˚77.5˚
상기 결과로부터, 다양한 기질의 표면 개질에 불포화 비고리 아민 화합물을 사용하는 경우 소수성 코팅을 제공한다는 사실을 확인할 수 있었다. 특정한 기질과 표면 개질 조건에 따라 개질된 표면의 성질이 다양하게 변할 수 있으며 표면 개질에 사용하는 불포화 비고리 아민 화합물을 적절히 선택함으로써 개질된 표면의 성질을 조정하는 것도 가능하다는 사실을 확인할 수 있었다. 통상의 기술자는 위 실험 결과로부터 원하는 성질을 갖는 기질 표면을 얻기 위해 적합한 화합물 및 표면 개질 조건을 최적화할 수 있을 것이다.From the above results, it was confirmed that the hydrophobic coating was provided when the unsaturated acyclic amine compound was used for surface modification of various substrates. It was confirmed that the properties of the modified surface can vary depending on a specific substrate and surface modification conditions, and it is possible to adjust the properties of the modified surface by appropriately selecting the unsaturated acyclic amine compound used for surface modification. A person skilled in the art will be able to optimize suitable compounds and surface modification conditions to obtain a substrate surface having desired properties from the above experimental results.
본 발명은 불포화 비고리 아민 화합물 또는 그의 올리고머 또는 (공)중합체가 기질에 비의존적으로 표면 개질된 기질 및 그 개질 방법에 관한 것으로서, 다양한 기질의 화학적 표면 개질에 사용할 수 있다. 특히, 소수성이 필요한 적용 분야에 사용되는 재료의 표면에 적합한 소수성을 부여하거나, 그 반대의 개질도 가능하다. 또한, 계면간의 접착력 향상을 위하여 한쪽 계면의 화학적 성질을 개질하거나, 고정 및/또는 분리하고자 하는 생화학물질의 성질에 맞도록 적절히 선택된 개질 화합물을 사용함으로써 생화학물질의 분리 수율 및 신뢰성을 높이는 것도 가능하므로, 본 발명을 이용할 수 있는 산업 분야는 무궁무진하다.The present invention relates to a substrate in which an unsaturated acyclic amine compound or an oligomer or (co)polymer thereof is surface-modified independently of a substrate and a method for modifying the same, and can be used for chemical surface modification of various substrates. In particular, it is possible to impart suitable hydrophobicity to the surface of the material used in applications where hydrophobicity is required, and vice versa. In addition, it is possible to improve the separation yield and reliability of biochemicals by modifying the chemical properties of one interface to improve the adhesion between the interfaces, or by using a modified compound appropriately selected to match the properties of the biochemical to be fixed and/or separated. , the industrial fields in which the present invention can be used are limitless.

Claims (15)

  1. 기질 표면의 적어도 일부에 하기 화학식 (I)의 불포화 비고리 아민 화합물을 표면개질제로 반응시켜, 화학식 (I)의 불포화 비고리 아민 화합물 또는 그의 올리고머 또는 (공)중합체로 표면개질된 기질.A substrate surface-modified with an unsaturated acyclic amine compound of Formula (I) or an oligomer or (co)polymer thereof by reacting at least a portion of the surface of the substrate with an unsaturated acyclic amine compound of the following formula (I) with a surface modifier.
    <화학식 (I)><Formula (I)>
    Figure PCTKR2022006417-appb-I000007
    Figure PCTKR2022006417-appb-I000007
    상기 식에서,In the above formula,
    X는 -NH2, -N=CH-OH, 또는 -N=O이고,X is -NH 2 , -N=CH-OH, or -N=O,
    R1은 수소, C1-C6 알킬, 또는 -CN이며,R 1 is hydrogen, C 1 -C 6 alkyl, or —CN,
    R2 및 R3은 각각 독립적으로 수소, C1-C6알킬, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 C1-C6알킬임)로 이루어진 군에서 선택되는 치환기이다. R 2 and R 3 are each independently hydrogen, C 1 -C 6 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or a substituent selected from the group consisting of C 1 -C 6 alkyl.
