WO2016186336A1 - Uv-sensitive self-healing polymer nanoparticles, preparation method therefor, and film using same - Google Patents

Uv-sensitive self-healing polymer nanoparticles, preparation method therefor, and film using same Download PDF

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WO2016186336A1
WO2016186336A1 PCT/KR2016/004438 KR2016004438W WO2016186336A1 WO 2016186336 A1 WO2016186336 A1 WO 2016186336A1 KR 2016004438 W KR2016004438 W KR 2016004438W WO 2016186336 A1 WO2016186336 A1 WO 2016186336A1
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healing polymer
sensitive self
self
polymer nanoparticles
healing
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PCT/KR2016/004438
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French (fr)
Korean (ko)
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이선종
정찬문
유환철
김동민
김선영
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한국생산기술연구원
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/48—Isomerisation; Cyclisation
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • 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
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups

Definitions

  • the present invention relates to UV-sensitive self-healing polymer nanoparticles and a method of manufacturing the same, and more particularly, UV-sensitive self-healing polymer nanoparticles prepared by emulsifying and photopolymerizing a monomer of the UV-sensitive self-healing polymer and its preparation
  • the present invention relates to a method and a UV-sensitive self-healing polymer film comprising the same.
  • the self-healing polymer is a polymer that can recognize and heal when a crack occurs in a material due to external stress. When a film is manufactured using the self-healing polymer, there is no need for repair even if a crack occurs in the film.
  • the monomer of the self-healing polymer is supported in a structure such as hollow fiber or microcapsules together with a catalyst and dispersed in a matrix of the film.
  • a technique related to a film that heals cracks while polymerizing monomers and catalysts supported by a stimulus source is disclosed.
  • the stimulus source for polymerizing the self-healing polymer may be a heat source and a light source, and in the case of the heat source, the heat source affects even the portion where the crack does not occur, causing deformation of the matrix, thereby healing the crack by the light source.
  • Research on self-healing polymers has been widely conducted.
  • Korean Patent Publication No. 101292677 provides a self-healing microcapsules manufacturing system and manufacturing method including a self-healing synthesis unit, a capsule material synthesis unit, a self-healing capsule synthesis unit, and a drying unit.
  • Korean Patent Publication No. 101168038 discloses a microcapsule comprising a core part including a self-healing material and a fluorescent material and a capsule film surrounding the core part, a composition for forming a self-healing coating agent, a capsule dispersing self-healing coating agent, and a A technique related to a manufacturing method is disclosed.
  • the above-described prior art proposes a microcapsule comprising a core part containing a self-healing material and a capsule part formed on an outer layer thereof, but this is complicated in the manufacturing step, and the stability of the material supported in the capsule part is low. Once this is broken and self-healing occurs, re-healing is difficult.
  • the present invention provides a UV-sensitive self-healing polymer nanoparticles and a method for producing the same that can be re-healed to improve the problems of the prior art.
  • UV-sensitive self-healing polymer nanoparticles according to the present invention comprises a single layer of self-healing polymer that does not require a support (hollow fiber or capsule) carrying a healing material, and improves the stability of the self-healing material
  • the UV-sensitive self-healing polymer is intended to solve the problem that the polymerization efficiency is hindered by the polymerization of the monomers inside the polymerization while preventing the transmission of ultraviolet rays.
  • the present invention relates to a UV-sensitive self-healing polymer nanoparticles comprising a self-healing polymer single layer, and provides a method for producing the same and a method for producing a film using the same.
  • the UV-sensitive self-healing polymer nanoparticles and the film using the same have the advantages of simple manufacturing method, high polymer polymerization efficiency, and repetitive healing of cracks caused by external stress.
  • the monomer in the polymerization of the UV-sensitive self-healing monomer, the monomer is emulsified in a small droplet on the aqueous solution to photopolymerize, thereby increasing the photopolymerization efficiency.
  • the ultraviolet-sensitive self-healing polymer nanoparticles according to the present invention includes a single layer of ultraviolet-sensitive self-healing polymer, and does not require an initiator in the method of manufacturing the UV-sensitive self-healing polymer nanoparticles easily by light irradiation. Particles can be prepared.
  • the UV-sensitive polymer film when a crack is generated by an external stimulus, may self-heae the crack by sensing and photopolymerization by ultraviolet rays, and there is an advantage of re-healing.
  • FIG. 1 is a schematic diagram showing a method of manufacturing UV-sensitive self-healing polymer nanoparticles according to an embodiment of the present invention.
  • Figure 2 is a schematic diagram showing the manufacturing process of the ultraviolet-sensitive self-healing polymer film according to an embodiment of the present invention.
  • Figure 3 is a schematic diagram showing the self-healing process of the ultraviolet-sensitive self-healing polymer according to an embodiment of the present invention.
  • Figure 4 is a schematic diagram showing the self-healing process of the ultraviolet-sensitive self-healing polymer film according to an embodiment of the present invention.
  • FIG. 5 is an SEM image of a UV-sensitive self-healing polymer film according to an embodiment of the present invention.
  • an embodiment of the present invention provides a nanoparticle formed of a UV-sensitive self-healing polymer single layer and a method of manufacturing the same.
  • the UV-sensitive self-healing polymer nanoparticles comprise a self-healing polymer monolayer, characterized in that it comprises a cyclobutane (cyclobutane) ring.
  • the cyclobutane ring is characterized in that it is ring-opened by cracks to form a carbon-carbon double bond, which is characterized in that the light-induced cyclization addition reaction by ultraviolet light.
  • another embodiment of the present invention provides a method for producing UV-sensitive self-healing polymer nanoparticles.
  • the UV-sensitive self-healing polymer nanoparticles manufacturing method comprises the steps of preparing an aqueous solution containing a monomer, adding an emulsifier to prepare an emulsion containing a monomer and irradiating the emulsion with light It comprises a step of preparing the nanoparticles, characterized in that it comprises a step of emulsifying and photopolymerization of the monomer.
  • the monomer of the UV-sensitive self-healing polymer is characterized in that the photo-induced cycloaddition reaction to form a polymer, comprising at least two carbon-carbon double bond substituents.
  • the photo-induced cycloaddition reaction to form a polymer comprising at least two carbon-carbon double bond substituents.
  • the ratio of emulsifier to monomer may be characterized as 1: 0.1 to 1: 1000.
  • preparing the emulsion may include stirring at 100 rpm or more to disperse the emulsion.
  • the wavelength of the light irradiated to the emulsion containing the monomer may be characterized in that 280nm to 380nm.
  • another embodiment of the present invention provides a UV-sensitive self-healing polymer coating agent.
  • the UV-sensitive self-healing polymer coating agent is characterized in that it comprises a curing agent for matrix formation and self-healing UV-sensitive polymer nanoparticles dispersed in the curing agent.
  • the UV-sensitive self-healing polymer coating agent comprises at least one material of an adhesion promoter, a dispersant, a stabilizer, an antifoaming agent and a curing accelerator, wherein the curing agent is polyvinyl alcohol.
  • the curing agent is polyvinyl alcohol.
  • the UV-sensitive self-healing polymer film characterized in that it comprises a thin film-type film substrate and UV-sensitive self-healing polymer nanoparticles provided on the film substrate can do.
  • the UV-sensitive self-healing polymer may be prepared by photopolymerizing a monomer including two or more double bond substituents capable of a photo-induced cycloaddition reaction.
  • a reaction in which two carbon-carbon double bonds form a cyclobutane ring by a photocatalyst such as ultraviolet light is called a photo-induced cyclization catalysis, and a compound having two or more substituents of a carbon-carbon double bond is used.
  • the monomer is irradiated with ultraviolet light (photocatalyst)
  • the monomer can be polymerized to form a polymer.
  • the present invention prepared the UV-sensitive self-healing polymer nanoparticles composed of a single layer of self-healing polymer by emulsifying and photopolymerizing the monomer having the above-described characteristics.
