KR102180456B1 - Polyurethane-based self-healability material and including the same - Google Patents
Polyurethane-based self-healability material and including the same Download PDFInfo
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/005—Repairing damaged coatings
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- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
- B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
Abstract
본 발명은 폴리우레탄 기반 자기치유 소재 및 그를 포함하는 물품에 관한 것으로, 더욱 자세하게는 OH기를 함유하는 고분자와 경화제로 이루어지는 우레탄 소재; 및 고리형 이종(heterocyclic) 구조 화합물을 포함하는 폴리우레탄 기반 자기치유 소재 및 그를 포함하는 물품에 관한 것이다.The present invention relates to a polyurethane-based self-healing material and an article comprising the same, and more specifically, a urethane material comprising a polymer and a curing agent containing an OH group; And a polyurethane-based self-healing material comprising a cyclic heterocyclic structure compound, and an article comprising the same.
Description
본 발명은 폴리우레탄 기반 자기치유 소재 및 그를 포함하는 물품에 관한 것으로서, 더욱 상세하게는 자기치유 성능이 향상된 폴리우레탄 기반 자기치유 소재 및 그를 포함하는 물품에 관한 것이다.The present invention relates to a polyurethane-based self-healing material and an article comprising the same, and more particularly, to a polyurethane-based self-healing material with improved self-healing performance, and an article comprising the same.
스크래치에 의한 표면손상이 발생하더라도 시간이 지남에 따라 자기 스스로 치유하는 회복력을 가져 스크래치가 잘 보이지 않고 거의 원상태로 돌아가는 소위 “스크래치 자기치유성”을 가진 소재가 최근 자동차의 최외곽 코팅층(클리어 코팅층)에 도입되고 있다.Even if surface damage caused by scratches occurs, a material with so-called “scratch self-healing” that has the resilience to self-heal over time, so that scratches are hard to see and return to its original state is the most recent outermost coating layer (clear coating layer) of automobiles. Is being introduced in.
국내에서 상용화된 자동차용 클리어코트 기술은 대부분 1액형 멜라민 고분자 가교 기반 기술로 구성되며, 일부 산 가교 형태의 화학적 반응을 통한 기술 및 고급화된 차량용으로 적용되는 2액형 우레탄 기반의 탄성형 제품이 적용되고 있다.Most of the clear coat technology for automobiles commercialized in Korea is composed of a one-component melamine polymer crosslinking-based technology, and a two-component urethane-based elastic product applied for advanced vehicles and technologies through chemical reactions in the form of acid crosslinking is applied. have.
하지만, 이러한 형태의 기존 클리어코트 기술은 지속적이면서 반복적인 자동차 표면의 스크래치 자기치유 특성을 제공하기 어려운 실정이다.However, the existing clear coat technology of this type is difficult to provide persistent and repetitive scratch self-healing properties on automobile surfaces.
한편, 종래의 폴리우레탄 기반 자기치유 소재는 단순히 폴리우레탄 탄성체의 유연성을 이용한 기술로서, 도막의 치밀성 및 가교도가 떨어져 표면 모듈러스와 도막 경도가 작고, 내후성 등의 문제점이 발생하였고, 극한 환경에서 발생하는 스크래치와 같은 손상에 대한 자기치유 회복율이 부족하다는 단점이 있었다.On the other hand, the conventional polyurethane-based self-healing material is simply a technology that uses the flexibility of a polyurethane elastomer, and the surface modulus and hardness of the coating film are low, and problems such as weather resistance have occurred due to low density and crosslinking of the coating film. There was a disadvantage that the self-healing recovery rate for damage such as scratches was insufficient.
이러한 종래의 폴리우레탄 기반 자기치유 소재의 단점을 보완하기 위하여 폴리우레탄 소재에 저분자량 디올을 첨가하는 시도가 한국 공개특허공보 제 2012-0088536 호(특허문헌 1) 및 한국 공개특허공보 제 2018-0011161 호(특허문헌 2)를 통해 이루어졌다. In order to compensate for the shortcomings of such conventional polyurethane-based self-healing materials, attempts to add low molecular weight diols to polyurethane materials are disclosed in Korean Patent Application Publication No. 2012-0088536 (Patent Document 1) and Korean Patent Publication No. 2018-0011161. It was made through the No.
