KR20220151376A - Surface-modified Substrate with Furfurylamine compound and Method for Surface-modification thereof - Google Patents

Abstract

The present invention relates to a substrate having a surface at least a portion of which is modified with a furfurylamine compound or an oligomer or (co)polymer thereof and a method for surface-modification thereof. In addition, the present invention provides the method for surface-modification of the substrate, which comprises the following steps of: providing an aqueous solution of a furfurylamine compound; bringing the aqueous solution into contact with at least a portion of the surface of the substrate; and washing and drying the substrate. According to the present invention, the surface of the substrate can be chemically modified independently of the substrate using the furfurylamine compound, and it is possible to carry out the chemical modification in a simple process without using special equipment or a processing means.

Description

Surface-modified Substrate with Furfurylamine compound and Method for Surface-modification thereof

The present invention relates to a substrate surface-modified with a furfurylamine compound or an oligomer or (co)polymer thereof and a method for modifying the same.

The technology of chemically modifying the surface of a substrate is an important technology required in various academic and applied technology fields. Basic methods for such chemical modification include surface treatment reactions and other physiochemical treatment techniques, which can impart desired chemical and/or physical properties to the surface of a substrate with little or no activity. In particular, most of the compounds used for chemical modification through surface treatment reaction have chemical functional groups at both ends. The functional group at one end is attached to the substrate through a chemical reaction, and the functional group at the other end itself is chemically attached to the surface of the substrate. It serves to provide functionality.

Among various substrates, in particular, polymeric materials widely used throughout the entire industrial field have lightness, flexibility, processability, insulation and transparency as inherent properties of the polymeric material itself. If the polymer surface can be modified into a surface having properties suitable for each application field without changing these inherent properties, not only the application field of the polymer can be further expanded, but also the polymer material can be used more effectively. The main reason why polymer materials sometimes have unsuitable surface properties is low surface tension and little reactivity. Therefore, if the surface tension of polymer materials can be increased or the distribution of reactive functional groups can be increased, the application fields of polymer materials will be very wide. Losing can result. In particular, since the hydrophilicity of polymer materials is an important property directly related to the adhesive strength, biocompatibility, colorability, printability, dyeability, and antistatic effect of polymer materials, various surface modification technologies are being developed to make surfaces with stronger hydrophilic properties. . Conversely, if the hydrophobicity of the surface of the polymer material is further increased, water repellency and stain resistance may be improved.

However, when chemical treatment is performed to modify the surface of a substrate, it is often limited by the nature of the substrate itself. For example, when modifying the surface of a substrate through a nucleophilic reaction, effective modification is difficult if the substrate itself does not have a nucleophilic reactive group or is present in a very low concentration, so a step of introducing a nucleophilic reactive group into the substrate in advance is necessary. . This additional step is never desirable in terms of time and cost, and there is also a problem that the properties of the modified surface change due to 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 the substrate.

Korean Patent Laid-open Publication No. 10-2003-0009732 describes an organic polymer substrate whose surface is coated with multiple aminoethyl molecule layers. Specifically, substrates made of various organic polymers or oligomers containing nucleophilic functional groups are reacted with aziridine or its derivatives to form a multi-aminoethyl molecular layer made of high-density polymers on the surface of the substrate, thereby improving the physicochemical properties of the substrate surface. A modified organic polymer substrate and a method for preparing the same are disclosed. However, since the surface modification method through a nucleophilic reaction is adopted, there is 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 mussel adhesive protein secreted from the bysal end of mussels is a typical substrate-independent natural adhesive. The adhesion mechanism of mussel adhesive proteins has been studied and techniques to imitate it have been developed. For example, dopamine containing both a catechol and an amine group or a compound similar thereto is used in an alkaline solution. U.S. Patent Nos. 8,541,060 and 8,999,452 relate to a multi-functional coating capable of surface modification independently of a substrate and applications thereof, using dopamine or a compound similar to dopamine as a surface modifier to treat a substrate and a substrate in an alkaline solution. A method of modifying the surface of a substrate by contact is proposed. However, several technical limitations exist in the based technology using dopamine or dopamine analogues. First of all, as described in the patent publication, the surface modification method can be performed only under alkaline conditions. Most of the experiments are performed in tris [tris (hydroxymethyl) aminomethane] buffer solution 10 mM pH 8.5, which is close to the pKa (dissociation constant) value of dopamine, which is approximately pH 9, so it is difficult to control the reactivity according to the need. There is a problem. In addition, dopamine or its analog compounds have two different types of reactive groups, such as at least two hydroxyl groups and one amino group, making it difficult to constantly control the functionality of the modified surface. Finally, the chemical structure of the compound used in the above method cannot have a large number of amino groups, thereby limiting the performance of subsequent applications based on modification of the amine structure.