  • the monomer is 1,1,1-tris (cinnamoyloxymethyl) ethane (hereinafter referred to as TCE), 1,1-di (cinnamoyl oxymethyl) ethane (hereinafter referred to as DCE) and 1,4-di (cinnamoyloxy) butane (hereinafter referred to as DCB), and the chemical structure thereof may be represented by Chemical Formulas 1 to 3, respectively.
  • TCE 1,1,1-tris (cinnamoyloxymethyl) ethane
  • DCE 1,1-di (cinnamoyl oxymethyl) ethane
  • DCB 1,4-di (cinnamoyloxy) butane
  • the UV-sensitive self-healing polymer nanoparticles formed by the photopolymerization of the above-mentioned monomers include a cyclobutane ring, wherein the carbon-carbon single bond contained in the cyclobutane ring has a binding energy compared to other bonds in the molecule.
  • the crack occurs in the UV-sensitive self-healing polymer film or matrix to the lower side, it may be characterized in that the carbon-carbon single bond of the cyclobutane ring is broken first.
  • the other bonds in the molecule refer to carbon-carbon single bonds, carbon-oxygen bonds, etc. in the ultraviolet-sensitive self-healing polymer main chain, and are shown in Table 1 for the bond types and binding energies included in the ultraviolet-sensitive self-healing polymer.
  • the cyclobutane ring opened by cracking the carbon-carbon single bond by cracks due to the difference in binding energy as shown in Table 1 returns to the same carbon-carbon double bond structure as the original monomer before photopolymerization.
  • the light-induced cycloaddition reaction can be characterized by exhibiting a property of healing cracks.
  • nanoparticles comprising a single layer of UV-sensitive self-healing polymer may be characterized in that the monomers are emulsified in small droplets and then photopolymerized in order to increase the polymerization efficiency.
  • the method for producing UV-sensitive self-healing polymer nanoparticles preparing an aqueous solution in which the monomer of the self-healing polymer is dispersed, adding an emulsifier to the aqueous solution to prepare an emulsion containing the monomer and the light to the emulsion It may be characterized in that it comprises the step of producing a UV-sensitive self-healing polymer nanoparticles by irradiation.
  • the weight ratio of the monomer to the emulsifier may be 1: 0.1 to 1: 1000, and the emulsifier is easily wrapped around the monomer remains to stabilize the nanoparticles. do.
  • the weight ratio of the emulsifier to the monomer is limited, but this can be changed as much according to the embodiment.
  • the step of preparing the UV-sensitive self-healing polymer nanoparticles may include stirring at 100rpm or more, preferably 3000rpm or more in order to prevent aggregation of monomer residues.
  • the emulsion When the emulsion including the monomer is stably formed, the emulsion is irradiated with light to perform a light-induced cycloaddition reaction.
  • the wavelength of the irradiated light may be 280 nm to 380 nm, and the light-induced cyclization addition reaction of the monomer sensitive to ultraviolet rays may occur effectively in the wavelength range as described above.
  • the UV-sensitive self-healing polymer coating agent may be characterized in that it comprises a UV-sensitive self-healing polymer nanoparticles dispersed in the curing agent for forming the matrix and the curing agent.
  • the UV-sensitive self-healing polymer coating agent may uniformly disperse the UV-sensitive self-healing polymer nanoparticles in the adhesion promoter for promoting adhesion to the substrate on which the coating agent is provided, the curing accelerator for promoting the curing of the curing agent, and the curing agent. Dispersant and antifoaming agent to prevent foaming.
  • the curing agent included in the UV-sensitive self-healing polymer coating agent may be characterized by including a compound such as polyvinyl alcohol, polyimide.
  • an embodiment of the present invention provides a method for producing a polymer film to which the ultraviolet-sensitive self-healing polymer nanoparticles are provided by providing the ultraviolet-sensitive self-healing polymer nanoparticles on the thin film type substrate.
  • FIG. 2 and FIG. 3 to FIG. 4 show crack healing mechanisms of the self-healing polymer film.
  • a preferred embodiment includes preparing an aqueous solution in which monomers TCE and DCE are dispersed, stirring the aqueous solution, and polya to stabilize monomer residues and form a film substrate.
  • the step of healing the cracks is characterized in that it can be repeatedly healed cracks occur.
  • TCE-co-DCE emulsion containing TCE and DCE
  • the mixture was stirred at 800 rpm for 30 minutes and irradiated with UV light to prepare poly (TCE-co-DCE) nanoparticles, cast it, and cast at 200 ° C.
  • Thermal imidization was performed for 60 minutes at to prepare a UV-sensitive self-healing polymer film including poly (TCE-co-DCE) nanoparticles on a polyimide film substrate.
  • UV-sensitive self-healing polymer nanoparticles prepared by scanning electron microscope (SEM) measurement were analyzed, and the results are shown in FIG. 5. Referring to this, it can be confirmed that spherical nanoparticles having a small size scattering were prepared according to an embodiment of the present invention, and the particle size was approximately 100 nm.

Abstract

The present invention relates to UV-sensitive self-healing polymer nanoparticles comprising a self-healing polymer single layer, and provides a preparation method therefor and a method for manufacturing a film using the UV-sensitive self-healing polymer nanoparticles. The UV-sensitive self-healing polymer nanoparticles and the film using the same have advantages of having a simple manufacturing method, having high polymer polymerization efficiency, and being able to repeatedly heal cracks caused by external stress.

Description

자외선 감응형 자가치유 고분자의 나노입자 및 이의 제조방법 및 이를 이용한 필름Nanoparticles of UV-sensitive Self-Healing Polymers, Manufacturing Method thereof and Film Using the Same
본 발명은 자외선 감응형 자가치유 고분자 나노입자 및 이의 제조방법에 관한 것으로 더욱 상세하게는, 자외선 감응형 자가치유 고분자의 단량체를 유화 및 광 중합하여 제조된 자외선 감응형 자가치유 고분자 나노입자 및 이의 제조방법과 이를 포함하는 자외선 감응형 자가치유 고분자 필름에 관한 기술이다.The present invention relates to UV-sensitive self-healing polymer nanoparticles and a method of manufacturing the same, and more particularly, UV-sensitive self-healing polymer nanoparticles prepared by emulsifying and photopolymerizing a monomer of the UV-sensitive self-healing polymer and its preparation The present invention relates to a method and a UV-sensitive self-healing polymer film comprising the same.
자가치유 고분자는 외부 응력에 의해 소재에 크랙이 발생하는 경우 이를 인지 및 치유 할 수 있는 고분자로 이를 활용하여 필름을 제조할 시, 상기 필름에 크랙이 발생하여도 보수의 필요가 없다는 이점이 있다. The self-healing polymer is a polymer that can recognize and heal when a crack occurs in a material due to external stress. When a film is manufactured using the self-healing polymer, there is no need for repair even if a crack occurs in the film.
자가치유 고분자를 활용한 필름에 있어서, 자가치유 고분자의 단량체를 촉매와 함께 중공섬유(hollow fiber) 또는 마이크로 캡슐과 같은 구조에 담지하고 이를 필름의 매트릭스에 분산시킨 형태이며, 필름에 크랙이 발생했을 때, 상기 중공섬유 또는 마이크로 캡슐이 파괴되어 담지하고 있던 단량체 및 촉매가 자극원에 의해 중합되면서 크랙을 치유하는 필름에 관련된 기술이 개시되어있다. In the film using the self-healing polymer, the monomer of the self-healing polymer is supported in a structure such as hollow fiber or microcapsules together with a catalyst and dispersed in a matrix of the film. When the hollow fiber or the microcapsules are broken, a technique related to a film that heals cracks while polymerizing monomers and catalysts supported by a stimulus source is disclosed.
자가치유 고분자를 중합시키기 위한 자극원은 열원 및 광원이 될 수 있으며, 열원의 경우 크랙이 발생하지 않은 부분까지도 열원이 영향을 미쳐 매트릭스의 변형을 야기하는 문제점이 있어, 광원에 의해 크랙을 치유하는 자가치유 고분자에 관련된 연구가 널리 진행되고 있다. The stimulus source for polymerizing the self-healing polymer may be a heat source and a light source, and in the case of the heat source, the heat source affects even the portion where the crack does not occur, causing deformation of the matrix, thereby healing the crack by the light source. Research on self-healing polymers has been widely conducted.