특허문헌 1은 주제와 경화제로 이루어지는 폴리우레탄 조성물에 부탄디올 또는 펜탄디올과 같은 저분자량 디올(diol)을 첨가하고 있고, 특허문헌 2는 주제와 경화제로 이루어지는 폴리우레탄 조성물에 사슬형 연장제로서 네오펜틸 글리콜, 에틸-헥산디올 및/또는 3-메틸-1,5-펜탄디올 또는 1,4-부탄디올과 같은 지방족 저분자량 디올을 첨가하고 있다. Patent Document 1 adds a low molecular weight diol such as butanediol or pentanediol to a polyurethane composition consisting of a main material and a curing agent, and Patent Literature 2 is a polyurethane composition consisting of a main material and a curing agent. Aliphatic low molecular weight diols such as glycol, ethyl-hexanediol and/or 3-methyl-1,5-pentanediol or 1,4-butanediol are added.
그러나, 주제와 경화제로 이루어지는 폴리우레탄 조성물에 일반 저분자량 디올이나 지방족 저분자량 디올을 첨가하는 경우에는 극한 상황에서도 100%에 가까운 높은 자기 치유 회복율을 보일 수 없고, 빠른 자기 치유 회복 속도를 나타내지 않는다. However, when a general low molecular weight diol or an aliphatic low molecular weight diol is added to a polyurethane composition consisting of a main material and a curing agent, a high self-healing recovery rate close to 100% cannot be shown even under extreme conditions, and a fast self-healing recovery rate is not shown.
따라서, 극한 상황에서도 100%에 가까운 높은 자기 치유 회복율을 보일 수 있고, 빠른 자기 치유 회복 속도를 나타내는 새로운 자기치유 소재가 요청된다. Therefore, a new self-healing material that can show a high self-healing recovery rate close to 100% even in extreme situations and exhibits a fast self-healing recovery rate is required.
따라서, 본 발명이 해결하려는 과제는 극한 환경에 노출되더라도 자동차용 코팅소재로서 높은 자기치유 회복율과 빠른 자기치유 속도를 구현할 수 있는 폴리우레탄 기반 자기치유 소재 및 그를 포함하는 물품을 제공하는 것이다.Accordingly, the problem to be solved by the present invention is to provide a polyurethane-based self-healing material capable of realizing a high self-healing recovery rate and a fast self-healing speed as a coating material for automobiles even when exposed to extreme environments, and an article including the same.
상술한 본 발명의 해결과제를 달성하기 위한 본 발명의 제 1 양태는 OH기를 함유하는 고분자와 경화제로 이루어지는 우레탄 소재; 및 고리형 이종(heterocyclic) 구조 화합물을 포함하는 폴리우레탄 기반 자기치유 소재를 특징징으로 한다. The first aspect of the present invention for achieving the above-described problem of the present invention is a urethane material comprising a polymer containing an OH group and a curing agent; And a polyurethane-based self-healing material comprising a cyclic heterocyclic structure compound.
본 발명의 제 1 양태에 따른 폴리우레탄 기반 자기치유 소재의 상기 고리형 이종 구조 화합물은, 고리형 이종 구조를 갖는 저분자량 디올을 포함하는데, 구체적으로는 2,5-비스히드록시메틸 테트라하이드로푸란(2,5-bishydroxymethyl tetrahydrofuran, BHM-THF), 1,4-디티안-2,5-디올(1,4-Dithiane-2,5-diol), trans-1,4-디옥산-2,5-디올(trans-1,4-Dioxane-2,3-diol), 또는 이들 중 2 종 이상의 혼합물을 포함한다. The cyclic heterostructure compound of the polyurethane-based self-healing material according to the first aspect of the present invention includes a low molecular weight diol having a cyclic heterostructure, specifically 2,5-bishydroxymethyl tetrahydrofuran (2,5-bishydroxymethyl tetrahydrofuran, BHM-THF), 1,4-Dithiane-2,5-diol (1,4-Dithiane-2,5-diol), trans-1,4-dioxane-2, 5-diol (trans-1,4-Dioxane-2,3-diol), or a mixture of two or more thereof.