  2. 제1항에 있어서,According to claim 1,
    상기 화학식 (I)에서,In the above formula (I),
    X는 -NH2이고,X is -NH 2 ,
    R1은 수소, C1-C3 알킬, 또는 -CN이며R 1 is hydrogen, C 1 -C 3 alkyl, or —CN
    R2 및 R3은 각각 독립적으로 수소, C1-C3알킬, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 C1-C3알킬임)로 이루어진 군에서 선택되는 치환기인 것을 특징으로 하는, 화학식 (I)의 불포화 비고리 아민 화합물 또는 그의 올리고머 또는 (공)중합체로 표면개질된 기질.R 2 and R 3 are each independently hydrogen, C 1 -C 3 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or C 1 -C 3 alkyl), characterized in that the unsaturated acyclic amine compound of Formula (I) or an oligomer or (co)polymer thereof, characterized in that it is a substituent selected from the group consisting of modified temperament.
  3. 제1항에 있어서,According to claim 1,
    상기 화학식 (I)에서,In the above formula (I),
    X는 -NH2이고,X is -NH 2 ,
    R1은 수소, 메틸, 또는 -CN이며R 1 is hydrogen, methyl, or —CN
    R2 및 R3은 각각 독립적으로 수소, 메틸, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 메틸임)로 이루어진 군에서 선택되는 치환기인 것을 특징으로 하는, 화학식 (I)의 불포화 비고리 아민 화합물 또는 그의 올리고머 또는 (공)중합체로 표면개질된 기질.R 2 and R 3 are each independently hydrogen, methyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 , wherein R 4 and R 5 is hydrogen or methyl), characterized in that it is a substituent selected from the group consisting of unsaturated acyclic amine compound of formula (I) or an oligomer or (co)polymer surface-modified substrate.
  4. 제1항에 있어서, 상기 화학식 (I)의 불포화 비고리 아민 화합물은 3-아미노크로톤산 메틸, 3-아미노크로톤산 에틸, N-비닐포름아미드, 3-아미노크로토니트릴, N[(2E)-3-니트로소부트-2-엔-2일]하이드록시아민, 디아미노말레오니트릴, 및 4-아미노펜트-3-엔-2-온으로 이루어진 군으로부터 선택되는 화합물인 것을 특징으로 하는, 화학식 (I)의 불포화 비고리 아민 화합물 또는 그의 올리고머 또는 (공)중합체로 표면개질된 기질.According to claim 1, wherein the unsaturated acyclic amine compound of formula (I) is 3-aminocrotonic acid methyl, 3-aminocrotonic acid ethyl, N-vinylformamide, 3-aminocrotonitrile, N[(2E) -3-nitrosobut-2-en-2yl]hydroxyamine, diaminomaleonitrile, and a compound selected from the group consisting of 4-aminopent-3-en-2-one, A substrate surface-modified with an unsaturated acyclic amine compound of formula (I) or an oligomer or (co)polymer thereof.
  5. 제1항 내지 제4항에 있어서, 상기 기질은 유리, 목재, 석재, 금속, 세라믹, 천연 및 합성 고분자로 이루어진 군으로부터 선택된 것을 특징으로 하는, 상기 화학식 (I)의 불포화 비고리 아민 화합물 또는 그의 올리고머 또는 (공)중합체로 표면개질된 기질.The unsaturated acyclic amine compound of formula (I) or its Substrates surface-modified with oligomers or (co)polymers.
  6. 제5항에 있어서, 상기 기질은 합성 고분자인 것을 특징으로 하는, 상기 화학식 (I)의 불포화 비고리 아민 화합물 또는 그의 올리고머 또는 (공)중합체로 표면개질된 기질.[Claim 6] The substrate surface-modified with the unsaturated acyclic amine compound of formula (I) or an oligomer or (co)polymer thereof according to claim 5, wherein the substrate is a synthetic polymer.
