WO2018062835A1 - Quinone curable compositions and adhesive compositions comprising same - Google Patents

Abstract

The present invention relates to a curable composition and a use thereof and, more particularly, to a curable composition and a use thereof, the curable composition comprising: (a) a compound capable of being denatured to a quinone-based compound by oxygen; (b) an amine-based polymeric compound; and (c) an oxygen clathrate structure. The curable composition is rapidly cured and can be cured not only at an interface of a conventional film but also to the inside of the film, such that the curable composition has uniform physical properties throughout the entire film and excellent physical properties compared to a cured film obtained by curing at an existing interface.

Description

Quinone Curable Compositions and Adhesive Compositions Comprising the Same

The present invention relates to a quinone curable composition capable of producing a cured film that is easily surface and internal curable and an adhesive composition comprising the same.

Biomimetics (biomimetics) means to develop new technologies by studying and imitating the characteristics of living organisms. Biomimetics, a study of biomimetics, has helped to create new biomaterials, design new intelligent systems, create new devices by mimicking biological structures, and design new optical systems.

Related examples of biomimetics include Gecko tapes using the gecko lizard's sole bristles, Whale Power, a wind turbine using uneven protrusions in the fins of whales, and a Shinkansen high-speed train with reduced noise, modeling the shape of a kingfisher's beak. And mussel adhesives imitated from the protein of mussel family.

Detailed description of the mussel adhesive is as follows. Mussels are strongly bonded to various surfaces in water, such as rocks, metals, and plastics. Analysis of the attached mussels results in a 3,4-dihydroxy-L-phenylalanine (DOPA) catechol. Contains a lot of call precursor

Although there is no clear understanding of the adhesive function of mussel glioma, it has been reported that many of the DOPA moieties are produced by oxidants or enzyme-promoted cross-linking. One theory is that during the formation of adhesive plaques, the quinone functionality crosslinks with other quinones via radical reactions, or with amines, thiols and Michael additions, to form crosslinks [V. Vreeland, JH Waite, and L. Epstein, J Phycol ., 34 , 1 (1998); CR Matos-Perez, JD White, and JJ Wilker, J. Am . Chem . Soc ., 134 , 9498 (2012); BP Lee, JL Dalsin, and PB Messersmith, Biomacromolecules. , 3 , 1038 (2002).] There is an opinion that three catechol functional groups crosslink through a single Fe (III) ion through metal ion coordination bonds [E. Faure, C. Falentin-Daudre, C. Jerome, J. Lyskawa, D. Fournier, P. Woisel, and C. Detrembleur, Prog . Polym . Sci ., 38 , 236 (2013); DG Barrett, DE Fullenkamp, L. He, N. Holten-Andersen, KYC Lee, and PB Messersmith, Adv . Funct . Mater ., 23 , 1111 (2013).].

Mussel adhesives have the ability to bond to a wide variety of surfaces, including inorganic, plastic, metal, glass and biomaterials. In addition, unlike conventional chemical adhesives that have low adhesion on wet surfaces or in water, mussel adhesives can be bonded in water. In addition, since it does not attack cells or cause an immune response even when used directly in a living body, it is also very easy for medical use.

Mussel adhesives for medical use are mainly used as tissue adhesives. As a result, mussel adhesive proteins were extracted and measured for adhesion to pig skin. However, they showed better adhesion than fibrin glue, but the curing time and bio temperature of 6 to 24 hours 37 A curing temperature of 45 ° C. outside of C was required and therefore unsuitable for medical use [HJ Cha et al ., Development of bioadhesives from matine mussels, Biotechnol. J. 3 , 631-638 (2008)].

Thus, research into adhesive polymers incorporating the catechol structure of DOPA that mimics the natural properties of adhesive proteins extracted from mussels has been conducted. Specifically, poly [(3,4-dihydroxystyrene) -co-styrene] (poly [(3) using 3,4-dihydroxystyrene, similar to a catechol functional group, , 4-dihydroxystyrene) -co-styrene]) was used to increase the adhesion and mechanical strength, but this also could not secure stable adhesion.