이와 관련된 일 예로, 대한민국 등록특허공보 제101292677호에는 자가치유제 합성부, 캡슐원료 합성부, 자가치유제캡슐 합성부 및 건조부를 구비한 자가치유용 마이크로캡슐 제조시스템 및 제조방법을 제공한다. In this regard, Korean Patent Publication No. 101292677 provides a self-healing microcapsules manufacturing system and manufacturing method including a self-healing synthesis unit, a capsule material synthesis unit, a self-healing capsule synthesis unit, and a drying unit.
또 다른 일 예로, 대한민국 등록특허공보 제101168038호는 자기치유 물질과 형광물질을 포함하는 코어부 및 코어부를 둘러싼 캡슐막을 포함하는 마이크로 캡슐, 자기치유 코팅제 형성용 조성물, 캡슐 분산형 자기치유 코팅제 및 그 제조방법에 관련된 기술을 개시하고 있다.As another example, Korean Patent Publication No. 101168038 discloses a microcapsule comprising a core part including a self-healing material and a fluorescent material and a capsule film surrounding the core part, a composition for forming a self-healing coating agent, a capsule dispersing self-healing coating agent, and a A technique related to a manufacturing method is disclosed.
상술한 종래 기술들은 자기치유 물질을 함유하는 코어부 및 그의 외층에 형성되는 캡슐부를 포함하는 마이크로 캡슐을 제안하고 있으나, 이는 제조단계가 복잡하며, 캡슐부 내에 담지된 물질의 안정성이 낮으며, 캡슐이 파괴되어 한번 자가치유가 일어나면 재치유가 어렵다는 단점이 있다.The above-described prior art proposes a microcapsule comprising a core part containing a self-healing material and a capsule part formed on an outer layer thereof, but this is complicated in the manufacturing step, and the stability of the material supported in the capsule part is low. Once this is broken and self-healing occurs, re-healing is difficult.
본 발명은 종래 기술의 문제점을 개선하기 위해 재치유가 가능한 자외선 감응형 자가치유 고분자 나노입자 및 이의 제조방법을 제공한다. The present invention provides a UV-sensitive self-healing polymer nanoparticles and a method for producing the same that can be re-healed to improve the problems of the prior art.
또한, 본 발명에 따른 자외선 감응형 자가치유 고분자 나노입자는 치유 물질을 담지하는 담지체(중공섬유 또는 캡슐)을 필요로 하지 않는 자가치유 고분자 단일 층을 포함하며, 자가치유 소재의 안정성을 향상시키는 것을 목적으로 한다. In addition, UV-sensitive self-healing polymer nanoparticles according to the present invention comprises a single layer of self-healing polymer that does not require a support (hollow fiber or capsule) carrying a healing material, and improves the stability of the self-healing material For the purpose of
또한, 자외선 감응형 자가치유 고분자는 중합되면서 자외선의 투과를 방해하며 내부의 단량체를 중합시키지 못하여 중합 효율이 저하되는 문제를 해결하고자 한다. In addition, the UV-sensitive self-healing polymer is intended to solve the problem that the polymerization efficiency is hindered by the polymerization of the monomers inside the polymerization while preventing the transmission of ultraviolet rays.
아울러, 자가치유 고분자의 나노입자를 구비한 코팅제 또는 박막형 필름을 제조하는 방법을 제공하여 자동차, 선박, 건축 외장재 및 페인트에 응용할 수 있게 하는 것을 달성하고자 하는 기술적 과제로 한다. In addition, to provide a method for producing a coating agent or a thin film having a nanoparticles of self-healing polymer to be applied to automobiles, ships, building exterior materials and paints as a technical problem to achieve.
본 발명이 이루고자 하는 기술적 과제는 이상에서 언급한 기술적 과제로 제한되지 않으며, 언급되지 않은 또 다른 기술적 과제들은 아래의 기재로부터 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 명확하게 이해될 수 있을 것이다.The technical problem to be achieved by the present invention is not limited to the technical problem mentioned above, and other technical problems not mentioned above may be clearly understood by those skilled in the art from the following description. There will be.
본 발명은 자가치유 고분자 단일 층을 포함하는 자외선 감응형 자가치유 고분자 나노입자에 관한 것으로 이의 제조방법 및 이를 이용한 필름의 제조방법을 제공한다. 상기 자외선 감응형 자가치유 고분자 나노입자 및 이를 이용한 필름은 제조방법이 간편하고 고분자 중합 효율이 높으며 외부 응력에 의한 크랙을 반복적으로 치유하는 이점이 있다. The present invention relates to a UV-sensitive self-healing polymer nanoparticles comprising a self-healing polymer single layer, and provides a method for producing the same and a method for producing a film using the same. The UV-sensitive self-healing polymer nanoparticles and the film using the same have the advantages of simple manufacturing method, high polymer polymerization efficiency, and repetitive healing of cracks caused by external stress.
본 발명의 실시예에 따르면, 자외선 감응형 자가치유 단량체를 중합하는데 있어서, 수용액 상에 단량체를 작은 유적으로 유화시켜 광 중합하여, 광 중합 효율을 증대시킬 수 있다. According to the embodiment of the present invention, in the polymerization of the UV-sensitive self-healing monomer, the monomer is emulsified in a small droplet on the aqueous solution to photopolymerize, thereby increasing the photopolymerization efficiency.
또한, 본 발명에 따른 자외선 감응형 자가치유 고분자 나노입자는 자외선 감응형 자가치유 고분자 단일 층을 포함하며, 그 제조방법에 있어서 개시제를 필요로 하지 않고 광 조사에 의해 쉽게 자외선 감응형 자가치유 고분자 나노입자를 제조할 수 있다. In addition, the ultraviolet-sensitive self-healing polymer nanoparticles according to the present invention includes a single layer of ultraviolet-sensitive self-healing polymer, and does not require an initiator in the method of manufacturing the UV-sensitive self-healing polymer nanoparticles easily by light irradiation. Particles can be prepared.
본 발명의 실시예에 따른 자외선 감응형 고분자 필름은 외부 자극에 의해 크랙이 발생하였을 때, 이를 감지 및 자외선에 의한 광 중합으로 크랙을 자가치유 할 수 있으며, 재치유가 가능한 장점이 있다. According to an embodiment of the present invention, when a crack is generated by an external stimulus, the UV-sensitive polymer film may self-heae the crack by sensing and photopolymerization by ultraviolet rays, and there is an advantage of re-healing.
본 발명의 효과는 상기한 효과로 한정되는 것은 아니며, 본 발명의 상세한 설명 또는 특허청구범위에 기재된 발명의 구성으로부터 추론 가능한 모든 효과를 포함하는 것으로 이해되어야 한다.The effects of the present invention are not limited to the above-described effects, but should be understood to include all the effects deduced from the configuration of the invention described in the detailed description or claims of the present invention.
도 1은 본 발명의 실시예에 따른 자외선 감응형 자가치유 고분자 나노입자의 제조방법을 나타낸 모식도이다.1 is a schematic diagram showing a method of manufacturing UV-sensitive self-healing polymer nanoparticles according to an embodiment of the present invention.
도 2는 본 발명의 실시예에 따른 자외선 감응형 자가치유 고분자 필름의 제조과정을 나타낸 모식도이다. Figure 2 is a schematic diagram showing the manufacturing process of the ultraviolet-sensitive self-healing polymer film according to an embodiment of the present invention.
도 3은 본 발명의 실시예에 따른 자외선 감응형 자가치유 고분자의 자가치유 과정을 나타내는 모식도이다. Figure 3 is a schematic diagram showing the self-healing process of the ultraviolet-sensitive self-healing polymer according to an embodiment of the present invention.