또한, 본 발명의 제 1 양태에 따른 폴리우레탄 기반 자기치유 소재의 상기 고리형 이종 구조 화합물은, 3각형 이상의 고리 구조를 가지면서 고리에 OH기가 한 개 이상 달려 있으며, 고리내에 탄소와 수소 이외의 원자를 한 개 이상 포함하고 있는 화합물을 포함한다. In addition, the cyclic heterostructure compound of the polyurethane-based self-healing material according to the first aspect of the present invention has a triangular or more ring structure and has at least one OH group in the ring, and other than carbon and hydrogen in the ring Includes compounds containing more than one atom.
본 발명의 제 1 양태에 따른 폴리우레탄 기반 자기치유 소재의 상기 OH기를 함유하는 고분자는, OH기를 함유하는 폴리아크릴레이트계 고분자, OH기를 함유하는 폴리메타크릴레이트계 고분자, OH기를 함유하는 폴리스티렌계 고분자, 또는 이들 중 2종 이상의 혼합물을 포함한다. The OH group-containing polymer of the polyurethane-based self-healing material according to the first aspect of the present invention is a polyacrylate-based polymer containing an OH group, a polymethacrylate-based polymer containing an OH group, and a polystyrene-based polymer containing an OH group. A polymer, or a mixture of two or more of them.
본 발명의 제 1 양태에 따른 폴리우레탄 기반 자기치유 소재의 상기 경화제는, 이소시아네이트계 화합물인 것을 특징으로 한다. The curing agent of the polyurethane-based self-healing material according to the first aspect of the present invention is characterized in that it is an isocyanate-based compound.
본 발명의 다른 일 측면으로서의 제 2 양태는 금속 기판; 및 상기 금속 기판에 코팅된 상기 제 1 양태에 따른 폴리우레탄 기반 자기치유 소재를 포함하는 물품이다. A second aspect as another aspect of the present invention is a metal substrate; And the polyurethane-based self-healing material according to the first aspect coated on the metal substrate.
본 발명의 또 다른 일 측면으로서의 제 3 양태는 플라스틱 기판; 및 상기 플라스틱 기판에 코팅된 상기 제 1 양태에 따른 폴리우레탄 기반 자기치유 소재를 포함하는 물품이다. A third aspect as another aspect of the present invention is a plastic substrate; And the polyurethane-based self-healing material according to the first aspect coated on the plastic substrate.
본 발명의 일 실시예에 따르면, 극한 환경에 노출되더라도 높은 자기치유 회복율과 빠른 자기치유 속도를 구현할 수 있는 자동차 최외곽 코팅용 폴리우레탄 기반 자기치유 소재를 구현할 수 있다.According to an embodiment of the present invention, it is possible to implement a polyurethane-based self-healing material for a car outermost coating capable of realizing a high self-healing recovery rate and a fast self-healing speed even when exposed to an extreme environment.
자동차뿐만 아니라, 극심한 외부 환경에 지속적인 노출이 이루어지는 항공기, 선박 등 수송기기용 코팅 분야 및 휴대폰, 태블릿 PC, 디스플레이 등의 전자제품의 외관 보전을 통한 품질향상을 기대할 수 있다.In addition to automobiles, quality improvement can be expected through the preservation of the exterior of electronic products such as mobile phones, tablet PCs, and displays, as well as the coating field for transportation devices such as aircraft and ships that are constantly exposed to extreme external environments.
본 명세서에 첨부되는 다음의 도면은 본 발명의 바람직한 실시예를 예시하는 것이며, 전술한 발명의 내용과 함께 본 발명의 기술사상을 더욱 이해시키는 역할을 하는 것이므로, 본 발명은 그러한 도면에 기재된 사항에만 한정되어 해석되어서는 아니 된다.
도 1은 본원의 일 실시예 및 일 비교예에 따른 폴리우레탄 소재 표면의 스크래치 부분의 시간에 따른 현상을 비교하여 나타낸 도면이다
도 2는 본원의 다른 실시예 및 비교예에 따른 폴리우레탄 소재 표면의 스크래치 부분의 시간에 따른 현상을 비교하여 나타낸 도면이다.