Korean Patent Publication No. 1831613 discloses a polymer surface-coated with an aromatic amine-based compound 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, so it requires the addition of a compound to cause an oxidation-reduction reaction, that is, promotes the oxidation of an aromatic amine-based compound and requires basic pH conditions for the subsequent reduction reaction. Therefore, there is still a need for a surface-modifying compound that does not require the addition of such a compound and has excellent reactivity and can effectively modify the surface of a substrate even under milder conditions.

Republic of Korea Patent Publication No. 10-2003-0009732 US Patent Publication No. US 8,541,060 US Patent Publication No. US 8,999,452 Korean Patent Publication No. 1831613

In order to solve the above problems, an object of the present invention is to provide a substrate modified with a furfurylamine compound or an oligomer or (co)polymer thereof.

In addition, an 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 a furfurylamine compound.

In order to achieve the above object, the present invention provides a substrate surface-modified with the compound or an oligomer or (co)polymer thereof by reacting a furfurylamine compound of formula (I) with a surface modifier on at least a portion of the surface of the substrate. do.

<Formula (I)>

The inventors of the present invention have disclosed amino unsaturated heterocyclic compounds having specific structures in Korean Patent Application Nos. A method for modifying the surface of a substrate with a cyclic compound, an amino cycloalkene compound, and a vinyl amino non-aromatic ring compound and a surface-modified substrate have been disclosed. The entire disclosure of the specifications of the above applications is incorporated herein by reference. The furfurylamine compound of the present invention does not belong to the formula defined in the above prior applications and can be used alone as well as together with the compounds mentioned in the above prior applications for surface modification.

In addition, it is also possible to use the furfuryl amine compound of formula (I) and the unsaturated acyclic amine compound of formula (II) together as a surface modifier.

<Formula (II)>

In the above formula,

X is -NH ₂ , -N=CH-OH, or -N=O;

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 (wherein , R ⁴ and R ⁵ are hydrogen or C ₁ -C ₆ alkyl).

Preferably, in the above formula (II),

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 (wherein , R ⁴ and R ⁵ are hydrogen or C ₁ -C ₃ alkyl).

More preferably, in the above formula (II),

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 hydrogen or methyl) is a substituent selected from the group consisting of.

Most preferably, the compound of formula (II) is selected from, for example, methyl 3-aminocrotonate, ethyl 3-aminocrotonate, N-vinylformamide, 3-aminocrotonitrile, N[(2E)-3- It is a compound selected from the group consisting of nitrosobut-2-en-2yl] hydroxyamine, diaminomaleonitrile, and 4-aminopent-3-en-2-one.

According to the present invention, the furfurylamine compound is expected to undergo a chain polymerization reaction between the furfurylamine compounds simultaneously with, or before and after the nucleophilic reaction by the nucleophile on the surface of the substrate. The polymerization reaction between furfurylamines appears to follow the Diels-Alder reaction pathway, as predicted from its structure. In addition, the main reaction route for the copolymerization reaction between furfurylamine and other compounds having double bonds is the Diels-Alder reaction between two double bonds of the furan ring of furfurylamine and the double bonds of other compounds. However, these expected reaction pathways are only for facilitating understanding of the present invention, and the scope of the present invention is not limited or particularly limited by these reaction pathways themselves.