도 4는 본 발명의 일 실시예에 따른 자외선 감응형 자가치유 고분자 필름의 자가치유 과정을 나타내는 모식도이다. Figure 4 is a schematic diagram showing the self-healing process of the ultraviolet-sensitive self-healing polymer film according to an embodiment of the present invention.
도 5는 본 발명의 일 실시예에 따른 자외선 감응형 자가치유 고분자 필름의 SEM 이미지이다.5 is an SEM image of a UV-sensitive self-healing polymer film according to an embodiment of the present invention.
상기 기술적 과제를 달성하기 위하여, 본 발명의 실시예는 자외선 감응형 자가치유 고분자 단일 층으로 형성된 나노입자 및 이의 제조방법을 제공한다.In order to achieve the above technical problem, an embodiment of the present invention provides a nanoparticle formed of a UV-sensitive self-healing polymer single layer and a method of manufacturing the same.
본 발명의 일 실시예에 있어서, 자외선 감응형 자가치유 고분자 나노입자는 자가치유 고분자 단일 층을 포함하며, 사이클로뷰테인(cyclobutane) 고리를 포함하는 것을 특징으로 한다. In one embodiment of the invention, the UV-sensitive self-healing polymer nanoparticles comprise a self-healing polymer monolayer, characterized in that it comprises a cyclobutane (cyclobutane) ring.
또한, 사이클로뷰테인 고리는 크랙에 의해 개환 되어 탄소-탄소 이중결합을 형성하는 것을 특징으로 하며, 이는 자외선에 의해 광-유도 고리화 첨가반응을 하는 것을 특징으로 한다. In addition, the cyclobutane ring is characterized in that it is ring-opened by cracks to form a carbon-carbon double bond, which is characterized in that the light-induced cyclization addition reaction by ultraviolet light.
상기 기술적 과제를 달성하기 위하여, 본 발명의 또 다른 실시예는 자외선 감응형 자가치유 고분자 나노입자의 제조방법을 제공한다.In order to achieve the above technical problem, another embodiment of the present invention provides a method for producing UV-sensitive self-healing polymer nanoparticles.
본 발명의 실시예에 있어서, 자외선 감응형 자가치유 고분자 나노입자의 제조방법은 단량체를 포함하는 수용액을 제조하는 단계, 유화제를 첨가하여 단량체를 포함하는 에멀젼을 제조하는 단계 및 에멀젼에 광을 조사하여 나노입자를 제조하는 단계를 포함하며, 단량체의 유화 및 광 중합 단계를 포함하는 것을 특징으로 한다. In the embodiment of the present invention, the UV-sensitive self-healing polymer nanoparticles manufacturing method comprises the steps of preparing an aqueous solution containing a monomer, adding an emulsifier to prepare an emulsion containing a monomer and irradiating the emulsion with light It comprises a step of preparing the nanoparticles, characterized in that it comprises a step of emulsifying and photopolymerization of the monomer.
본 발명의 실시예에 있어서, 자외선 감응형 자가치유 고분자의 단량체는 광-유도 고리화 첨가 반응하여 중합체를 형성하는 것을 특징으로 하며, 탄소-탄소 이중결합 치환기를 2개 이상 포함하는 것을 특징으로 할 수 있다. In an embodiment of the present invention, the monomer of the UV-sensitive self-healing polymer is characterized in that the photo-induced cycloaddition reaction to form a polymer, comprising at least two carbon-carbon double bond substituents. Can be.
또한, 자외선 감응형 자가치유 고분자 나노입자의 제조방법에 있어서, 유화제 대 단량체의 비율은 1:0.1 내지 1:1000 인 것을 특징으로 할 수 있다. In addition, in the method for producing UV-sensitive self-healing polymer nanoparticles, the ratio of emulsifier to monomer may be characterized as 1: 0.1 to 1: 1000.
자외선 감응형 자가치유 고분자 나노입자의 제조방법에 있어서, 에멀젼을 제조하는 단계는, 에멀젼을 분산시키기 위하여 100rpm 이상으로 교반하는 단계를 포함할 수 있다. In the method for preparing UV-sensitive self-healing polymer nanoparticles, preparing the emulsion may include stirring at 100 rpm or more to disperse the emulsion.
또한, 자외선 감응형 자가치유 고분자 나노입자의 제조방법에 있어서, 단량체를 포함하는 에멀젼에 조사되는 광의 파장은 280nm 내지 380nm 인 것을 특징으로 할 수 있다. In addition, in the method for producing UV-sensitive self-healing polymer nanoparticles, the wavelength of the light irradiated to the emulsion containing the monomer may be characterized in that 280nm to 380nm.
상기 기술적 과제를 달성하기 위하여, 본 발명의 또 다른 실시예는 자외선 감응형 자가치유 고분자 코팅제를 제공한다. In order to achieve the above technical problem, another embodiment of the present invention provides a UV-sensitive self-healing polymer coating agent.
본 발명의 실시예에 있어서, 자외선 감응형 자가치유 고분자 코팅제는 매트릭스 형성용 경화제 및 경화제 내에 분산된 자가치유 자외선 감응형 고분자 나노입자를 포함하는 것을 특징으로 한다. In an embodiment of the present invention, the UV-sensitive self-healing polymer coating agent is characterized in that it comprises a curing agent for matrix formation and self-healing UV-sensitive polymer nanoparticles dispersed in the curing agent.
이때, 본 발명의 또 다른 실시예는 자외선 감응형 자가치유 고분자 코팅제에 접착 증진제, 분산제, 안정제, 소포제 및 경화 촉진제 중 1종 이상의 물질을 포함하는 것을 특징으로 할 수 있으며, 경화제로는 폴리비닐알코올, 폴리염화비닐, 폴리메틸메타크릴레이트, 폴리스티렌, 폴리디메틸실록세인, 폴리에스테르, 에폭시, 폴리에테르, 폴리이미드, 폴리카보네이트 및 폴리벤질메타크릴레이트 중 1종 이상의 화합물을 포함하는 것을 특징으로 한다. At this time, another embodiment of the present invention may be characterized in that the UV-sensitive self-healing polymer coating agent comprises at least one material of an adhesion promoter, a dispersant, a stabilizer, an antifoaming agent and a curing accelerator, wherein the curing agent is polyvinyl alcohol. , Polyvinyl chloride, polymethylmethacrylate, polystyrene, polydimethylsiloxane, polyester, epoxy, polyether, polyimide, polycarbonate and polybenzyl methacrylate.
상기 기술적 과제를 달성하기 위하여, 본 발명의 또 다른 실시예는 자외선 감응형 자가치유 고분자 필름에 있어서, 박막형의 필름 기재 및 상기 필름 기재에 마련된 자외선 감응형 자가치유 고분자 나노입자를 포함하는 것을 특징으로 할 수 있다.In order to achieve the above technical problem, another embodiment of the present invention, in the UV-sensitive self-healing polymer film, characterized in that it comprises a thin film-type film substrate and UV-sensitive self-healing polymer nanoparticles provided on the film substrate can do.
이하에서는 첨부한 도면을 참조하여 본 발명을 설명하기로 한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며, 따라서 여기에서 설명하는 실시예로 한정되는 것은 아니다. 그리고 도면에서 본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 유사한 부분에 대해서는 유사한 도면 부호를 붙였다.Hereinafter, with reference to the accompanying drawings will be described the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.
명세서 전체에서, 어떤 부분이 다른 부분과 "연결(접속, 접촉, 결합)"되어 있다고 할 때, 이는 "직접적으로 연결"되어 있는 경우뿐 아니라, 그 중간에 다른 부재를 사이에 두고 "간접적으로 연결"되어 있는 경우도 포함한다. 또한 어떤 부분이 어떤 구성요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 구비할 수 있다는 것을 의미한다.Throughout the specification, when a part is said to be "connected (connected, contacted, coupled)" with another part, it is not only "directly connected" but also "indirectly connected" with another member in between. "Includes the case. In addition, when a part is said to "include" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.
본 명세서에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 명세서에서, "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, action, component, part, or combination thereof described on the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.