In another attempt, Korean Patent Laid-Open Publication No. 2015-0144846 uses a catechol-based organic compound and an amine polymer to prepare a functional film (ie, cured film) at an interface between a liquid phase and a gaseous phase, and the functional film is a biomaterial. It has been disclosed that it can be applied to various fields such as hemostatic agents, biocatalysts and membranes. The curing reaction occurs mainly on the surface of the functional film in the presence of oxygen, the inside of the water is present in the physical properties of the film is low (e.g., recognized strength, durability, etc.) is difficult to apply to the product substantially, the curing rate is The formation of the cured film is limited on the surface through which oxygen does not pass because it is slow and forms the functional film only at the interface with oxygen.

(Patent Document 1) Korean Patent Publication No. 2015-0144846

(Non-Patent Document 1) V. Vreeland, JH Waite, and L. Epstein, J Phycol ., 34 , 1 (1998)

(Non-Patent Document 2) CR Matos-Perez, JD White, and JJ Wilker, J. Am . Chem . Soc ., 134 , 9498 (2012)

(Non-Patent Document 3) BP Lee, JL Dalsin, and PB Messersmith, Biomacromolecules. , 3 , 1038 (2002)

(Non-Patent Document 4) E. Faure, C. Falentin-Daudre, C. Jerome, J. Lyskawa, D. Fournier, P. Woisel, and C. Detrembleur, Prog . Polym . Sci ., 38 , 236 (2013)

(Non-Patent Document 5) DG Barrett, DE Fullenkamp, L. He, N. Holten-Andersen, KYC Lee, and PB Messersmith, Adv . Funct . Mater ., 23 , 1111 (2013)

(Non-Patent Document 6) HJ Cha et al ., Development of bioadhesives from matine mussels, Biotechnol. J. 3 , 631-638 (2008)

Accordingly, the present inventors conducted various studies to increase the curing rate of the compound having a catechol structure and the amine polymer and to improve the physical properties of the obtained functional film. The present invention was completed by confirming that internal curing may be simultaneously performed to improve the physical properties of the film and to shorten the curing time by using a material capable of supplying oxygen, that is, an oxygen inclusion structure, so that curing can be achieved.

Accordingly, an object of the present invention is to provide a curable composition capable of curing the air / solution interface and solution inside, and to prepare a cured film having a fast curing rate.

Another object of the present invention is to provide a use of the curable composition.

In order to achieve the above object, the present invention (a) catechol-based organic compound capable of denaturation to quinone by oxidation; (b) amine polymer compounds; And (c) provides a curable composition comprising an oxygen inclusion structure.

At this time, the oxygen inclusion structure is characterized in that it comprises an aerogel, web, sheet, foam, sphere, tube, porous structure or lattice structure containing 1 to 99% oxygen.

The present invention also provides the use of the curable composition as an adhesive and a coating agent.

Curable composition according to the present invention is hardened at a faster rate than the existing composition does not contain an oxygen trapping structure, the curing occurs by the oxygen released from the oxygen trapping structure even inside the solution, it serves to cure evenly as a whole Compared to the composition, it has excellent physical properties when used as an adhesive and a coating. The characteristics include adhesion, cohesion, strength, and the like. The curable compositions are applicable and applicable throughout most industries where cured films are required.

1 is a graph showing the change in dissolved oxygen amount of water according to the amount of airgel.

FIG. 2 is a photograph comparing the catechol-based organic compound solution (Comparative Example 1) that does not include an airgel and Examples 1, 2 and 3 including an airgel by concentration (1%, 2%, 3%) (a) Is taken within 5 minutes of mixing, and (b) is taken after 24 hours.

Figure 3 (a) is a photograph of the adhesive cross-section of Comparative Example 1 applied to the two metal cross-section facing the solution containing no airgel, (b) of Example 1 applied to the metal cross-section facing the solution containing aerogel Adhesive cross section photo. (c) and (d) are the images which observed the cross section of (a) and (b) with the cross-sectional scanning electron microscope, respectively.

Hereinafter, the present invention will be described in more detail.

The curable composition according to the present invention undergoes curing through the quinone curing mechanism.