  7. 제6항에 있어서, 상기 기질은 폴리올레핀, 폴리올레핀 엘라스토머, 할로겐화폴리올레핀, 폴리스티렌, 폴리비닐알코올, 폴리아세탈, 폴리비닐아세테이트, 폴리아크릴로니트릴, 폴리부타디엔, 폴리이소프렌, 페놀수지, 에폭시수지, 폴리아미드, 폴리에스테르, 폴리이미드, 폴리아미드이미드, 폴리에테르이미드, 폴리아크릴레이트, 폴리우레탄, 폴리실록산, 폴리나프탈렌, 폴리티오펜, 폴리아닐린, 폴리파라페닐렌설파이드, 폴리클로로프렌, 스티렌-부타디엔 고무, 니트릴고무, 실리콘고무 및 이들의 공중합체로 이루어진 군으로부터 선택된 것을 특징으로 하는, 상기 화학식 (I)의 불포화 비고리 아민 화합물 또는 그의 올리고머 또는 (공)중합체로 표면개질된 기질.7. The method of claim 6, wherein the substrate is polyolefin, polyolefin elastomer, halogenated polyolefin, polystyrene, polyvinyl alcohol, polyacetal, polyvinyl acetate, polyacrylonitrile, polybutadiene, polyisoprene, phenolic resin, epoxy resin, polyamide, Polyester, polyimide, polyamideimide, polyetherimide, polyacrylate, polyurethane, polysiloxane, polynaphthalene, polythiophene, polyaniline, polyparaphenylene sulfide, polychloroprene, styrene-butadiene rubber, nitrile rubber, silicone A substrate surface-modified with an unsaturated acyclic amine compound of formula (I) or an oligomer or (co)polymer thereof, characterized in that it is selected from the group consisting of rubber and copolymers thereof.
  8. 하기 화학식 (I)의 불포화 비고리 아민 화합물의 수용액을 제조하는 단계,preparing an aqueous solution of an unsaturated acyclic amine compound of formula (I),
    상기 수용액을 기질 표면의 적어도 일부에 접촉시키는 단계, contacting the aqueous solution to at least a portion of the substrate surface;
    상기 기질을 세척 및 건조하는 단계를 포함하는 것을 특징으로 하는 기질의 표면개질 방법.A method for surface modification of a substrate, comprising washing and drying the substrate.
    <화학식 (I)><Formula (I)>
    Figure PCTKR2022006417-appb-I000008
    Figure PCTKR2022006417-appb-I000008
    상기 식에서,In the above formula,
    X는 -NH2, -N=CH-OH, 또는 -N=O이고,X is -NH 2 , -N=CH-OH, or -N=O,
    R1은 수소, C1-C6 알킬, 또는 -CN이며,R 1 is hydrogen, C 1 -C 6 alkyl, or —CN,
    R2 및 R3은 각각 독립적으로 수소, C1-C6알킬, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 C1-C6알킬임)로 이루어진 군에서 선택되는 치환기이다.R 2 and R 3 are each independently hydrogen, C 1 -C 6 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or a substituent selected from the group consisting of C 1 -C 6 alkyl.
  9. 제8항에 있어서,9. The method of claim 8,
    상기 화학식 (I)에서,In the above formula (I),
    X는 -NH2이고,X is -NH 2 ,
    R1은 수소, C1-C3 알킬, 또는 -CN이며R 1 is hydrogen, C 1 -C 3 alkyl, or —CN
    R2 및 R3은 각각 독립적으로 수소, C1-C3알킬, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 C1-C3알킬임)로 이루어진 군에서 선택되는 치환기인 것을 특징으로 하는, 기질의 표면개질 방법.R 2 and R 3 are each independently hydrogen, C 1 -C 3 alkyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 where , R 4 and R 5 are hydrogen or C 1 -C 3 alkyl) A method for surface modification of a substrate, characterized in that it is a substituent selected from the group consisting of.