이하 첨부된 도면을 참고하여 본 발명의 실시예를 상세히 설명하기로 한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
자외선 감응형 자가치유 고분자는 광-유도 고리화 첨가 반응을 할 수 있는 이중결합 치환기를 2개 이상 포함하는 단량체를 광 중합하여 제조될 수 있다. The UV-sensitive self-healing polymer may be prepared by photopolymerizing a monomer including two or more double bond substituents capable of a photo-induced cycloaddition reaction.
이와 관련하여 후술하는 반응식 1을 참조하여 상세히 설명한다.This will be described in detail with reference to Scheme 1 described later.
[반응식 1] Scheme 1
Figure PCTKR2016004438-appb-I000001
Figure PCTKR2016004438-appb-I000001
2개의 탄소-탄소 이중결합이 자외선과 같은 광 촉매에 의해 사이클로뷰테인 고리를 형성하는 반응을 광-유도 고리화 촉매 반응이라고 하며, 탄소-탄소 이중결합의 치환기를 2개 이상 보유하고 있는 화합물을 단량체로 하여, 자외선(광 촉매)을 조사하면 단량체가 중합하여 중합체를 형성할 수 있다.A reaction in which two carbon-carbon double bonds form a cyclobutane ring by a photocatalyst such as ultraviolet light is called a photo-induced cyclization catalysis, and a compound having two or more substituents of a carbon-carbon double bond is used. When the monomer is irradiated with ultraviolet light (photocatalyst), the monomer can be polymerized to form a polymer.
본 발명은 상술한 특징을 갖는 단량체를 유화 및 광 중합하여 자가치유 고분자 단일 층으로 이루어진 자외선 감응형 자가치유 고분자 나노입자를 제조하였다. The present invention prepared the UV-sensitive self-healing polymer nanoparticles composed of a single layer of self-healing polymer by emulsifying and photopolymerizing the monomer having the above-described characteristics.
본 발명의 실시예에서 단량체는 1,1,1-tris(cinnamoyloxymethyl)ethane(이하 TCE), 1,1-di(cinnamoyl oxymethyl)ethane(이하 DCE) 및 1,4-di(cinnamoyloxy) butane(이하 DCB) 중 1종 일 수 있으며, 이의 화학구조는 각각 화학식 1 내지 화학식 3을 참조한다.In an embodiment of the present invention, the monomer is 1,1,1-tris (cinnamoyloxymethyl) ethane (hereinafter referred to as TCE), 1,1-di (cinnamoyl oxymethyl) ethane (hereinafter referred to as DCE) and 1,4-di (cinnamoyloxy) butane (hereinafter referred to as DCB), and the chemical structure thereof may be represented by Chemical Formulas 1 to 3, respectively.
Figure PCTKR2016004438-appb-C000001
Figure PCTKR2016004438-appb-C000001
Figure PCTKR2016004438-appb-C000002
Figure PCTKR2016004438-appb-C000002
Figure PCTKR2016004438-appb-C000003
Figure PCTKR2016004438-appb-C000003
이하, TCE 및 DCB의 광-유도 고리화 첨가 반응을 나타낸 반응식을 각각 반응식 2와반응식 3에 나타내었다.Hereinafter, schemes showing the photo-induced cycloaddition reaction of TCE and DCB are shown in Scheme 2 and Scheme 3, respectively.
[반응식 2]Scheme 2
Figure PCTKR2016004438-appb-I000002
Figure PCTKR2016004438-appb-I000002
[반응식 3]Scheme 3
Figure PCTKR2016004438-appb-I000003
Figure PCTKR2016004438-appb-I000003
상술한 단량체의 광 중합으로 형성된 자외선 감응형 자가치유 고분자 나노입자는 사이클로뷰테인 고리를 포함하고 있으며, 이때 상기 사이클로뷰테인 고리에 포함된 탄소-탄소 단일결합은 분자 내의 다른 결합들에 비하여 결합에너지가 낮은 편으로 자외선 감응형 자가치유 고분자 필름 또는 매트릭스에 크랙이 발생할 시, 상기 사이클로뷰테인 고리의 탄소-탄소 단일결합이 먼저 끊어지는 특성을 나타내는 것을 특징으로 할 수 있다.The UV-sensitive self-healing polymer nanoparticles formed by the photopolymerization of the above-mentioned monomers include a cyclobutane ring, wherein the carbon-carbon single bond contained in the cyclobutane ring has a binding energy compared to other bonds in the molecule. When the crack occurs in the UV-sensitive self-healing polymer film or matrix to the lower side, it may be characterized in that the carbon-carbon single bond of the cyclobutane ring is broken first.
여기서 상기 분자 내의 다른 결합들은 자외선 감응형 자가치유 고분자 주사슬 내의 탄소-탄소 단일결합, 탄소-산소 결합 등을 말하며 자외선 감응형 자가치유 고분자에 포함된 결합 종류와 결합에너지에 대하여 표 1에 나타냈다.Herein, the other bonds in the molecule refer to carbon-carbon single bonds, carbon-oxygen bonds, etc. in the ultraviolet-sensitive self-healing polymer main chain, and are shown in Table 1 for the bond types and binding energies included in the ultraviolet-sensitive self-healing polymer.
결합 종류Combination type 결합 에너지 [kcal/mol]Binding energy [kcal / mol]
C - CC-C 8484
C - HC-H 97.597.5
C - OC-O 8888
C - C (사이클로뷰테인 고리 내)C-C (in cyclobutane ring) 7474
C - H (사이클로뷰테인 고리 내)C-H (in cyclobutane ring) 106106
표1에 나타낸 바와 같은 결합에너지 차이로 크랙에 의해 탄소-탄소 단일결합이 끊어져 개환된 사이클로뷰테인 고리는 광 중합하기 전 본래의 단량체와 같은 탄소-탄소 이중결합 구조로 되돌아가며, 다시 광 조사에 의해 광-유도 고리화 첨가 반응을 일으켜 크랙을 치유하는 특성을 나타내는 것을 특징으로 할 수 있다.The cyclobutane ring opened by cracking the carbon-carbon single bond by cracks due to the difference in binding energy as shown in Table 1 returns to the same carbon-carbon double bond structure as the original monomer before photopolymerization. By the light-induced cycloaddition reaction can be characterized by exhibiting a property of healing cracks.
다음으로 본 발명의 실시예에 따른 자외선 감응형 자가치유 고분자 나노입자를 제조하는 방법을 설명한다. Next, a method of manufacturing UV-sensitive self-healing polymer nanoparticles according to an embodiment of the present invention will be described.
본 발명은 자외선 감응형 자가치유 고분자 단일 층을 포함하는 나노입자를 제조하는데 있어서, 중합 효율을 높이기 위하여 단량체를 작은 유적으로 유화시킨 후 광 중합하는 것을 특징으로 할 수 있다. In the present invention, nanoparticles comprising a single layer of UV-sensitive self-healing polymer may be characterized in that the monomers are emulsified in small droplets and then photopolymerized in order to increase the polymerization efficiency.
이에 관하여 도 1을 참조하여 상세하게 설명한다. This will be described in detail with reference to FIG. 1.
자외선 감응형 자가치유 고분자 나노입자의 제조방법에 있어서, 자가치유 고분자의 단량체를 분산시킨 수용액을 제조하는 단계, 상기 수용액에 유화제를 첨가하여 상기 단량체를 포함하는 에멀젼을 제조하는 단계 및 상기 에멀젼에 광을 조사하여 자외선 감응형 자가치유 고분자 나노입자를 제조하는 단계를 포함하는 것을 특징으로 할 수 있다. In the method for producing UV-sensitive self-healing polymer nanoparticles, preparing an aqueous solution in which the monomer of the self-healing polymer is dispersed, adding an emulsifier to the aqueous solution to prepare an emulsion containing the monomer and the light to the emulsion It may be characterized in that it comprises the step of producing a UV-sensitive self-healing polymer nanoparticles by irradiation.