As shown in Scheme 1, the quinone curing mechanism is converted into a quinone structure by oxidation, and the quinone is subjected to a chain-forming reaction with a polymer compound containing an amine group (NH ₂ ). It means that hardening takes place.

Scheme 1

Such quinone curing can be easily proceeded by oxygen in the air without the consumption of energy applied externally, that is, heat or UV light irradiation, such as conventional thermal curing or photocuring.

In order to enable the quinone curing mechanism, the curable composition according to the present invention includes a catechol-based organic compound and an amine-based polymer compound capable of oxidizing to a quinone-based compound by oxygen as a reaction material. Curing occurs by the reaction between the catechol-based organic compound and the amine-based polymer compound, but at this time, the curing is performed only at an interface capable of reacting with oxygen, and is limited within the cured film applied for curing, thereby adhering or There are many limitations in using the coating material.

Accordingly, in the present invention, curing is performed not only at the interface but also at the inside of the cured film, and an oxygen inclusion structure is used to improve the curing reaction rate.

The oxygen inclusion structure may contain oxygen in the structure, and means a material capable of supplying oxygen so that the oxidation reaction of the catechol-based organic compound may proceed.

The oxygen inclusion structure that can be used is not particularly limited in the present invention, but it is preferable that the oxygen inclusion amount is high and oxygen can be easily supplied into the cured film.

The oxygen inclusion amount of the oxygen inclusion structure is 1 to 99%, preferably 3 to 90%. In addition, the oxygen may be used in addition to oxygen contained in the air, high purity or high compression oxygen.

In addition, the oxygen inclusion structure preferably has a porosity characteristic of the pores in the structure so that oxygen can be easily supplied in order to smoothly oxidize the catechol organic compound. At this time, depending on the shape of the structure, it is advantageous to have a porosity of 10 to 99%, preferably 15 to 96%.

In addition, the oxygen inclusion structure of the present invention preferably does not lower the physical properties of the cured film formed after the application of the curable composition, it is more preferable to improve its physical properties. The oxygen inclusion structure is preferably uniformly applied in the cured film so that internal curing can occur at a high speed at the same time. If the particles are too large or heavy, curing may occur only at one side (lower side) and only at the interface at the other side (upper side and side).

Preferable oxygen inclusion structure can be any property as long as oxygen supply is possible, and is not specifically limited in this invention. Representatively, they may be aerogels, webs, sheets, foams, spheres, tubes, porous structures or lattice structures, preferably in the form of gels, webs, microspheres.

The term 'gel' refers to a solid substance that is filled with gas instead of liquid in the gel. The airgel is made up of 90 to 99.9% of air, the density is 3 to 150 mg / cm ³ , forms a porous structure having a pore of 0.1 to 100nm level in the shape of a mesh, and has hydrophilicity as it is. The airgel may be made of various materials, and these may include an airgel made of silica, aluminum, chromium, tin, carbon, sodium, calcium, and the like, and an airgel made of two or more materials thereof.

The term 'web' means that the fiber aggregates or films are bonded to each other by mechanical or suitable moisture or heat by physical or chemical means. Such a web is a plane made by tangling various fibers of glass, metal, polymer, or a hybrid material thereof according to mutual characteristics to form a sheet-shaped web, and then joining them by a mechanical or physical method. Refers to structural molded products. The average pore of the web is 1nm to 100㎛, has a porosity of 1 to 70%, and has a thickness of 1nm to 1000㎛.

The term 'sheet' refers to a porous sheet produced through wet coating, extrusion process, sheet molding or calendar molding. The sheet may be a metal, a metal oxide, a polymer, or a hybrid material thereof. The average pore is 1 nm to 100 μm, has a porosity of 1 to 70%, and has a thickness of 1 nm to 1000 μm.

The term 'foam' is also called a sponge (sponge), and more than 90% of the volume to form a pore, that is, a complete open cell (pore), forming a three-dimensional network structure, each of the pores are completely continuous structure Have The sponge is manufactured by foaming, and the material may be any metal or polymer that can be foamed, and examples thereof include Ti sponge, polyethylene sponge, polyurethane sponge, rubber sponge, polyvinyl alcohol sponge, and the like. It has excellent hydrophilicity depending on the material. At this time, the density of the sponge is 1 to 300 mg / cm ³ , the pores are nano-level to micron level, having a variety of pores of various sizes.