도 3 내지 도 5는 본원의 일 실시예 및 일 비교예에 따른 폴리우레탄 소재 표면의 스크래치 부분의 시간에 따른 현상을 하중에 따라 비교하여 나타낸 도면이다.The following drawings attached to the present specification illustrate preferred embodiments of the present invention, and serve to further understand the technical idea of the present invention together with the content of the above-described invention, so the present invention is limited to the matters described in such drawings. It is limited and should not be interpreted.
1 is a view showing a comparison of phenomena over time of a scratch portion on a surface of a polyurethane material according to an embodiment of the present application and a comparative example
2 is a view showing a comparison of phenomena over time of scratches on a surface of a polyurethane material according to another example and a comparative example of the present application.
3 to 5 are diagrams showing a time-dependent phenomenon of a scratch portion of a polyurethane material surface according to an exemplary embodiment and a comparative example of the present application compared with a load.
이하, 본 발명을 상세히 설명하기로 한다. 이에 앞서, 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Hereinafter, the present invention will be described in detail. Prior to this, terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventors appropriately explain the concept of terms in order to explain their own invention in the best way. Based on the principle that it can be defined, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.
따라서, 본 명세서에 기재된 실시예에 도시된 구성은 본 발명의 가장 바람직한 일 실시예에 불과할 뿐이고 본 발명의 기술적 사상에 모두 대변하는 것은 아니므로, 본 출원 시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다.Therefore, the configuration shown in the embodiments described in the present specification is only the most preferred embodiment of the present invention, and does not represent all of the technical idea of the present invention, and various equivalents that can replace them at the time of the present application And it should be understood that there may be variations.
본 발명의 일 측면에 따른 폴리우레탄 기반 자기치유 소재는, OH기를 함유하는 고분자와 경화제로 이루어지는 우레탄 소재; 및 고리형 이종(heterocyclic) 구조 화합물을 포함하는 것을 특징으로 한다.A polyurethane-based self-healing material according to an aspect of the present invention includes a urethane material comprising a polymer containing an OH group and a curing agent; And it characterized in that it comprises a cyclic heterocyclic (heterocyclic) structure compound.
본 발명에 따르면, OH기를 함유하는 고분자와 경화제로 이루어지는 기존의 우레탄 소재에, 고리형 이종(heterocyclic) 구조 화합물이 도입됨으로써, 높은 자기치유 회복율과 빠른 자기치유 속도를 구현할 수 있게 된다.According to the present invention, a high self-healing recovery rate and a fast self-healing speed can be implemented by introducing a cyclic heterocyclic structure compound into an existing urethane material comprising a polymer containing an OH group and a curing agent.
이는 본원의 고리형 이종 구조 화합물과 비슷한 분자 길이를 가지는 지방족 화합물을 기존의 우레탄 소재(OH기를 함유하는 고분자와 경화제로 구성)에 도입할 경우 우레탄 소재만으로 이루어진 것과 비슷한 자기치유 특성을 나타내는 것으로 보아, 본원의 고리형 이종 구조 화합물을 도입하였을 때에만 자기치유 특성이 더욱 향상되는 결과가 발생된다는 것을 알 수 있다.It is believed that when an aliphatic compound having a molecular length similar to that of the cyclic heterostructure compound of the present application is introduced into an existing urethane material (composed of a polymer containing OH groups and a curing agent), it is considered to exhibit self-healing properties similar to that of only urethane materials. It can be seen that the self-healing properties are further improved only when the cyclic heterostructure compound of the present application is introduced.
이때, 본 발명의 폴리우레탄 기반 자기치유 소재를 구성하는 OH기를 함유하는 고분자와 경화제 및 고리형 이종 구조 화합물간의 함량비는 다음의 식으로 정의될 수 있다. 즉, 다음의 식을 만족할 수 있도록 OH기를 함유하는 고분자와 경화제 및 고리형 이종 구조 화합물간의 함량비는 적절히 조절될 수 있다. At this time, the content ratio between the polymer containing the OH group constituting the polyurethane-based self-healing material of the present invention, the curing agent, and the cyclic heterostructure compound may be defined by the following equation. That is, the content ratio between the polymer containing the OH group and the curing agent and the cyclic heterostructure compound may be appropriately adjusted so as to satisfy the following equation.