상술한 단량체를 분산시킨 수용액에 유화제를 첨가하는데 있어서, 유화제 대비 단량체의 중량비는 1:0.1 내지 1:1000 인 것을 특징으로 할 수 있으며, 유화제는 단량체 유적을 감싸 안정화시켜 나노입자의 제조를 용이하게 한다. In adding the emulsifier to the aqueous solution in which the above-described monomer is dispersed, the weight ratio of the monomer to the emulsifier may be 1: 0.1 to 1: 1000, and the emulsifier is easily wrapped around the monomer remains to stabilize the nanoparticles. do.
이때, 유화제의 양이 단량체에 비해 너무 적으면 단량체 유적을 안정화시키지 못하여 나노입자를 제조하기 어려울 수 있으며, 유화제의 양이 과다하면 오히려 단량체 유적의 응집을 야기하여 나노입자를 제조하기 곤란할 수 있기 때문에 상기와 같이 유화제 대 단량체의 중량비를 한정하였으나 이는 실시예에 따라 얼마든지 변형이 가능함을 명시한다. In this case, when the amount of the emulsifier is too small compared to the monomer, it may be difficult to prepare the nanoparticles because it does not stabilize the monomer remains, and if the amount of the emulsifier is excessive, it may be difficult to produce nanoparticles by causing aggregation of the monomer residues. As described, the weight ratio of the emulsifier to the monomer is limited, but this can be changed as much according to the embodiment.
또한, 자외선 감응형 자가치유 고분자 나노입자를 제조하는 단계는 단량체 유적의 응집을 방지하기 위하여 100rpm 이상, 바람직하게는 3000rpm 이상으로 교반하는 단계를 포함할 수 있다. In addition, the step of preparing the UV-sensitive self-healing polymer nanoparticles may include stirring at 100rpm or more, preferably 3000rpm or more in order to prevent aggregation of monomer residues.
단량체를 포함하는 에멀젼이 안정하게 형성되면, 상기 에멀젼에 광을 조사하여 광-유도 고리화 첨가 반응을 수행한다. 이때 조사되는 광의 파장은 280nm 내지 380nm 인 것을 특징으로 할 수 있으며, 상기와 같은 파장 범위에서 자외선에 감응하는 단량체의 광-유도 고리화 첨가반응이 효과적으로 일어날 수 있다.When the emulsion including the monomer is stably formed, the emulsion is irradiated with light to perform a light-induced cycloaddition reaction. In this case, the wavelength of the irradiated light may be 280 nm to 380 nm, and the light-induced cyclization addition reaction of the monomer sensitive to ultraviolet rays may occur effectively in the wavelength range as described above.
본 발명의 또 다른 실시예는 자외선 감응형 자가치유 고분자 코팅제에 있어서, 매트릭스 형성용 경화제 및 경화제 내에 분산되는 자외선 감응형 자가치유 고분자 나노입자를 포함하는 것을 특징으로 할 수 있다. Another embodiment of the present invention, the UV-sensitive self-healing polymer coating agent, it may be characterized in that it comprises a UV-sensitive self-healing polymer nanoparticles dispersed in the curing agent for forming the matrix and the curing agent.
이때, 자외선 감응형 자가치유 고분자 코팅제는 코팅제가 마련되는 기재에 대하여 접착성을 증진시키기 위한 접착 증진제, 경화제의 경화를 촉진하는 경화촉진제 및 경화제 내에 자외선 감응형 자가치유 고분자 나노입자를 균일하게 분산시키기 위한 분산제 및 거품 생성을 방지하는 소포제를 포함할 수도 있다. In this case, the UV-sensitive self-healing polymer coating agent may uniformly disperse the UV-sensitive self-healing polymer nanoparticles in the adhesion promoter for promoting adhesion to the substrate on which the coating agent is provided, the curing accelerator for promoting the curing of the curing agent, and the curing agent. Dispersant and antifoaming agent to prevent foaming.
자외선 감응형 자가치유 고분자 코팅제에 포함되는 경화제로는 폴리비닐알코올, 폴리이미드와 같은 화합물을 포함하는 것을 특징으로 할 수 있다. The curing agent included in the UV-sensitive self-healing polymer coating agent may be characterized by including a compound such as polyvinyl alcohol, polyimide.
아울러, 본 발명의 실시예는 박막형의 필름 기재에 자외선 감응형 자가치유 고분자 나노입자를 마련하여 자외선 감응형 자가치유 특성이 부여된 고분자 필름을 제조하는 방법을 제공한다. In addition, an embodiment of the present invention provides a method for producing a polymer film to which the ultraviolet-sensitive self-healing polymer nanoparticles are provided by providing the ultraviolet-sensitive self-healing polymer nanoparticles on the thin film type substrate.
이하, 본 발명의 실시예에 따른 자외선 감응형 자가치유 고분자 필름의 제조과정을 나타낸 도 2, 자가치유 고분자 필름의 크랙 치유 메커니즘을 나타낸 도 3 내지 도 4를 참조하여 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail with reference to FIG. 2 and FIG. 3 to FIG. 4 which show crack healing mechanisms of the self-healing polymer film.
자외선 감응형 자가치유 고분자를 포함하는 필름을 제조하는데 있어서, 바람직한 실시예는, 단량체인 TCE 및 DCE를 분산시킨 수용액을 제조하는 단계, 상기 수용액을 교반하며 단량체 유적의 안정화 및 필름 기재 형성을 위한 폴리아믹산(polyamic acid)을 첨가하여 TCE 및 DCE를 포함하는 에멀젼을 형성시키는 단계, 이에 광을 조사하여 TCE 및 DCE의 중합체로 이루어진 나노입자를 제조하는 단계 및 상기 나노입자를 열 이미드화 시켜 필름을 제조하는 단계를 포함하는 것을 특징으로 할 수 있다.In preparing a film including an ultraviolet-sensitive self-healing polymer, a preferred embodiment includes preparing an aqueous solution in which monomers TCE and DCE are dispersed, stirring the aqueous solution, and polya to stabilize monomer residues and form a film substrate. Forming an emulsion comprising TCE and DCE by adding polyamic acid, irradiating light to produce nanoparticles consisting of polymers of TCE and DCE, and thermally imidating the nanoparticles to prepare a film. It may be characterized in that it comprises a step.
다음으로 자외선 감응형 자가치유 고분자 필름의 자가치유 메커니즘에 있어서 도 3 및 도 4를 참조하면, 자외선 감응형 자가치유 고분자 필름에 크랙이 발생하고, 상기 크랙에 의해 자가치유 고분자에 포함된 사이클로뷰테인 고리 내의 탄소-탄소 단일결합이 끊어져 탄소-탄소 이중결합 치환기를 포함하는 본래의 단량체 구조로 되돌아가며, 이에 자외선(광 촉매)이 조사되면 탄소-탄소 이중결합이 광-유도 고리화 첨가 반응하여 소재 스스로 크랙을 치유할 수 있다. Next, referring to FIGS. 3 and 4 in the self-healing mechanism of the UV-sensitive self-healing polymer film, cracks are generated in the UV-sensitive self-healing polymer film, and the cyclobutane contained in the self-healing polymer by the cracks. The carbon-carbon single bond in the ring is broken to return to the original monomer structure including a carbon-carbon double bond substituent. When ultraviolet light (photocatalyst) is irradiated, the carbon-carbon double bond is photo-induced cyclization addition reaction. You can heal the cracks yourself.
또한, 상기 크랙을 치유하는 단계는 반복적으로 발생하여 크랙을 재치유 할 수 있는 것을 특징으로 한다. In addition, the step of healing the cracks is characterized in that it can be repeatedly healed cracks occur.
이하 본 발명의 구체적인 실시예 및 이를 이용한 실험예를 참고하여 본 발명의 효과를 상세하게 설명한다.Hereinafter, the effects of the present invention will be described in detail with reference to specific examples of the present invention and experimental examples using the same.