The term 'microsphere' refers to particles in the form of spheres, and may be nanospheres having a diameter of nanoscale, or microspheres having a diameter of a micrometer, depending on the size thereof. It may be a hollow sphere or a porous sphere with pores formed therein. In one example, the hollow nanospheres may be hollow and have a nanoscale diameter size. The diameter of the sphere is 1nm to 100㎛ pore, has a porosity of 10 to 99%, and has a thickness of 1nm to 1000㎛

The term 'tube' refers to a cylinder, cylindrical or spiral cylindrical structure, and oxygen can be contained in the tube and the space between the tubes. Preferably, the tube may be a metal nanotube, a metal oxide nanotube and a carbon nanotube, the diameter may be 1 to 5000nm, has a length of 1nm to 1000㎛.

The term 'porous structure' refers to a structure having about 15 to 95% of the volume of pores and having new properties or not imparted to existing dense materials.

The term 'lattice structure' refers to a structure having a structure in which pores arranged connected to each other in a lattice form are stacked. The pores may be connected to each other to form open pores, the average pore is 1nm to 100㎛, has a porosity of 10 to 99%, 1nm to. The lattice structure may have a thickness of 1000 μm. A well-known method may be used as the lattice structure by laminating wires, by three-dimensional assembling, or by manufacturing and removing a structure for forming pores.

At this time, the material of the oxygen inclusion structure is not particularly limited and may be used in the form of one or more selected from the group consisting of metals, metal oxides, glass, carbon materials and polymers, or two or more kinds thereof.

As a metal material, since water is used as a solvent of the curable composition and should include oxygen, a material that is not corrosive to water and oxygen may be preferable, but is not particularly limited. Do. For example, W, Mo, V, Ti, Al, Be, Zr, Au, Pt, Cu, Cr, Zn, Mo, Ag, Rh, Pa, La, Ir, Kr, Nd, Nb, Se, Sc, Ru, At least one selected from the group consisting of In, Y, Z, and stainless steel, or a mixture of two or more thereof, and preferably Ti.

As the metal oxide, at least one compound selected from the group consisting of SiO ₂ , TiO ₂ , ZrO ₂ , CeO ₂ , Al ₂ O ₃ , B ₂ O ₃ , ZnO, BaO, MgO, CaO, and BaCa (CO ₃ ) ₂ It may be made of, preferably SiO ₂ is used.

As glass, well-known glass, such as a soda lime glass, calcium lime glass, lead glass, barium glass, and a silicate glass, can be used, It does not specifically limit in this invention.

The carbon material may be carbon fiber, carbon black, carbon nanotubes (CNT), graphite, graphene, activated carbon, and the like, and is not particularly limited in the present invention.

The polymer material may be both a natural polymer and a synthetic polymer, and the synthetic polymer may be both a thermoplastic resin and a thermosetting resin. For example, thermoplastic resins include polyethylene, polypropylene, polycarbonate, polystyrene, polyacrylate, nylon, polyester, polyvinyl alcohol, polyamide, polyimide, polyacetal, polysulfone, polyethersulfone, polyketone, and the like. The thermosetting resin may be a phenol resin, melamine resin, epoxy resin, unsaturated polyester resin, or the like. In addition to this, a variety of known polymer materials may be used, and are not particularly limited in the present invention.

Preferably, the oxygen inclusion structure proposed in the present invention is activated carbon, activated carbon fiber, TiO ₂ halosphere, glass web, silica aerogel, fume silica nanoparticles, SiO ₂ hollow particles, TiO in consideration of both material and properties ₂ hollow particles, silica nanotubes and carbon nanotubes are possible

Such oxygen inclusion structure depends on the oxygen inclusion ratio but is used in the range of 1 to 99% by weight, preferably 2 to 99% by weight in the curable composition based on the solid content. If the content is less than the above range, the inside of the cured film may be uncured. If the content exceeds the above range, the physical properties of the cured film may be deteriorated. Therefore, it is preferable to use the cured film appropriately within the above range.