According to another aspect of the present invention, preparing an aqueous solution of the furfurylamine compound of formula (I), contacting the aqueous solution to at least a portion of the surface of the substrate, washing and drying the substrate It provides a method for modifying a substrate, characterized in that.

<Formula (I)>

According to another aspect of the present invention, preparing an aqueous solution of a furfurylamine compound of formula (I) and an unsaturated acyclic amine compound of formula (II), contacting the aqueous solution to at least a portion of the substrate surface , It provides a method for modifying a substrate comprising the steps of washing and drying the substrate.

<Formula (I)>

<Formula (II)>

In the above formula,

X is -NH ₂ , -N=CH-OH, or -N=O;

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 (wherein , R ⁴ and R ⁵ are hydrogen or C ₁ -C ₆ alkyl).

Preferably, in the above formula (II),

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 (wherein , R ⁴ and R ⁵ are hydrogen or C ₁ -C ₃ alkyl).

More preferably, in the above formula (II),

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 hydrogen or methyl) is a substituent selected from the group consisting of.

Most preferably, the compound of formula (II) is selected from, for example, methyl 3-aminocrotonate, ethyl 3-aminocrotonate, N-vinylformamide, 3-aminocrotonitrile, N[(2E)-3- It is a compound selected from the group consisting of nitrosobut-2-en-2yl] hydroxyamine, diaminomaleonitrile, and 4-aminopent-3-en-2-one.

According to the present invention, the surface of a substrate can be chemically modified using a furfurylamine compound independently of the substrate, and can be carried out in a simple process without using special equipment or processing means.

In addition, the furfurylamine compound used as a surface modifier in the present invention has better reactivity than the aromatic amine compound, which is a surface modifier disclosed in the prior invention, and can effectively modify the surface of a substrate. Compared to unsaturated heterocycle compounds, vinyl heterocycle compounds, amino cycloalkene compounds and vinyl amino non-aromatic ring compounds, it is advantageous in terms of cost and can be advantageously applied to applications where toxicity is sensitive, such as food packaging materials this exists

The term "oligomer" as used herein refers to a polymer composed of a relatively small number of repeating units, on the order of 100 or less. In this case, the repeating unit may be composed of identical molecules or may be composed of molecules different from each other.

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 oligomers, and is produced by bonding between different molecules. It is specifically referred to as a "copolymer". The copolymer may have various forms such as an alternating copolymer, a random copolymer, a block copolymer, and a graft copolymer.

As used herein, the term "modification" or "surface modification" means that the furfurylamine compound of Formula (I) acts as a surface modifier to form the compound, an oligomer or (co)polymer thereof on the surface of a substrate through chemical bonding. means attached.

The method for modifying a substrate according to the present invention comprises the steps of preparing an aqueous solution of the furfurylamine compound of formula (I), contacting the aqueous solution to at least a part of the surface of the substrate, and washing and drying the substrate. to be characterized

In the substrate modification method according to the present invention, the aqueous solution of the furfurylamine 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) and the like can be used as a solvent, but are not particularly limited thereto. Aqueous solutions are 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.

A container having a volume sufficient to accommodate the substrate to be modified is filled with the solution prepared as described above, 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 certain period of time, any method other than immersing the substrate in the aqueous solution is possible. For example, it is possible to contact the substrate and the aqueous solution by spraying the aqueous solution on the surface of the substrate so that the surface of the substrate can sufficiently contact the aqueous solution or by a method used in various coating processes.

Modification according to the present invention can be carried out only by incubation 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 introduced, but it is not absolutely necessary. The reaction time and reaction temperature are not particularly limited, and can be appropriately selected and adjusted by a person skilled in the art according to the type of specific compound and substrate used. 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.

After a period of incubation, 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.

When used together with other surface modifiers, it is sufficient to prepare an aqueous solution containing both the furfurylamine compound and other surface modifier compounds of the present invention and apply it as it is to the above preparation method.

In the present invention, the substrate may be glass, wood, stone, metal, ceramic, natural and synthetic polymers, and the like, and is not particularly limited.

Metal substrates include, for example, iron, copper, aluminum, zinc, tin, silver, gold, titanium, tungsten, nickel, molybdenum, cobalt, magnesium, and alloys thereof, but are not particularly limited thereto.