실시예 1: 자외선 감응형 자가치유 고분자 필름의 제조Example 1 Preparation of UV Sensitive Self-Healing Polymer Film
단량체인 TCE 및 DCE를 물에 분산시킨 수용액에 안정제로 폴리아믹산(polyamic acid)를 첨가하여 8000rpm으로 10분간 교반한다. TCE 와 DCE를 포함하는 에멀젼(이하 TCE-co-DCE)이 형성되면 800rpm으로 30분간 교반하며 자외선을 조사하여 poly(TCE-co-DCE) 나노입자를 제조하고, 이를 캐스팅(casting)하고 200℃에서 60분간 열 이미드화(thermal imidization) 시켜 폴리이미드 필름 기재에 poly(TCE-co-DCE) 나노입자를 포함하는 자외선 감응형 자가치유 고분자 필름을 제조하였다.To the aqueous solution in which the monomers TCE and DCE were dispersed in water, polyamic acid was added as a stabilizer and stirred at 8000 rpm for 10 minutes. When an emulsion containing TCE and DCE (hereinafter referred to as TCE-co-DCE) was formed, the mixture was stirred at 800 rpm for 30 minutes and irradiated with UV light to prepare poly (TCE-co-DCE) nanoparticles, cast it, and cast at 200 ° C. Thermal imidization was performed for 60 minutes at to prepare a UV-sensitive self-healing polymer film including poly (TCE-co-DCE) nanoparticles on a polyimide film substrate.
실험예 1: 자외선 감응형 자가치유 고분자 나노입자의 구조 및 크기 분석Experimental Example 1: Analysis of structure and size of UV-sensitive self-healing polymer nanoparticles
전자주사현미경(Scanning Electron Microscope, SEM) 측정을 통하여 제조된 자외선 감응형 자가치유 고분자 나노입자의 구조 및 크기를 분석하였고, 이에 대한 결과를 도 5에 나타내었다. 이를 참조하면, 본 발명의 실시예에 따라 크기 산포가 적은 구형의 나노입자가 제조되었음을 확인할 수 있고, 입자크기는 대략 100nm 인 것을 알 수 있다.The structure and size of UV-sensitive self-healing polymer nanoparticles prepared by scanning electron microscope (SEM) measurement were analyzed, and the results are shown in FIG. 5. Referring to this, it can be confirmed that spherical nanoparticles having a small size scattering were prepared according to an embodiment of the present invention, and the particle size was approximately 100 nm.
전술한 본 발명의 설명은 예시를 위한 것이며, 본 발명이 속하는 기술분야의 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 쉽게 변형이 가능 하다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다. 예를 들어, 단일형으로 설명되어 있는 각 구성 요소는 분산되어 실시될 수도 있으며, 마찬가지로 분산된 것으로 설명되어 있는 구성 요소들도 결합 된 형태로 실시될 수 있다.The foregoing description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.
본 발명의 범위는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.The scope of the present invention is represented by the following claims, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present invention.

Claims (18)

  1. 자외선 감응형 자가치유 고분자 나노입자에 있어서, UV-sensitive self-healing polymer nanoparticles,
    자가치유 고분자 단일 층을 포함하며, Self-healing polymer monolayer,
    상기 자가치유 고분자는 사이클로뷰테인(cyclobutane) 고리를 포함하는 것을 특징으로 하는 자외선 감응형 자가치유 고분자 나노입자.The self-healing polymer is a UV-sensitive self-healing polymer nanoparticles, characterized in that it comprises a cyclobutane (cyclobutane) ring.
  2. 제1항에 있어서,The method of claim 1,
    상기 사이클로뷰테인 고리는 크랙(crack)에 의해 개환 되어 탄소-탄소 이중결합을 형성하는 것을 특징으로 하는 자외선 감응형 자가치유 고분자 나노입자.The cyclobutane ring is UV-opened self-healing polymer nanoparticles, characterized in that ring is opened by a crack (crack) to form a carbon-carbon double bond.
  3. 제2항에 있어서,The method of claim 2,
    상기 탄소-탄소 이중결합은 자외선에 의해 광-유도 고리화 첨가 반응을 하는 것을 특징으로 하는 자외선 감응형 자가치유 고분자 나노입자.The carbon-carbon double bond is UV-sensitive self-healing polymer nanoparticles, characterized in that the light-induced cycloaddition reaction by ultraviolet light.
  4. 자외선 감응형 자가치유 고분자 나노입자의 제조방법에 있어서,In the manufacturing method of ultraviolet-sensitive self-healing polymer nanoparticles,
    단량체를 포함하는 수용액을 제조하는 단계;Preparing an aqueous solution comprising a monomer;
    상기 수용액에 유화제를 첨가하여 단량체를 포함하는 에멀젼을 제조하는 단계; 및 Preparing an emulsion comprising a monomer by adding an emulsifier to the aqueous solution; And
    상기 에멀젼에 광을 조사하여 자외선 감응형 자가치유 고분자 나노입자를 제조하는 단계; Irradiating the emulsion to produce ultraviolet-sensitive self-healing polymer nanoparticles;
    를 포함하는 것을 특징으로 하는 자외선 감응형 자가치유 고분자 나노입자의 제조방법.UV-sensitive self-healing polymer nanoparticles manufacturing method comprising a.
  5. 제4항에 있어서,The method of claim 4, wherein
    상기 자외선 감응형 자가치유 고분자 나노입자의 제조방법은,The manufacturing method of the ultraviolet-sensitive self-healing polymer nanoparticles,
    단량체의 유화 및 광 중합 단계를 포함하는 것을 특징으로 하는 자외선 감응형 자가치유 고분자 나노입자의 제조방법.Method for producing a UV-sensitive self-healing polymer nanoparticles comprising the step of emulsifying and photopolymerization of the monomer.
  6. 제4항에 있어서,The method of claim 4, wherein
    상기 단량체는 광-유도 고리화 첨가 반응하여 중합체를 형성하는 것을 특징으로 하는 자외선 감응형 자가치유 고분자 나노입자의 제조방법.The monomer is a method of producing a UV-sensitive self-healing polymer nanoparticles, characterized in that the light-induced cycloaddition reaction to form a polymer.
  7. 제4항에 있어서,The method of claim 4, wherein
    상기 단량체는 탄소-탄소 이중결합 치환기를 2개 이상 포함하는 것을 특징으로 하는 자외선 감응형 자가치유 고분자 나노입자의 제조방법.The monomer is a method of producing a UV-sensitive self-healing polymer nanoparticles, characterized in that it comprises two or more carbon-carbon double bond substituents.
  8. 제4항에 있어서,The method of claim 4, wherein
    상기 유화제 대비 단량체의 중량비는 1:0.1 내지 1:1000 인 것을 특징으로 하는 자외선 감응형 자가치유 고분자 나노입자의 제조방법.The weight ratio of the monomer to the emulsifier is 1: 0.1 to 1: 1000 method for producing a UV-sensitive self-healing polymer nanoparticles, characterized in that.
  9. 제4항에 있어서,The method of claim 4, wherein
    상기 단량체를 포함하는 에멀젼을 제조하는 단계는,Preparing an emulsion comprising the monomer,
    상기 에멀젼을 분산시키기 위하여 100rpm 이상으로 교반하는 단계를 포함하는 것을 특징으로 하는 자외선 감응형 자가치유 고분자 나노입자의 제조방법.Method for producing a UV-sensitive self-healing polymer nanoparticles comprising the step of stirring at 100rpm or more to disperse the emulsion.
  10. 제4항에 있어서,The method of claim 4, wherein
    상기 에멀젼에 조사되는 광의 파장은 280nm 내지 380nm 인 것을 특징으로 하는 자외선 감응형 자가치유 고분자 나노입자의 제조방법.The wavelength of the light irradiated to the emulsion is a method for producing ultraviolet-sensitive self-healing polymer nanoparticles, characterized in that 280nm to 380nm.