In the case of a web, a sheet, or a foam, the oxygen inclusion structure is preferably 10 to 99% by weight, more preferably 15 to 99% by weight in the curable composition based on the solid content. In other words, since the polymer itself is coated on the web, sheet, and foam, the solid content of the oxygen inclusion structure must be relatively high.)

The shape of the oxygen inclusion structure is preferably 1 to 50% by weight, more preferably 1 to 20% by weight in the curable composition based on the solid content in the case of aerogel, sphere, tube, lattice structure, and polymer fiber.

The curable composition according to the present invention, as already mentioned, comprises a catechol-based organic compound and an amine-based high molecular compound for quinone curing.

The catechol-based organic compound means a compound having a structure in which two hydroxy groups are linked to a benzene ring, and a compound having a characteristic capable of being oxidized to a quinone state through reaction with oxygen is applicable thereto. It can have many different functional groups. The catechol-based organic compounds include L-Dopa, Pyrogallol, Dopamine, Pyrocatechol, norepinephrine, and 3,4-dihydride in the following formulas: It may be at least one selected from the group consisting of oxycinnamic acid (3,4-dihydroxycinnamic acid, DHCA), preferably may be pyrogalol fast oxidation characteristics by oxygen.

The catechol-containing compound may be the single compound, but may be any type of compound as long as they are present in the molecular structure. For example, the catechol-based organic compound may have a form attached to a functional group in the main chain or the side chain of the polymer.

The content of the catechol-based organic compound may vary depending on the properties or the purpose of the final cured film to be obtained, it is used in 3 to 90% by weight, preferably 5 to 50% by weight in the curable composition based on the solid content. If the content is less than the above range, the quinone hardening does not occur sufficiently and the properties of the cured film (strength and adhesive strength, etc.) are lowered. On the contrary, if the content is exceeded, the content of the other composition is relatively reduced, which also lowers the properties of the cured film. Since it may become, it uses suitably within the said range.

The amine-based high molecular compound is a material containing an amine group in the molecular structure, the amine group is cured through a chemical bond with the quinone of the catechol-based organic compound oxidized as shown in Scheme 1.

In this case, an amine polymer having an amine group in the main chain, the side chain, or the terminal is preferably used for forming a cured film, and the representative amine polymer is not limited in the present invention, and all polymers known in the art may be used. Preferably, the amine-based polymer is polyethyleneimine, polyamines, polyamideamine, polyvinylamine, polyamidoimine, polyallylamine, polyallylamine, poly Lysine (poly-L-lysine), chitosan (chitosan) alone, copolymers thereof, one selected from a blend thereof is possible, preferably polyimine-based polymer (polyethyleneimine), polyamine-based polyethyleneamine , Polyethylenediamine, polydiaminepropane, polyhexamethylenediamine, and the like, and more preferably polyethyleneimine.

The content of the amine-based polymer compound may vary depending on the physical properties and the purpose of the final cured film to be obtained, it is used in 3 to 90% by weight, preferably 60 to 90% by weight in the curable composition based on the solid content. If the content is less than the above range, it may be difficult to form a cured film. On the contrary, if the content exceeds the above range, the content of other compositions may be reduced, which may lower the physical properties of the cured film. do.

The curable composition comprising the oxygen inclusion structure, the catechol-based organic compound, and the amine-based high molecular compound as described above may further include additives as known in various fields depending on the use thereof.

The additives that can be used include plasticizers, colorants, preservatives, heat dispersants, biocompatible agents, preservatives, stabilizers, and the like, but are not particularly limited thereto. At this time, the content of the additive is added within a range that does not affect the curing, preferably 10% by weight or less in the total composition.

The curable composition as described above is converted to quinone by oxidation of the catechol derivative, and they cause a curing reaction with the amine polymer compound to produce a cured film.

The cured film has an advantage in that not only the surface but also internal hardening occurs, thereby providing excellent adhesion, cohesion, strength, durability, and curing time. Any field can be used as long as it can form a cured film, and the present invention is not particularly limited.