(고분자 내 OH기의 수 + 고리형 이종 구조 화합물내 OH기의 수)= 이소시아네이트 기의 수(The number of OH groups in the polymer + the number of OH groups in the cyclic heterostructure compound) = number of isocyanate groups
일반적으로, 우레탄 소재는 모든 OH기와 모든 이소시아네이트기를 반응시킴으로써 경화도 100%를 맞추지만, 응용 분야나 주변 상황에 따라 경화도는 조절될 수 있다. 즉, 응용 분야 및 주변환경에 따라 “모든 OH기의 수=모든 이소시아네이트기의 수”라는 등식을 만족할 필요는 없다. In general, urethane materials have a degree of curing of 100% by reacting all OH groups with all isocyanate groups, but the degree of curing may be adjusted according to the application field or surrounding conditions. That is, it is not necessary to satisfy the equation of “the number of all OH groups = the number of all isocyanate groups” depending on the application field and the surrounding environment.
본 발명에 따른 상기 고리형 이종 구조 화합물은 고리형 이종 구조를 갖는 저분자량 디올인 것이 바람직하지만, 3각형 이상의 고리 구조를 가지면서 고리에 OH기가 한 개 이상 달려 있으며, 고리내에 탄소와 수소 이외의 원자(산소, 황, 질소 등)를 한 개 이상 포함하고 있는 화합물도 포함할 수 있다. The cyclic heterostructure compound according to the present invention is preferably a low molecular weight diol having a cyclic heterostructure, but has a triangular or more ring structure and has at least one OH group in the ring, and other than carbon and hydrogen in the ring Compounds containing one or more atoms (oxygen, sulfur, nitrogen, etc.) may also be included.
상기 고리형 이종 구조를 갖는 저분자량 디올은, 다음의 화학식 1 내지 화학식 3으로 정의되는 2,5-비스히드록시메틸 테트라하이드로푸란(2,5-bishydroxymethyl tetrahydrofuran, BHM-THF), 1,4-디티안-2,5-디올(1,4-Dithiane-2,5-diol), trans-1,4-디옥산-2,5-디올(trans-1,4-Dioxane-2,3-diol), 또는 이들 중 2종 이상의 혼합물을 포함할 수 있다. 물론, 본 발명이 아래의 화학식 1 내지 화학식 3에 예시된 구조의 화합물로 한정되는 것이 아님은 물론이다. The low molecular weight diol having a cyclic heterostructure is 2,5-bishydroxymethyl tetrahydrofuran (2,5-bishydroxymethyl tetrahydrofuran, BHM-THF), 1,4-, defined by the following Chemical Formulas 1 to 3 Dithiane-2,5-diol (1,4-Dithiane-2,5-diol), trans-1,4-dioxane-2,5-diol (trans-1,4-Dioxane-2,3-diol ), or a mixture of two or more of them. Of course, it goes without saying that the present invention is not limited to the compounds of the structures illustrated in Chemical Formulas 1 to 3 below.
<2,5-비스히드록시메틸 테트라하이드로푸란(2,5-bishydroxymethyl tetrahydrofuran, BHM-THF)><2,5-bishydroxymethyl tetrahydrofuran (BHM-THF)>
<1,4-디티안-2,5-디올(1,4-Dithiane-2,5-diol)><1,4-Dithiane-2,5-diol>
<trans-1,4-디옥산-2,5-디올(trans-1,4-Dioxane-2,3-diol)><trans-1,4-dioxane-2,5-diol (trans-1,4-Dioxane-2,3-diol)>
또한, 상기 3각형 이상의 고리 구조를 가지면서 고리에 OH기가 한 개 이상 달려 있으며, 고리내에 탄소와 수소 이외의 원자(산소, 황, 질소 등)를 한 개 이상 포함하고 있는 화합물의 예로서는 아래의 화학식 4를 참조한다. 물론, 본 발명이 아래의 화학식 4에 예시된 구조의 화합물로 한정되는 것이 아님은 물론이다. In addition, as an example of a compound having a triangular or more ring structure, one or more OH groups on the ring, and containing one or more atoms (oxygen, sulfur, nitrogen, etc.) other than carbon and hydrogen in the ring, the following formula See 4. Of course, it goes without saying that the present invention is not limited to the compounds of the structure illustrated in Formula 4 below.