Ceramics are inorganic compounds of metals, nonmetals, or metalloids, such as zinc oxide, zirconium oxide, titanium oxide, aluminum borate, iron oxide, calcium carbonate, barium carbonate, lead oxide, tin oxide, cerium oxide, lithium oxide, calcium oxide, Magnesium oxide, trimanganese tetroxide, niobium oxide, tantalum oxide, tungsten oxide, antimony oxide, aluminum phosphate, calcium silicate, zirconium silicate, ITO (tin-containing indium oxide), titansilicate, barium titanate, strontium titanate, calcium titanate, montmorillonite, sandpaper Nitride, vermiclite, hydrotalcite, kaolinite, carnemite, margadiite, kenite, silica, alumina, zeolite, lithium nitride, lithium silicate, lithium borate, lithium aluminate, lithium phosphate, lithium phosphorus oxynite Lide, lithium silicon sulfide, lithium lanthanum oxide, lithium titanium oxide, lithium borosulfide, lithium aluminosulfide, lithium phosphosulfide, aluminum titanium oxide, and the like, but are not particularly limited thereto.

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., such as polyethylene, polypropylene, polymethylpentene, polyolefins including polybutene-1, polyisobutylene, and ethylene-propylene rubber. , polyolefin elastomers including ethylene-propylene-diene rubber (EPDM), etc., halogenated polyolefins including polyvinyl chloride, polyvinylidene chloride, polychlorotrifluoroethylene, polyvinylidene fluoride, polytetrafluoroethylene, etc. Polyesters including polystyrene, polyvinyl alcohol, polyacetal, polyvinyl acetate, polyacrylonitrile, polybutadiene, polyisoprene, phenol resin, epoxy resin, polyamide, polyethylene terephthalate and polybutylene terephthalate, etc. polyimide, polyamideimide, polyetherimide, polyacrylate, polyurethane, polysiloxane, polynaphthalene, polythiophene, polyaniline, polyparaphenylene sulfide, polychloroprene, styrene-butadiene rubber, nitrile rubber, silicone rubber and these and the like, and is not particularly limited thereto.

The shape of the substrate may also be powder, bead, plate, rod, tube, or any three-dimensional shape and is not particularly limited. In addition, it is also possible to modify only a portion of the substrate by bringing only a portion of the substrate into contact with the aqueous solution of the compound of formula (I), if necessary.

<Example>

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 later. A person skilled in the art can understand that the compounds, substrates, and implementation techniques exemplified in the Examples represent representative examples in practicing the present invention. In addition, those skilled in the art may change the specific embodiments described based on the disclosed information in various ways and obtain similar results without departing from the technical spirit and protection scope of the present invention.

Example 1a: Modification of furfurylamine on a glass slide in a weakly basic solution at room temperature

A solution having a concentration of 1 mg/1 mL was prepared by adding furfurylamine to borate buffer (50 mM) at pH 9.0. A glass slide was immersed in the solution at room temperature for 20 hours. The glass slide was 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.

Example 1b: Copolymer modification of furfurylamine and methyl 3- aminocrotonate on a glass slide in a weakly basic solution at room temperature

Furfurylamine and methyl 3-aminocrotonate were added to borate buffer (50 mM) at pH 9.0 to prepare solutions of 1mg/1mL and 1.7mg/1mL concentrations for the two solutes, respectively. In the subsequent process, a modified sample was prepared in the same manner as in Example 1a.

Comparative Example 1

A glass slide of the same standard as that used in Example 1 was immersed in borate buffer (50 mM) at pH 9.0 at room temperature for 20 hours. The glass slide was 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.

Example 2a: Modification of furfurylamine on glass slides in strong basic solution at room temperature

A solution having a concentration of 1mg/1mL was prepared by adding furfurylamine to an 8% aqueous solution of dimethylethanolamine having a pH of 13. A glass slide was immersed in the solution at room temperature for 12 hours. The glass slide was 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.