For example, it can be applied to adhesives, coatings for various adhesives, separators that can selectively permeate gas or liquid, biocatalysts containing proteins and cells in the biomedical field, hemostatic agents to stop bleeding or prevent bleeding It can be applied to a barrier to block moisture, a scaffold for tissue construction, and the like. In addition, it is possible to bond a wide range of adherends such as paper, metal, fiber, wood, plastic, glass, ceramics, etc. as industrial use. It can also be used as a functional adhesive for parts, optical fibers, and lenses.

In one example, the curable composition according to the invention can be used as an adhesive.

An adhesive has a special property of bonding an object to an object, and in order to serve as an adhesive, first, the adhesive needs to be in close contact with the object to be bonded, and secondly, the adhesive itself must be of an appropriate strength after bonding. The curable composition according to the present invention is instantaneously reacted by the quinonation of the catechol and the reaction with the amine, thereby adhering and increasing the adhesion between the adherends with high adhesive strength.

At this time, the adherend is not limited to the material in the present invention, for example, can be applied to various places such as metal, paper, fiber, silicon substrate, glass, the cured film formed after the application of the curable composition according to the present invention is a high level It can be seen that the adhesive strength is excellent due to the shear strength (see Experimental Examples 2 to 4).

The curable composition concerning this invention can be used suitably as a medical adhesive agent also in an adhesive agent.

Medical adhesives must be in direct contact with skin or tissues, so they must be toxic and non-hazardous under strict conditions and require more rigorous biocompatibility and biodegradability. Medical adhesives currently in use include cyanoacrylate instant adhesives, fibrin glues, gelatin glues, and polyurethane-based adhesives, but do not sufficiently satisfy the above conditions. Recently, polyethyleneimine-based (PEI) adhesives have been proposed, which has a problem that the adhesive is toxic for medical use.

Thus, the curable composition of the present invention can be suitably used as a substitute material for a conventional medical adhesive by the use of an amine polymer compound and a catechol-based organic compound.

In particular, it can be used for tissue rebonding among medical adhesives. Rebonding of the damaged tissue was performed using a mechanical bonding material such as sutures, staplers, wires, etc., but when using the curable composition according to the present invention can be easily applied to the wound site. As a result, compared with sutures and staplers, there are fewer secondary wounds, fewer pains, no need to remove sutures, and hemostatic effect and air leakage prevention effect.

At this time, for use as a medical adhesive may further comprise a therapeutic drug. The therapeutic drug may include a poorly soluble drug, a therapeutic peptide, a protein or an antibody, and human growth hormone, erythropoietin, interferon, insulin, interleukin, calcitonin, growth factor (G-CSF), angiotropin, VEGF-Trap, monoclonal antibodies, antibody fragments may be included, hemostatic proteins, antibiotics, analgesics may be further included in the curable composition, used for sublingual immunotherapy for angina, asthma and allergic rhinitis Allergen extract (allergen extract), antihistamine, may include anti-allergic agents, etc., is not particularly limited

Hereinafter, preferred examples and comparative examples of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

EXAMPLE

Experimental Example 1 Analysis of Dissolved Oxygen Change According to Oxygen Inclusion Structure

In order to confirm the change of dissolved oxygen amount by the oxygen inclusion structure, the airgel (main silica, porosity of 90% or more, hydrophilicity, Guangdong Alison High-tech Co., Ltd.) was dispersed in 15 mL water at concentrations of 10, 20 and 30 mg / mL. The amount of dissolved oxygen was analyzed.

1 is a result of measuring the amount of dissolved oxygen dissolved in water at a temperature of 25.6 ± 0.2 ℃. Referring to FIG. 1, 6.6 ppm of oxygen is dissolved in water without using the oxygen inclusion structure, but when the oxygen inclusion structure is contained at concentrations of 10, 20, and 30 mg / mL, respectively, 6.9, 7.1, and 7.2 ppm Showed the amount of dissolved oxygen.

As shown in FIG. 1, the oxygen inclusions contained in the oxygen inclusions were increased, and the dissolved oxygen content of the water increased as the concentration thereof increased. As a result, it was confirmed that the oxygen inclusion structures could provide oxygen.