  11. 제4항에 있어서,The method of claim 4, wherein
    상기 자외선 감응형 자가치유 고분자 나노입자는 직경이 10nm 내지 600nm인 것을 특징으로 하는 자외선 감응형 자가치유 고분자 나노입자의 제조방법.The ultraviolet-sensitive self-healing polymer nanoparticles is a method for producing ultraviolet-sensitive self-healing polymer nanoparticles, characterized in that the diameter of 10nm to 600nm.
  12. 제4항에 있어서,The method of claim 4, wherein
    상기 자외선 감응형 자가치유 고분자 나노입자는 사이클로뷰테인 고리를 포함하는 것을 특징으로 하는 자외선 감응형 자가치유 고분자 나노입자의 제조방법.The ultraviolet-sensitive self-healing polymer nanoparticles is a method for producing ultraviolet-sensitive self-healing polymer nanoparticles comprising a cyclobutane ring.
  13. 제12항에 있어서,The method of claim 12,
    상기 사이클로뷰테인 고리는 크랙에 의해 개환 되어 탄소-탄소 이중결합을 형성하는 것을 특징으로 하는 자외선 감응형 자가치유 고분자 나노입자의 제조방법.The cyclobutane ring is ring-opened by cracks to form a carbon-carbon double bond, characterized in that for producing a UV-sensitive self-healing polymer nanoparticles.
  14. 제13항에 있어서,The method of claim 13,
    상기 탄소-탄소 이중결합은 자외선에 의해 광-유도 고리화 첨가 반응을 하는 것을 특징으로 하는 자외선 감응형 자가치유 고분자 나노입자의 제조방법.The carbon-carbon double bond is a method for producing ultraviolet-sensitive self-healing polymer nanoparticles, characterized in that the light-induced cycloaddition reaction by ultraviolet light.
  15. 자외선 감응형 자가치유 고분자 코팅제에 있어서,UV-sensitive self-healing polymer coating agent,
    매트릭스 형성용 경화제; 및 Curing agents for matrix formation; And
    상기 경화제 내에 분산되며 제1항에 따른 자가치유 자외선 감응형 고분자 나노입자; Self-healing UV-sensitive polymer nanoparticles dispersed in the curing agent according to claim 1;
    를 포함하는 것을 특징으로 하는 자외선 감응형 자가치유 고분자 코팅제.UV-sensitive self-healing polymer coating agent comprising a.
  16. 제15항에 있어서,The method of claim 15,
    상기 자외선 감응형 자가치유 고분자 코팅제는 접착 증진제, 분산제, 안정제, 소포제 및 경화촉진제 중 1종 이상을 물질을 포함하는 것을 특징으로 하는 자외선 감응형 자가치유 고분자 코팅제.The UV-sensitive self-healing polymer coating agent is an ultraviolet-sensitive self-healing polymer coating agent, characterized in that it comprises at least one of an adhesion promoter, a dispersant, a stabilizer, an antifoaming agent and a curing accelerator.
  17. 제15항에 있어서,The method of claim 15,
    상기 경화제는 폴리비닐알코올, 폴리염화비닐, 폴리메틸메타크릴레이트, 폴리스티렌, 폴리디메틸실록세인, 폴리에스테르, 에폭시, 폴리에테르, 폴리이미드, 폴리카보네이트 및 폴리벤질메타크릴레이트 중 1종 이상의 화합물을 포함하는 것을 특징으로 할 수 있다. The curing agent includes at least one compound of polyvinyl alcohol, polyvinyl chloride, polymethylmethacrylate, polystyrene, polydimethylsiloxane, polyester, epoxy, polyether, polyimide, polycarbonate and polybenzyl methacrylate. It can be characterized by.
  18. 자외선 감응형 자가치유 고분자 필름에 있어서, In the ultraviolet-sensitive self-healing polymer film,
    박막형의 필름 기재; 및Thin film type substrate; And
    상기 필름 기재에 마련되며 제1항에 따른 자외선 감응형 자가치유 고분자 나노입자; UV-sensitive self-healing polymer nanoparticles provided on the film base material according to claim 1;
    를 포함하는 것을 특징으로 하는 자외선 감응형 자가치유 고분자 필름.UV-sensitive self-healing polymer film comprising a.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10357921B2 (en) 2017-05-24 2019-07-23 International Business Machines Corporation Light generating microcapsules for photo-curing
US10392452B2 (en) 2017-06-23 2019-08-27 International Business Machines Corporation Light generating microcapsules for self-healing polymer applications
US10900908B2 (en) 2017-05-24 2021-01-26 International Business Machines Corporation Chemiluminescence for tamper event detection
CN113121996A (en) * 2021-04-19 2021-07-16 河南国网电缆集团有限公司 High-molecular polymer material for wires and cables and preparation method thereof

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019117330A1 (en) * 2017-12-12 2019-06-20 한국생산기술연구원 Scratch self-healing clearcoat composition for automobiles using charge transfer complex, clearcoat comprising same, and method for producing same
KR102092785B1 (en) * 2018-03-20 2020-03-24 국방과학연구소 Method for producing UV sensitive self-healing coating material
KR102115798B1 (en) * 2018-11-26 2020-05-27 한국생산기술연구원 Uv sensitive self-healing polymer and manufacturing method of the same and film with the same
KR102542888B1 (en) * 2022-01-11 2023-06-14 주식회사 한국씨앤에스 Self-healing highly water-repellent coating composition and coating film thereby
KR102644505B1 (en) * 2022-12-19 2024-03-07 주식회사 한국씨앤에스 Self-healing high-hardness, high-water-repellent coating composition and coating film thereby

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090043726A (en) * 2007-10-30 2009-05-07 포항공과대학교 산학협력단 A self-healing conductive composite
KR101168038B1 (en) * 2011-12-15 2012-07-27 한국건설생활환경시험연구원 Microcapsule, self-healing coating material forming composition, capsule dispersion type self-healing coating material and manufacturing method of the coating material
KR101498361B1 (en) * 2013-05-10 2015-03-11 연세대학교 산학협력단 Microcapsules having self-healing composition and manufacturing method of the microcapsule, and coating material composition and self-healing flim having the same
KR20150041207A (en) * 2013-10-04 2015-04-16 (주)엘지하우시스 self-healing flooring materials

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101470462B1 (en) * 2011-02-14 2014-12-08 주식회사 엘지화학 Uv curable coating composition having self-healing property, coating film, and preparation method of coating film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090043726A (en) * 2007-10-30 2009-05-07 포항공과대학교 산학협력단 A self-healing conductive composite
KR101168038B1 (en) * 2011-12-15 2012-07-27 한국건설생활환경시험연구원 Microcapsule, self-healing coating material forming composition, capsule dispersion type self-healing coating material and manufacturing method of the coating material
KR101498361B1 (en) * 2013-05-10 2015-03-11 연세대학교 산학협력단 Microcapsules having self-healing composition and manufacturing method of the microcapsule, and coating material composition and self-healing flim having the same
KR20150041207A (en) * 2013-10-04 2015-04-16 (주)엘지하우시스 self-healing flooring materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHO, S. Y. ET AL.: "Photochemical Crack Healing in Cinnamate-based Polymers", JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, vol. 10, no. 10, 2010, pages 6972 - 6976 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10357921B2 (en) 2017-05-24 2019-07-23 International Business Machines Corporation Light generating microcapsules for photo-curing
US10900908B2 (en) 2017-05-24 2021-01-26 International Business Machines Corporation Chemiluminescence for tamper event detection
US10926485B2 (en) 2017-05-24 2021-02-23 International Business Machines Corporation Light generating microcapsules for photo-curing
US10392452B2 (en) 2017-06-23 2019-08-27 International Business Machines Corporation Light generating microcapsules for self-healing polymer applications
US10696761B2 (en) 2017-06-23 2020-06-30 International Business Machines Corporation Light generating microcapsules for self-healing polymer applications
US10703834B2 (en) 2017-06-23 2020-07-07 International Business Machines Corporation Light generating microcapsules for self-healing polymer applications
CN113121996A (en) * 2021-04-19 2021-07-16 河南国网电缆集团有限公司 High-molecular polymer material for wires and cables and preparation method thereof

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