Example 2b: Copolymer modification of furfurylamine and methyl 3- aminocrotonate on a glass slide in a strong basic solution at room temperature

Furfurylamine and methyl 3-aminocrotonate were added to an 8% aqueous solution of dimethylethanolamine at pH 13 to prepare solutions having concentrations of 1mg/1mL and 1.7mg/1mL for the two solutes, respectively. In the subsequent process, a modified sample was prepared in the same manner as in Example 2a.

Comparative Example 2

A glass slide of the same standard as that used in Example 2 was immersed in borate buffer (50 mM) at pH 9.0 at room temperature for 12 hours. The glass slide was 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.

Example 3a: on a polyimide film in a weakly basic solution at room temperature Modified furfurylamine

A surface modified film was prepared in the same manner as in Example 1a, except that a polyimide (PI) film was used.

Example 3b: on a polyimide film in a weakly basic solution at room temperature Copolymer modification of furfurylamine and 3-aminocrotonic acid methyl

A surface modified film was prepared in the same manner as in Example 1b, except that a polyimide (PI) film was used.

Comparative Example 3

Samples were prepared in the same manner as in Comparative Example 1, except that a polyimide (PI) film was used.

Example 4: 50° C. On a polyimide film in a weak basic solution Modified furfurylamine

A solution having a concentration of 1 mg/1 mL was prepared by adding furfurylamine to a borate buffer (50 mM) at pH 9.0. A polyimide (PI) film was immersed in the solution and incubated at 50° C. for 3 hours. The PI film was 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.

Comparative Example 4

A PI film of the same standard as that used in Example 4a was immersed in borate buffer (50 mM) at pH 9.0 and incubated at 50° C. for 3 hours. The PI film was 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 PI film was washed with HCl solution for 20 seconds, washed with a sufficient amount of water, and then dried at 70 °C for 5 minutes.

Example 5: 70° C. On a polyimide film in a weak basic solution Modified furfurylamine

A solution having a concentration of 1 mg/1 mL was prepared by adding furfurylamine to a borate buffer (50 mM) at pH 9.0. A polyimide (PI) film was immersed in the solution and incubated at 70° C. for 20 hours. In the subsequent process, a modified sample was prepared in the same manner as in Example 4.

Comparative Example 5

A PI film of the same standard as that used in Example 5 was immersed in borate buffer (50 mM) at pH 9.0 and incubated at 70° C. for 20 hours. In the subsequent process, a modified sample was prepared in the same manner as in Comparative Example 4.

Example 6a: on a polyimide film in a strong basic solution at room temperature Modified furfurylamine

A surface modified film was prepared in the same manner as in Example 2a, except that a polyimide (PI) film was used.

Example 6b: on a polyimide film in a strong basic solution at room temperature Copolymer modification of furfurylamine and 3-aminocrotonic acid methyl

A surface modified film was prepared in the same manner as in Example 2b, except that a polyimide (PI) film was used.

Comparative Example 6

Samples were prepared in the same manner as in Comparative Example 2, except that a polyimide (PI) film was used.

Example 7: On polyimide film in 70° C. strong basic solution Modified furfurylamine

A solution having a concentration of 1mg/1mL was prepared by adding furfurylamine to an 8% aqueous solution of dimethylethanolamine having a pH of 13. A polyimide (PI) film was immersed in the solution and incubated at 70° C. for 20 hours. The PI film was 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.

Comparative Example 7

A PI film of the same standard as that used in Example 7 was immersed in an 8% aqueous solution of dimethylethanolamine at pH 13 and incubated at 70° C. for 20 hours. The glass slide was 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.

Example 8a: on a polyethylene film in a weakly basic solution at room temperature Modified furfurylamine

A surface-modified film was prepared in the same manner as in Example 1a, except that a polyethylene (PE) film for food packaging (composite film in which a printing surface film and an aluminum film are present between double-sided polyethylene films) was used.

Example 8b: on a polyethylene film in a weakly basic solution at room temperature Copolymer modification of furfurylamine and 3-aminocrotonic acid methyl

A surface modified film was prepared in the same manner as in Example 1b, except that a polyethylene (PE) film for food packaging was used.