Experimental Example  2: oxygen Inclusion  Of catechol compounds with or without structure Oxidation Promotion

In order to confirm the oxidation of the catechol compound according to the use of the oxygen clathrate structure, four tubes were prepared and the degree of oxidation (color change) of the solution was compared by varying the content of the oxygen clathrate structure for each tube. In the case of the quinone organic compound, the color is dark brown, indicating that oxidation proceeds as the color of the catechol organic compound turns brown.

Among the oxygen inclusion structures, an airgel (preferred silica, porosity of 90% or more, hydrophilicity, Guangdong Alison High-tech Co., Ltd.) was selected, and pyrogalol solution (0.2M) was prepared by putting 25.2 g of pyrogallol in 1L of water. Oxygen inclusion structure was put into each tube by 0 (Preparation Example 1), 10, 20 and 30 mg (Preparation Examples 2, 3 and 4), respectively. 1 mL of 0.2 M pyrogallol solution was added to each tube to prepare a pyrogallol / aerogel mixed solution. The color change was confirmed immediately after vortexing for 30 seconds and even after 24 hours for even mixing. A photograph comparing the oxidation degree of the catechol compound is shown in FIG. 2.

Figure 2 (a) is a photograph immediately after stirring 30 seconds after mixing the airgel, (b) is a photograph after 24 hours, wherein Only PG is a pyrogallol solution of Preparation Example 1, 10 mg / mL, 20 mg / mL, and 30 mg / mL each are pyrogallol / aerogel mixed solution.

2 (a) shows that 'Only PG' of Comparative Example 1 maintained a transparent color immediately after mixing because the oxidation of the catechol compound was slow. In comparison, the pyrogallol / aerogel mixed solution including the aerogel was confirmed to rapidly oxidize the catechol derivative by supplying oxygen inside the solution through the pores of the aerogel.

Figure 2 (b) is a photo showing the oxidation after 24 hours can be seen that the pyrogallol solution turned pale yellow light, the pyrogallol / aerogel mixed solution including the airgel is not only the air / liquid interface but also the top of the submerged airgel Also shows that the oxidation proceeds more specifically.

When using the oxygen inclusion structure according to the present invention through the results of (a) and (b) of Figure 2, it is confirmed that the oxidation of catechol derivatives is promoted by receiving oxygen from the oxygen inclusion structure as well as the air / liquid interface Could.

Experimental Example 3 Analysis of Adhesion of Metal Specimens According to Types of Oxygen Inclusion Structures

(1) curable composition

A 20 wt / vol% solution of PEI (polyethylenimine, Mw: 750 kDa) was prepared using water as a solvent. 0.2 g solution of pyrogallol was prepared using water as a solvent. Various oxygen inclusion structures were mixed with a pyrogallol solution and a PEI solution to prepare a curable composition as shown in Table 1 below.

Oxygen clathrates include aerogels (silicate silica, hydrophilicity, 90% or more porosity, Guangdong Alison High-tech), fume silica nanoparticles (silica, hydrophilic, Evonik, AEROSIL® 200), silica hollow particles (silicate silica , Hydrophilicity, diameter 80nm, RS, Korea Innotech Co., Ltd., silica nanotubes (preferred silica, hydrophilicity, diameter 100nm, SNT, Korea Innotech Co., Ltd.), and glass web (presence silica, hydrophilicity, 1035MS, Asahikasei) Evaluated.

(2) adhesive force measurement

Prepare two Cu Plates (thickness 1.2mm) in the size of 30 x 15 mm ² to confirm the adhesion, and then apply two thin plates of 10 x 15 mm ² to each specimen and thinly apply them. It was left for 5 hours at 50 ℃ to induce quinone curing.

In the case of using the glass web as an oxygen cladding structure (Example 5), the glass web was cut into an adhesive specimen area size of 10 × 15 mm ² .

Shear strength was measured by applying tensile force at a rate of 5 mm / min to the substrates prepared in Examples and Comparative Examples using a universal testing machine (INSTRON 5583). At this time, the result was measured by the average of five samples, the higher the value means that the adhesion is excellent.