  10. 제8항에 있어서,9. The method of claim 8,
    상기 화학식 (I)에서,In the above formula (I),
    X는 -NH2이고,X is -NH 2 ,
    R1은 수소, 메틸, 또는 -CN이며R 1 is hydrogen, methyl, or —CN
    R2 및 R3은 각각 독립적으로 수소, 메틸, -CN, -OH, -NH2, -NH-OH, -C(O)R4 및 -C(O)OR5 (여기서, R4 및 R5는 수소 또는 메틸임)로 이루어진 군에서 선택되는 치환기인 것을 특징으로 하는, 기질의 표면개질 방법.R 2 and R 3 are each independently hydrogen, methyl, -CN, -OH, -NH 2 , -NH-OH, -C(O)R 4 and -C(O)OR 5 , wherein R 4 and R 5 is hydrogen or methyl), characterized in that the substituent selected from the group consisting of, the surface modification method of the substrate.
  11. 제8항에 있어서, 상기 화학식 (I)의 불포화 비고리 아민 화합물은 3-아미노크로톤산 메틸, 3-아미노크로톤산 에틸, N-비닐포름아미드, 3-아미노크로토니트릴, N[(2E)-3-니트로소부트-2-엔-2일]하이드록시아민, 디아미노말레오니트릴, 및 4-아미노펜트-3-엔-2-온으로 이루어진 군으로부터 선택되는 화합물인 것을 특징으로 하는, 기질의 표면개질 방법.According to claim 8, wherein the unsaturated acyclic amine compound of formula (I) is 3-aminocrotonic acid methyl, 3-aminocrotonic acid ethyl, N-vinylformamide, 3-aminocrotonitrile, N[(2E) -3-nitrosobut-2-en-2yl]hydroxyamine, diaminomaleonitrile, and a compound selected from the group consisting of 4-aminopent-3-en-2-one, A method for surface modification of a substrate.
  12. 제8항 내지 제11항 중 어느 한 항에 있어서, 상기 수용액은 산성 용액, 중성 용액 또는 염기성 용액 중 어느 하나인 것을 특징으로 하는 기질의 표면개질 방법.The method according to any one of claims 8 to 11, wherein the aqueous solution is any one of an acidic solution, a neutral solution, and a basic solution.
  13. 제8항 내지 제11항 중 어느 한 항에 있어서, 상기 기질은 유리, 목재, 석재, 금속, 세라믹, 천연 및 합성 고분자로 이루어진 군으로부터 선택된 것을 특징으로 하는 기질의 표면개질 방법.12. The method according to any one of claims 8 to 11, wherein the substrate is selected from the group consisting of glass, wood, stone, metal, ceramic, natural and synthetic polymers.
  14. 제13항에 있어서, 상기 기질은 합성 고분자인 것을 특징으로 하는 기질의 표면개질 방법.The method of claim 13, wherein the substrate is a synthetic polymer.
  15. 제14항에 있어서, 상기 기질은 폴리올레핀, 폴리올레핀 엘라스토머, 할로겐화폴리올레핀, 폴리스티렌, 폴리비닐알코올, 폴리아세탈, 폴리비닐아세테이트, 폴리아크릴로니트릴, 폴리부타디엔, 폴리이소프렌, 페놀수지, 에폭시수지, 폴리아미드, 폴리에스테르, 폴리이미드, 폴리아미드이미드, 폴리에테르이미드, 폴리아크릴레이트, 폴리우레탄, 폴리실록산, 폴리나프탈렌, 폴리티오펜, 폴리아닐린, 폴리파라페닐렌설파이드, 폴리클로로프렌, 스티렌-부타디엔 고무, 니트릴고무, 실리콘고무 및 이들의 공중합체로 이루어진 군으로부터 선택된 것을 특징으로 하는 기질의 표면개질 방법.15. The method of claim 14, wherein the substrate is polyolefin, polyolefin elastomer, halogenated polyolefin, polystyrene, polyvinyl alcohol, polyacetal, polyvinyl acetate, polyacrylonitrile, polybutadiene, polyisoprene, phenolic resin, epoxy resin, polyamide, Polyester, polyimide, polyamideimide, polyetherimide, polyacrylate, polyurethane, polysiloxane, polynaphthalene, polythiophene, polyaniline, polyparaphenylene sulfide, polychloroprene, styrene-butadiene rubber, nitrile rubber, silicone A method for surface modification of a substrate, characterized in that it is selected from the group consisting of rubber and copolymers thereof.
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