Comparative Example 8

Samples were prepared in the same manner as in Comparative Example 1, except that a polyethylene (PE) film for food packaging was used.

Example 9a: on a polyethylene film in a strong basic solution at room temperature Modified furfurylamine

A surface modified film was prepared in the same manner as in Example 2a, except that a polyethylene (PE) film for food packaging was used.

Example 9b: on a polyethylene film in a strong basic solution at room temperature Copolymer modification of furfurylamine and 3-aminocrotonic acid methyl

A surface modified film was prepared in the same manner as in Example 2b, except that a polyethylene (PE) film for food packaging was used.

Comparative Example 9

Samples were prepared in the same manner as in Comparative Example 2, except that a polyethylene (PE) film for food packaging was used.

<Measurement of contact angle>

To measure the contact angle, a goniometer (model 300) from Ramehart Instruments, New Jersey, USA was used. Using a microsyringe, a droplet of 2 µl of the sample solution (15% aqueous solution of dimethylethanolamine or distilled water) was placed on the sample surface on the goniometer sample stage. After taking a side picture showing the contact state between the sample liquid drop placed on the sample stage of the goniometer and the sample surface, the goniometer's DROPImage software is used to find out the quantitative information of the contact angle. The contact angle was measured using this method.

Tables 1 to 9 show the results of measuring the contact angles of all the sample films of Examples and each of the sample films of Comparative Examples in the same manner as above. "Drip" means the sample liquid used for measuring the contact angle.

Contact angle measurement results of Example 1a and 1b samples and Comparative Example 1 samples drip: water Example 1a Example 1b Comparative Example 1 One 70.0˚ 68.0˚ 48.2˚ 2 63.6˚ 66.4˚ 52.5˚ 3 63.6˚ 65.8˚ 53.2˚ 4 65.0˚ 61.8˚ 51.0˚ 5 63.6˚ 64.8˚ 54.0˚ Average 65.2˚ 65.4˚ 51.8˚

Contact angle measurement results of Example 2a and 2b samples and Comparative Example 2 samples drip: water Example 2a Example 2b Comparative Example 2 One 29.6˚ 47.2˚ 32.9˚ 2 23.0˚ 35.0˚ 35.6˚ 3 22.4˚ 43.2˚ 27.9˚ 4 32.2˚ 41.9˚ 30.6˚ 5 36.2˚ 50.6˚ 28.2˚ Average 28.7˚ 43.6˚ 31.0˚

Contact angle measurement results of Example 3a and 3b samples and Comparative Example 3 samples drip: water Example 3a Example 3b Comparative Example 3 One 72.0˚ - 73.0˚ 2 85.6˚ 75.4˚ 70.6˚ 3 82.8˚ 76.4˚ 65.4˚ 4 71.6˚ 75.6˚ 73.0˚ 5 63.8˚ 70.8˚ 67.6˚ Average 75.2˚ 74.6˚ 69.9˚

Contact angle measurement results of the sample of Example 4 and the sample of Comparative Example 4 drip: water Drops: 15% DMEA aqueous solution Example 4 Comparative Example 4 Example 4 Comparative Example 4 One 84.6˚ 82.3˚ 62.3˚ 44.2˚ 2 88.4˚ 73.6˚ 46.0˚ 55.0˚ 3 82.0˚ 77.9˚ 50.3˚ 47.5˚ Average 85.0˚ 77.9˚ 52.9˚ 48.9˚

Contact angle measurement results of the samples of Example 5 and Comparative Example 5 drip: water Drops: 15% DMEA aqueous solution Example 5 Comparative Example 5 Example 5 Comparative Example 5 One 85.7˚ 62.4˚ 45.0˚ 45.0˚ 2 68.6˚ 78.6˚ 51.2˚ 45.2˚ 3 75.6˚ 75.4˚ 45.8˚ 46.9˚ 4 75.4˚ 67.8˚ 53.4˚ 51.1˚ 5 75.4˚ 67.6˚ 48.4˚ 40.5˚ Average 76.1˚ 70.4˚ 48.8˚ 45.7˚