(여기서, 상기 x, y, y', z는 0이상의 정수, 육각형의 경우 ortho, meta, para 위치중 하나)(Where, the x, y, y', z are integers of 0 or more, in the case of a hexagon, one of ortho, meta, and para positions)
본 발명에 따른 상기 OH기를 함유하는 고분자는, OH기를 함유하는 폴리아크릴레이트계 고분자, OH기를 함유하는 폴리메타크릴레이트계 고분자, OH기를 함유하는 폴리스티렌계 고분자, 또는 이들 중 2종 이상의 혼합물을 포함한다.The OH group-containing polymer according to the present invention includes a polyacrylate polymer containing an OH group, a polymethacrylate polymer containing an OH group, a polystyrene polymer containing an OH group, or a mixture of two or more of them do.
그리고, 본 발명에 따른 상기 경화제는, 이소시아네이트계 화합물일 수 있다.And, the curing agent according to the present invention may be an isocyanate-based compound.
한편, 본 발명의 다른 측면에 따르면, 금속 기판; 및 상기 금속 기판에 코팅된 전술한 본 발명에 따른 폴리우레탄 기반 자기치유 소재를 포함하는 물품과, 플라스틱 기판; 및 상기 플라스틱 기판에 코팅된 전술한 본 발명에 따른 폴리우레탄 기반 자기치유 소재를 포함하는 물품이 제공된다.On the other hand, according to another aspect of the present invention, a metal substrate; And an article comprising the polyurethane-based self-healing material according to the present invention coated on the metal substrate, and a plastic substrate; And there is provided an article comprising the polyurethane-based self-healing material according to the present invention coated on the plastic substrate.
상기 물품들의 구체적인 예로는, 자동차, 항공기, 선박 등의 수송기기일 수 있고, 태블릿 PC, 디스플레이, 스마트폰, 웨어러블 디바이스 등의 정보전자제품일 수 있으며, 국방 안보제품, 생활용품, 건축/공업용제 등 다양한 분야의 물품들일 수 있다.Specific examples of the above items may be transportation devices such as automobiles, aircraft, ships, etc., information and electronic products such as tablet PCs, displays, smartphones, wearable devices, and defense and security products, household goods, construction/industrial solvents, etc. It can be articles of various fields.
이하, 본 발명의 이해를 돕기 위하여 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 하기 실시예에 한정되는 것으로 해석되어서는 안 된다. 본 발명의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, examples will be described in detail to aid understanding of the present invention. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the following examples. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.
실시예 1Example 1
OH기를 함유하는 고분자를 형성하게 될 단량체로 높은 유리전이온도(Tg = 50℃)를 갖는 아크릴레이트 단량체 3g, 경화제로 HDI Trimer Isocyanate 1g 및 고리형 이종 구조 화합물인 2,5-비스히드록시메틸 테트라하이드로푸란(BHM-THF) 0.1g를 혼합하고, 뷰틸 아세테이트(butyl acetate) 용매로 용해한 후 페이스트 믹서를 사용하여 상온에서 3분간 교반한 후 2분간 탈포하였다. 그 후, 생성된 용액을 기판 위에 코팅한 후 150℃에서 30분간 건조함으로써 실시예 1에 따른 자기 치유 소재를 제조하였다.As a monomer that will form a polymer containing an OH group, 3 g of an acrylate monomer having a high glass transition temperature (Tg = 50°C), 1 g of HDI Trimer Isocyanate as a curing agent, and 2,5-bishydroxymethyl tetra, a cyclic heterostructure compound 0.1 g of hydrofuran (BHM-THF) was mixed, dissolved in a butyl acetate solvent, stirred for 3 minutes at room temperature using a paste mixer, and defoamed for 2 minutes. Thereafter, the resulting solution was coated on a substrate and dried at 150° C. for 30 minutes to prepare a self-healing material according to Example 1.