(3) results

Table 1 shows the results of the composition of the curable composition and thus the shear strength. At this time, Comparative Example 1 does not use an oxygen inclusion structure, Comparative Example 2 means that a commercial adhesive (cyanoacrylate) was used.

division	PEI solution (20 wt / vol%)	Pyrogallol Solution (0.2M)	Oxygen inclusion structure		Shear strength (MPa)
			Kinds	content
Example 1	1 ml	1 ml	Airgel	60 mg	0.99
Example 2	1 ml	1 ml	Fume Silica Nanoparticles	60 mg	0.98
Example 3	1 ml	1 ml	Silica hollow particles	60 mg	0.65
Example 4	1 ml	1 ml	Silica nanotubes	60 mg	0.71
Example 5	1 ml	1 ml	Glass web	4.6 mg (Size 10X15 mm 2 )	0.95
Comparative Example 1	1 ml	1 ml	-	-	0.42
Comparative Example 2	-	-	-	-	1.15

Referring to Table 1, the cured film prepared in Examples 1 to 5 using the oxygen inclusion structure according to the present invention can be seen that the shear strength is excellent.

Figure 3 (a) is a photograph showing an adhesive cross section of Comparative Example 1 does not include an airgel, the edge portion means that the curing was made by oxygen but the inside is not cured because the air is blocked.

Figure 3 (b) is an image showing the adhesive cross section of Example 1 including an airgel, compared with (a), the color is changed evenly means that the curing was made to the inside.

3C is a cross-sectional scanning microscope image of Comparative Example 1, and (d) is a cross-sectional scanning microscope image of Example 1. FIG. By comparing (c) and (d), (d) shows the surface containing particles compared to (c) showing a smooth surface, thereby confirming the presence of the airgel.

Claims (15)

1. (a) a catechol organic compound capable of being denatured to quinone by oxidation;

   (b) amine polymer compounds; And

   (c) A curable composition comprising an oxygen inclusion structure.
2. The method of claim 1,

   The oxygen inclusion structure is curable composition, characterized in that contained in 1 to 99% by weight in the total curable composition.
3. The method of claim 1,

   The catechol-based organic compound includes a functional group of two or more hydroxy groups in the benzene ring, the curable composition, characterized in that the compound oxidizable by oxygen.
4. The method of claim 3,

   The catechol-based organic compounds include L-Dopa, L-Dopa, pyrogallol, dopamine, pyrocatechol, pyrecatechol, norepinephrine and 3,4-dihydroxy cinnamic acid (3). , 4-dihydroxycinnamic acid, DHCA) at least one member selected from the group consisting of.
5. The method of claim 1,

   The amine-based polymer compound is a curable composition, characterized in that the polymer having an amine group in the molecular structure.
6. The method of claim 5,

   The polymer having an amine group is a curable composition, characterized in that at least one selected from the group consisting of polyethyleneimine, polyamine, polyamideamine, polyvinylamine, polyamidoimine, polyallylamine, polylysine and chitosan.
7. The method of claim 1,

   The oxygen inclusion structure is a curable composition characterized in that it has at least one shape selected from the group consisting of aerogel, web, sheet, foam, sphere, tube, porous structure and lattice structure.
8. The method of claim 1,

   The oxygen inclusion structure is selected from the group consisting of activated carbon, activated carbon fiber, TiO ₂ halosphere, glass web, silica aerogel, fume silica nanoparticles, SiO ₂ hollow particles, TiO ₂ hollow particles, silica nanotubes and carbon nanotubes Curable composition characterized by the above-mentioned.
9. The method of claim 1,

   The oxygen inclusion structure is a curable composition, characterized in that the oxygen inclusion amount of 1 to 99%.
10. The method of claim 1,

    The oxygen inclusion structure has a porosity of 10 to 99% curable composition.
11. The method of claim 1,

    The oxygen inclusion structure is a curable composition, characterized in that the material is at least one selected from the group consisting of metals, metal oxides, glass, carbon materials and polymers.
12. The method of claim 1,

    The curable composition is curable composition, characterized in that the curing in the presence of oxygen.
13. The method of claim 1,

    Wherein the curable composition is internally cured from oxygen provided by the oxygen inclusion structure.
14. An adhesive composition comprising the curable composition of claim 1.
15. A coating composition comprising the curable composition according to claim 1.

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