Contact angle measurement results of Example 6a and 6b samples and Comparative Example 6 samples drip: water Drops: 15% DMEA aqueous solution Example 6a Example 6b Comparative Example 6 Example 6a Example 6b Comparative Example 6 One 55.8˚ 68.8˚ < 10˚ 34.9˚ 32.0˚ - 2 53.6˚ 72.4˚ < 10˚ 34.4˚ 37.4˚ 21.8˚ 3 47.9˚ 70.8˚ < 15˚ 45.0˚ 22.0˚ 25.8˚ 4 49.7˚ 56.8˚ - 37.2˚ - 28.3˚ 5 42.6˚ - - 42.4˚ - 33.0˚ Average 49.9˚ 67.2˚ < 15˚ 38.8˚ 67.2˚ 27.2˚

Contact angle measurement results of the sample of Example 7 and the sample of Comparative Example 7 drip: water Drops: 15% DMEA aqueous solution Example 7 Comparative Example 7 Example 7 Comparative Example 7 One 53.6˚ 45.0˚ 21.7˚ < 15˚ 2 45.4˚ 48.0˚ 15.4˚ < 15˚ 3 45.6˚ 50.1˚ 21.8˚ < 15˚ 4 44.3˚ 30.2˚ 21.2˚ < 15˚ 5 38.1˚ 25.8˚ - < 15˚ Average 45.4˚ 39.8˚ 48.8˚ < 15˚

Contact angle measurement results of Example 8a and 8b samples and Comparative Example 8 samples drip: water Drops: 15% DMEA aqueous solution Example 8a Example 8b Comparative Example 8 Example 8a Example 8b Comparative Example 8 One 96.9˚ 102.5˚ 95.8˚ 93.8˚ 85.5˚ 85.9˚ 2 102.6˚ 97.2˚ 91.2˚ 77.2˚ 92.6˚ 77.2˚ 3 101.5˚ 104.0˚ 87.9˚ 90.8˚ 93.2˚ 64.6˚ 4 97.2˚ 104.5˚ 93.4˚ 80.8˚ 92.5˚ 90.1˚ 5 99.2˚ 91.7˚ 90.6˚ 90.4˚ 82.6˚ 86.6˚ Average 99.5˚ 100.0˚ 91.8˚ 86.6˚ 89.3˚ 80.1˚

Contact angle measurement results of Examples 9a and 9b samples and Comparative Example 9 samples Drops: 15% DMEA aqueous solution Example 9a Example 9b Comparative Example 9 One 78.6˚ 82.9˚ 74.7˚ 2 - 86.3˚ 76.3˚ 3 93.3˚ 95.1˚ 74.1˚ 4 87.9˚ 87.3˚ 86.3˚ 5 86.0˚ 85.9˚ 76.0˚ Average 85.2˚ 87.5˚ 77.5˚

From the above results, it was confirmed that furfurylamine was used alone or in combination with methyl 3-aminocrotonate to provide a hydrophobic coating for surface modification of various substrates. Depending on the specific substrate and surface modification conditions, the properties of the modified surface can vary, and when two compounds, furfurylamine and methyl 3-aminocrotonate, are used together, a more hydrophobic coating tends to be obtained. . 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 a furfurylamine compound or an oligomer or (co)polymer thereof is surface-modified independently of the substrate and a method for modifying the same, which can be used for chemical surface modification of various substrates. In particular, suitable hydrophobicity can be imparted to the surface of materials used in applications requiring hydrophobicity, or vice versa. In addition, it is also possible to improve the separation yield and reliability of biochemicals by modifying the chemical properties of one interface in order to improve the adhesion between the interfaces or by using a modified compound appropriately selected to match the properties of the biochemicals to be fixed and/or separated. , The industrial fields in which the present invention can be used are infinite.