실시예 2Example 2
OH기를 함유하는 고분자를 형성하게 될 단량체로 낮은 유리전이온도(Tg = 10℃)를 갖는 아크릴레이트 단량체 3g, 경화제로 HDI Trimer Isocyanate 1g 및 고리형 이종 구조 화합물인 2,5-비스히드록시메틸 테트라하이드로푸란(BHM-THF) 0.1g를 혼합하고, 뷰틸 아세테이트(butyl acetate) 용매로 용해한 후 페이스트 믹서를 사용하여 상온에서 3분간 교반한 후 2분간 탈포하였다. 그 후, 생성된 용액을 기판 위에 코팅한 후 150℃에서 30분간 건조함으로써 실시예 2에 따른 자기 치유 소재를 제조하였다.As a monomer that will form a polymer containing an OH group, 3 g of an acrylate monomer having a low glass transition temperature (Tg = 10°C), 1 g of HDI Trimer Isocyanate as a curing agent, and 2,5-bishydroxymethyl tetra, a cyclic heterostructure compound 0.1 g of hydrofuran (BHM-THF) was mixed, dissolved in a butyl acetate solvent, stirred for 3 minutes at room temperature using a paste mixer, and defoamed for 2 minutes. Thereafter, the resulting solution was coated on a substrate and dried at 150° C. for 30 minutes to prepare a self-healing material according to Example 2.
비교예 1Comparative Example 1
OH기를 함유하는 고분자를 형성하게 될 단량체로 높은 유리전이온도(Tg = 50℃)를 갖는 아크릴레이트 단량체 3g, 경화제로 HDI Trimer Isocyanate 1g을 혼합하고, 뷰틸 아세테이트(butyl acetate) 용매로 용해한 후 페이스트 믹서를 사용하여 상온에서 3분간 교반한 후 2분간 탈포하였다. 그 후, 생성된 용액을 기판 위에 코팅한 후 150℃에서 30분간 건조함으로써 비교예 1에 따른 자기 치유 소재를 제조하였다.As a monomer that will form a polymer containing an OH group, 3 g of an acrylate monomer having a high glass transition temperature (Tg = 50°C), and 1 g of HDI Trimer Isocyanate as a curing agent are mixed, dissolved in a butyl acetate solvent, and then mixed with a paste mixer. After stirring for 3 minutes at room temperature using, defoaming for 2 minutes. Thereafter, the resulting solution was coated on a substrate and dried at 150° C. for 30 minutes to prepare a self-healing material according to Comparative Example 1.
비교예 2Comparative Example 2
OH기를 함유하는 고분자를 형성하게 될 단량체로 낮은 유리전이온도(Tg = 10℃)를 갖는 아크릴레이트 단량체 3g, 경화제로 HDI Trimer Isocyanate 1g을 혼합하고, 뷰틸 아세테이트(butyl acetate) 용매로 용해한 후 페이스트 믹서를 사용하여 상온에서 3분간 교반한 후 2분간 탈포하였다. 그 후, 생성된 용액을 기판 위에 코팅한 후 150℃에서 30분간 건조함으로써 비교예 2에 따른 자기 치유 소재를 제조하였다.As a monomer that will form a polymer containing an OH group, 3g of an acrylate monomer having a low glass transition temperature (Tg = 10℃), and 1g of HDI Trimer Isocyanate as a curing agent are mixed, dissolved in a butyl acetate solvent, and then mixed with a paste mixer. After stirring for 3 minutes at room temperature using, defoaming for 2 minutes. Thereafter, the resulting solution was coated on a substrate and dried at 150° C. for 30 minutes to prepare a self-healing material according to Comparative Example 2.
<스크래치 자기치유 테스트><Scratch self-healing test>
Hardness Test Pencil 318S을 사용하였다. 스크래치 팁은 텅스텐 1.0mm ISO 규격을 사용하여 상기 실시예 및 비교예들에서 제조된 소재에 1kg의 하중으로 스크래치를 긁었다. 그 후 75℃ 열을 가하여 시간의 경과에 따라 스크래치 부분의 표면현상을 동영상 촬영을 통해 정성적으로 관찰하고 이를 도 1 및 도 2에 나타내었다. Hardness Test Pencil 318S was used. As for the scratch tip, tungsten 1.0mm ISO standard was used, and the scratch was scratched with a load of 1 kg on the material prepared in the above Examples and Comparative Examples. Thereafter, heat was applied at 75° C. to qualitatively observe the surface phenomenon of the scratch portion over time through video recording, and are shown in FIGS. 1 and 2.
