WO2018062835A1 - Compositions durcissables à base de quinone et compositions adhésives les comprenant - Google Patents

Compositions durcissables à base de quinone et compositions adhésives les comprenant Download PDF

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WO2018062835A1
WO2018062835A1 PCT/KR2017/010695 KR2017010695W WO2018062835A1 WO 2018062835 A1 WO2018062835 A1 WO 2018062835A1 KR 2017010695 W KR2017010695 W KR 2017010695W WO 2018062835 A1 WO2018062835 A1 WO 2018062835A1
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Prior art keywords
curable composition
oxygen
group
catechol
oxygen inclusion
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PCT/KR2017/010695
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English (en)
Korean (ko)
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황홍구
한정석
이해신
왕윤선
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코오롱인더스트리 주식회사
한국과학기술원
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Priority claimed from KR1020170123517A external-priority patent/KR102283811B1/ko
Application filed by 코오롱인더스트리 주식회사, 한국과학기술원 filed Critical 코오롱인더스트리 주식회사
Priority to CN201780068202.1A priority Critical patent/CN109906248B/zh
Priority to US16/337,179 priority patent/US11001683B2/en
Priority to EP17856721.0A priority patent/EP3521372B1/fr
Priority to JP2019516205A priority patent/JP6831007B2/ja
Publication of WO2018062835A1 publication Critical patent/WO2018062835A1/fr

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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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives 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 C09J161/00 - C09J177/00
    • C09J179/02—Polyamines

Definitions

  • 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 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.
  • 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.
  • Mussel adhesives have the ability to bond to a wide variety of surfaces, including inorganic, plastic, metal, glass and biomaterials.
  • surfaces including inorganic, plastic, metal, glass and biomaterials.
  • mussel adhesives can be bonded in water.
  • Mussel adhesives for medical use are mainly used as tissue adhesives.
  • mussel adhesive proteins were extracted and measured for adhesion to pig skin.
  • 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)].
  • 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)
  • 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.
  • 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.
  • 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.
  • 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.
  • the curable composition according to the present invention undergoes curing through the quinone curing mechanism.
  • 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.
  • 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.
  • 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.
  • 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%.
  • the oxygen may be used in addition to oxygen contained in the air, high purity or high compression oxygen.
  • 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.
  • a porosity 10 to 99%, preferably 15 to 96%.
  • 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.
  • 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 ⁇ m, has a porosity of 1 to 70%, and has a thickness of 1nm to 1000 ⁇ m.
  • 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 ⁇ m, has a porosity of 1 to 70%, and has a thickness of 1 nm to 1000 ⁇ m.
  • 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
  • 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.
  • 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 ⁇ m pore, has a porosity of 10 to 99%, and has a thickness of 1nm to 1000 ⁇ m
  • 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.
  • 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 ⁇ m.
  • '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 ⁇ m, has a porosity of 10 to 99%, 1nm to.
  • the lattice structure may have a thickness of 1000 ⁇ m.
  • 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.
  • 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.
  • a material that is not corrosive to water and oxygen may be preferable, but is not particularly limited.
  • Do. 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.
  • 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.
  • 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.
  • CNT carbon nanotubes
  • the polymer material may be both a natural polymer and a synthetic polymer
  • the synthetic polymer may be both a thermoplastic resin and a thermosetting resin.
  • 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.
  • a variety of known polymer materials may be used, and are not particularly limited in the present invention.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • PEI polyethyleneimine-based
  • 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.
  • the curable composition according to the present invention can be easily applied to the wound site.
  • a mechanical bonding material such as sutures, staplers, wires, etc.
  • 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
  • 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 °C.
  • 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.
  • 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.
  • 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.
  • 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.
  • PEI polyethylenimine, Mw: 750 kDa
  • 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.
  • aerogels silicate silica, hydrophilicity, 90% or more porosity, Guangdong Alison High-tech
  • fume silica nanoparticles sica, hydrophilic, Evonik, AEROSIL® 200
  • silica hollow particles silicate silica , Hydrophilicity, diameter
  • 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.
  • Comparative Example 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.
  • 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
  • (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.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne une composition durcissable et une utilisation associée, et, plus particulièrement, une composition durcissable et une utilisation associée, la composition durcissable comprenant : (a) un composé pouvant être dénaturé en un composé à base de quinone par de l'oxygène ; (b) un composé polymère à base d'amine ; et (c) une structure de clathrate d'oxygène. La composition durcissable est rapidement durcie et peut être durcie non seulement au niveau d'une interface d'un film classique mais également à l'intérieur du film, de telle sorte que la composition durcissable présente des propriétés physiques uniformes dans tout le film et d'excellentes propriétés physiques comparées à celle d'un film durci obtenu par durcissement au niveau d'une interface existante.
PCT/KR2017/010695 2016-09-28 2017-09-27 Compositions durcissables à base de quinone et compositions adhésives les comprenant WO2018062835A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201780068202.1A CN109906248B (zh) 2016-09-28 2017-09-27 醌可固化组合物和包含其的粘合剂组合物
US16/337,179 US11001683B2 (en) 2016-09-28 2017-09-27 Quinone curable compositions and adhesive compositions comprising same
EP17856721.0A EP3521372B1 (fr) 2016-09-28 2017-09-27 Compositions durcissables à base de quinone et compositions adhésives les comprenant
JP2019516205A JP6831007B2 (ja) 2016-09-28 2017-09-27 キノン硬化型組成物及びこれを含む接着剤組成物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20160124795 2016-09-28
KR10-2016-0124795 2016-09-28
KR1020170123517A KR102283811B1 (ko) 2016-09-28 2017-09-25 퀴논 경화형 조성물 및 이를 포함하는 접착제 조성물
KR10-2017-0123517 2017-09-25

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WO2018062835A1 true WO2018062835A1 (fr) 2018-04-05

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US20190390090A1 (en) * 2018-06-26 2019-12-26 Samsung Electronics Co., Ltd. Adhesive for pellicle, pellicle for photo mask and method for manufacturing the same
CN111978856A (zh) * 2020-07-20 2020-11-24 华南理工大学 超亲水/水下超疏油铜网及其制备方法与分离乳化水包油的应用
US20220135855A1 (en) * 2020-11-02 2022-05-05 Samsung Electronics Co., Ltd. Adhesive composition, method for preparing the same, reticle assembly including the same, and method for fabricating reticle assembly including the same

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KR20150144846A (ko) * 2014-06-17 2015-12-29 한국과학기술원 카테콜 아민 기반의 다기능성 필름 및 이의 제조 방법
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* Cited by examiner, † Cited by third party
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US20190390090A1 (en) * 2018-06-26 2019-12-26 Samsung Electronics Co., Ltd. Adhesive for pellicle, pellicle for photo mask and method for manufacturing the same
CN111978856A (zh) * 2020-07-20 2020-11-24 华南理工大学 超亲水/水下超疏油铜网及其制备方法与分离乳化水包油的应用
CN111978856B (zh) * 2020-07-20 2021-12-17 华南理工大学 超亲水/水下超疏油铜网及其制备方法与分离乳化水包油的应用
US20220135855A1 (en) * 2020-11-02 2022-05-05 Samsung Electronics Co., Ltd. Adhesive composition, method for preparing the same, reticle assembly including the same, and method for fabricating reticle assembly including the same
US12018183B2 (en) * 2020-11-02 2024-06-25 Samsung Electronics Co., Ltd. Adhesive composition, method for preparing the same, reticle assembly including the same, and method for fabricating reticle assembly including the same

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