Claims (17)

A substrate surface-modified with a furfurylamine compound of formula (I) or an oligomer or (co)polymer thereof by reacting a furfurylamine compound of formula (I) with a surface modifier on at least a portion of a substrate surface.
<Formula (I)>

The furfurylamine compound of formula (I) or an oligomer or (co)polymer thereof according to claim 1, characterized in that the unsaturated acyclic amine compound of formula (II) is reacted with an additional surface modifier. temperament
<Formula (II)>

In the above formula (II),
X is -NH ₂ , -N=CH-OH, or -N=O;
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 (wherein , R ⁴ and R ⁵ are hydrogen or C ₁ -C ₆ alkyl).
According to claim 2,
In the above formula (II),
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 (wherein , R ⁴ and R ⁵ are hydrogen or C ₁ -C ₃ alkyl) characterized by being a substituent selected from the group consisting of furfurylamine compound of formula (I) or its oligomer or (co)polymer surface modification temperament.
According to claim 2,
In the above formula (II),
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 hydrogen or methyl), a substrate surface-modified with a furfurylamine compound of formula (I) or an oligomer or (co)polymer thereof, characterized in that it is a substituent selected from the group consisting of
According to claim 2,
The unsaturated acyclic amine compound of Formula (II) is 3-aminocrotonate methyl, 3-aminocrotonate ethyl, N-vinylformamide, 3-aminocrotonitrile, N[(2E)-3-nitrosobut -2-en-2yl] hydroxyamine, diaminomaleonitrile, and 4-aminopent-3-en-2-one, characterized in that the compound selected from the group consisting of, A substrate surface-modified with a furylamine compound or an oligomer or (co)polymer thereof.
The method of claim 1 to 5, characterized in that the substrate is selected from the group consisting of glass, wood, stone, metal, ceramic, natural and synthetic polymers,
A substrate surface-modified with the furfurylamine compound of formula (I) or an oligomer or (co)polymer thereof.
The method of claim 6, characterized in that the substrate is a synthetic polymer,
A substrate surface-modified with the furfurylamine compound of formula (I) or an oligomer or (co)polymer thereof.
The method of claim 7, 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 Characterized in that it is selected from the group consisting of rubber and copolymers thereof,
A substrate surface-modified with the furfurylamine compound of formula (I) or an oligomer or (co)polymer thereof.
Preparing an aqueous solution of a furfurylamine compound of formula (I),
contacting the aqueous solution to at least a portion of the substrate surface;
Method for modifying the surface of a substrate comprising the steps of washing and drying the substrate
<Formula (I)>

Preparing an aqueous solution of a furfurylamine compound of Formula (I) and an unsaturated acyclic amine compound of Formula (II) below;
contacting the aqueous solution to at least a portion of the substrate surface;
Method for modifying the surface of a substrate comprising the steps of washing and drying the substrate
<Formula (I)>

<Formula (II)>

In the above formula (II),
X is -NH ₂ , -N=CH-OH, or -N=O;
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 (wherein , R ⁴ and R ⁵ are hydrogen or C ₁ -C ₆ alkyl).
According to claim 10,
In the above formula (II),
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 (wherein , R ⁴ and R ⁵ are hydrogen or C ₁ -C ₃ alkyl) characterized in that the substituent selected from the group consisting of, surface modification method of the substrate.
According to claim 10,
In the above formula (II),
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 hydrogen or methyl), characterized in that the substituent selected from the group consisting of, surface modification method of the substrate.
According to claim 10,
The unsaturated acyclic amine compound of Formula (II) is 3-aminocrotonate methyl, 3-aminocrotonate ethyl, N-vinylformamide, 3-aminocrotonitrile, N[(2E)-3-nitrosobut -2-en-2yl] hydroxyamine, diaminomaleonitrile, and 4-aminopent-3-en-2-one, characterized in that the compound selected from the group consisting of, surface modification method of the substrate.
14. The method for surface modification of a substrate according to any one of claims 9 to 13, wherein the aqueous solution is any one of an acidic solution, a neutral solution, and a basic solution.
14. The method for surface modification of a substrate according to any one of claims 9 to 13, wherein the substrate is selected from the group consisting of glass, wood, stone, metal, ceramic, and natural and synthetic polymers.
16. The method of claim 15, wherein the substrate is a synthetic polymer.
The method of claim 16, 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.