도 1 및 도 2를 참조하면, 실시예 1 및 실시예 2의 경우는 스크래치가 가해진 후 90분이 경과함에 따라 스크래치가 사라져서 자기 치유되었음을 확인할 수 있으나, 비교예 1 및 비교예 2의 경우는 스크래치가 가해진 후 120분이 경과해도 스크래치가 사라지지 않음을 확인할 수 있다. 이를 통해, 본 발명에 따른 고리형 이종 구조 화합물을 포함하는 우레탄 소재가 기존의 우레탄 소재에 비해 자기치유회복율 및 자기치유속도가 매우 뛰어남을 알 수 있다. 1 and 2, in the case of Examples 1 and 2, the scratch disappeared and self-healing was confirmed as 90 minutes elapsed after the scratch was applied, but in Comparative Examples 1 and 2, the scratch was It can be seen that the scratch does not disappear even after 120 minutes have elapsed after application. Through this, it can be seen that the urethane material including the cyclic heterostructure compound according to the present invention has very excellent self-healing recovery rate and self-healing speed compared to the existing urethane material.
<사파이어 팁 테스트><Sapphire tip test>
실시예 1 및 비교예 1에서 제조된 자기 치유 소재에 대해, 규격 사파이어를 사용하여 특정 하중(5N, 10N, 15N)에서 100m/s의 속도로 순간적으로 도막의 표면을 긁어내는 스크래치 실험을 한 후, 자기 치유를 확인하기 위해 75℃의 열을 가하고 Optical microscopy를 통해 그 표면을 관찰하고 이를 도 3, 도 4 및 도 5를 통해 나타내었다. For the self-healing material prepared in Example 1 and Comparative Example 1, a scratch experiment was performed in which the surface of the coating film was scraped instantly at a speed of 10,000 m /s under a specific load (5N, 10N, 15N) using standard sapphire. After that, in order to confirm self-healing, heat of 75° C. was applied and the surface was observed through optical microscopy, and this was shown through FIGS. 3, 4 and 5.
도 3(5N), 도 4(10N) 및 도 5(15N)를 참조하면, 실시예 1의 경우는 스크래치가 가해진 후 10분이 경과함에 따라 스크래치가 사라져서 자기 치유되었음을 확인할 수 있으나, 비교예 1의 경우는 스크래치가 가해진 후 60분이 경과해도 스크래치가 사라지지 않음을 확인할 수 있다. 이를 통해, 본 발명에 따른 고리형 이종 구조 화합물을 포함하는 우레탄 소재가 기존의 우레탄 소재에 비해 자기치유회복율 및 자기치유속도가 매우 뛰어남을 알 수 있다. 3(5N), 4(10N), and 5(15N), in the case of Example 1, it can be confirmed that the scratch disappeared and self-healed as 10 minutes elapsed after the scratch was applied. In the case, it can be confirmed that the scratch does not disappear even after 60 minutes elapsed after the scratch was applied. Through this, it can be seen that the urethane material including the cyclic heterostructure compound according to the present invention has very excellent self-healing recovery rate and self-healing speed compared to the existing urethane material.
Claims (8)
이소시아네이트계 화합물; 및
아래 화학식의 1,4-디티안-2,5-디올(1,4-Dithiane-2,5-diol)을 포함하는 폴리우레탄 기반 자기치유 소재.
Isocyanate compounds; And
Polyurethane-based self-healing material containing 1,4-Dithiane-2,5-diol of the formula below.
이소시아네이트계 화합물; 및
아래 화학식의 trans-1,4-디옥산-2,5-디올(trans-1,4-Dioxane-2,3-diol)을 포함하는 폴리우레탄 기반 자기치유 소재.
Isocyanate compounds; And
Polyurethane-based self-healing material containing trans-1,4-dioxane-2,5-diol of the following formula.
상기 금속 기판에 코팅된 제 1 항 또는 제 2 항에 따른 폴리우레탄 기반 자기치유 소재를 포함하는 물품.Metal substrate; And
An article comprising the polyurethane-based self-healing material according to claim 1 or 2 coated on the metal substrate.
상기 플라스틱 기판에 코팅된 제 1 항 또는 제 2 항에 따른 폴리우레탄 기반 자기치유 소재를 포함하는 물품.Plastic substrate; And
An article comprising the polyurethane-based self-healing material according to claim 1 or 2 coated on the plastic substrate.
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