KR20190027436A - Organic -inorganic hybrid coating composition including nano-cellulose particle - Google Patents
Organic -inorganic hybrid coating composition including nano-cellulose particle Download PDFInfo
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- 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
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/02—Cellulose; Modified cellulose
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
Description
본 발명은 유-무기 하이브리드 코팅 조성물에 관한 것으로서, 더욱 상세하게는 나노셀룰로오스 입자를 포함하여, 강도와 유연성이 우수한 코팅막을 형성할 수 있는 유-무기 하이브리드 코팅 조성물에 관한 것이다.The present invention relates to an organic-inorganic hybrid coating composition, and more particularly, to an organic-inorganic hybrid coating composition capable of forming a coating film having excellent strength and flexibility, including nanocellulose particles.
코팅제는 다양한 제품의 표면에 도포되어 해당 제품 내부로 수분이 흡수되거나 이 물질이 들어가는 것을 방지하는 역할을 한다. 또한 물리적인 힘에 의해 제품이 손상되지 않도록 제품을 직접적으로 보호하는 역할을 한다. 코팅제는 사용되는 제품의 사용 환경에 따라 다르지만 고온에 녹거나 타지 않아야 하고 제품에 코팅된 뒤, 제품을 구부렸을 때 깨지지 않아야 한다. 코팅제가 고온에 녹아버리면 코팅제로서의 역할을 하지 못하고, 구부렸을 때 깨지면 코팅 기능을 상실하게 된다. 코팅이 불투명화되면 외관상의 기능도 떨어진다. 일상에서 사용되는 코팅제는 물건 표면에 고르게 부착되어 흠집이 나지 않으면서 매끄러워야 우수한 코팅제이다. 코팅제의 경도가 약해 코팅된 표면에 스크래치가 나거나 파손되면 새로운 코팅제로 교체해야 하는 수고스러움이 있다. Coatings are applied to the surface of various products to prevent water from being absorbed into the product or from entering the product. It also protects the product from direct damage by physical force. Coatings should not melt or burn at high temperatures, but should not break when the product is bent after being coated on the product, depending on the environment in which the product is used. If the coating melts at a high temperature, it does not function as a coating agent, and when it is bent, the coating function is lost. If the coating becomes opaque, its apparent function is also impaired. The coating agent used in everyday life is an excellent coating agent because it is smoothly adhered evenly on the surface of the article and not scratched. If the hardness of the coating is weak and the coated surface is scratched or broken, it is laborious to replace it with a new coating.
종래의 코팅제는 고분자 등의 유기물로 이루어지거나, 실리카 등의 무기물로 이루어진다. 유기물로 형성된 코팅막은 유연성이 우수하지만 강도가 낮고, 무기물로 형성된 코팅층은 강도가 높지만 유연성이 낮은 단점이 있다. 따라서, 유기물과 무기물을 혼합한 코팅제가 개발되고 있으나, 유기물과 무기물의 장점을 보다 효과적으로 발휘할 수 있는 코팅 조성물의 개발이 필요한 실정이다.Conventional coatings are made of organic materials such as polymers or inorganic materials such as silica. The coating layer formed of an organic material is excellent in flexibility but has a low strength and a coating layer formed of an inorganic material has a disadvantage of high strength but low flexibility. Accordingly, although a coating agent containing an organic material and an inorganic material has been developed, it is necessary to develop a coating composition capable of more effectively exhibiting the advantages of organic materials and inorganic materials.
본 발명의 목적은, 종래의 유기 또는 무기 코팅 조성물의 단점을 개선하여, 강도와 유연성이 우수한 코팅막을 형성할 수 있는 유-무기 하이브리드 코팅 조성물을 제공하는 것이다. It is an object of the present invention to provide an oil-and-inorganic hybrid coating composition capable of improving the drawbacks of conventional organic or inorganic coating compositions to form coating films excellent in strength and flexibility.
상기 목적을 달성하기 위하여, 본 발명은 평균 입자 크기가 30μm 내지 50μm 인 셀루로오스 입자; 테트라알콕시실란(알콕시기의 탄소수는 1 내지 3개임); 실란 커플링제; 및 용매를 포함하는 유-무기 하이브리드 코팅 조성물을 제공한다.In order to accomplish the above object, the present invention relates to cellulose particles having an average particle size of 30 μm to 50 μm; Tetraalkoxysilane (the number of carbon atoms of the alkoxy group is 1 to 3); Silane coupling agents; And an organic-inorganic hybrid coating composition comprising a solvent.
본 발명에 따른 유-무기 하이브리드 코팅 조성물은, 종래의 유기 또는 무기 코팅 조성물의 단점을 개선하여, 강도와 유연성이 우수한 코팅막을 형성할 수 있다.The organic-inorganic hybrid coating composition according to the present invention improves disadvantages of conventional organic or inorganic coating compositions, and can form a coating film having excellent strength and flexibility.
이하, 본 발명을 더욱 상세히 설명한다. Hereinafter, the present invention will be described in more detail.
본 발명에 따른 유-무기 하이브리드 코팅 조성물은 나노 사이즈의 셀룰로오스 입자와 테트라알콕시실란 성분을 포함하여, 나노 사이즈의 셀룰로오스가 분산된 실리카 코팅막을 형성한다. 형성된 실리카 코팅막은 유기물과 무기물이 하이브리드화되어, 셀룰로오스 유기 고분자의 강점과 무기 실리카 코팅막의 강점을 모두 가진다. 여기서, “하이브리드화”는 서로 다른 재료를 원자나 분자 레벨로 미시적으로 혼합시켜, 원자간 또는 분자간 상호 작용에 의해, 새로운 기능을 발휘하게 하는 것이다. The organic-inorganic hybrid coating composition according to the present invention comprises a nano-sized cellulose particle and a tetraalkoxy silane component to form a silica coating film in which nano-sized cellulose is dispersed. The formed silica coating film has both the strength of the cellulose organic polymer and the strength of the inorganic silica coating film because the organic material and the inorganic material are hybridized. Here, " hybridization " is to mix different materials microscopically at the atomic or molecular level and to bring out new functions by interatomic or intermolecular interactions.
본 발명에 따른 유-무기 하이브리드 코팅 조성물은 셀룰로오스 입자, 테트라알콕시실란(알콕시기의 탄소수는 1 내지 3개임), 실란 커플링제 및 용매를 포함한다. 본 발명의 코팅 조성물에 있어서, 상기 셀룰로오스 입자의 함량은 0.35 내지 0.45 중량%, 바람직하게는 0.39 내지 0.41 중량%이고, 상기 테트라알콕시실란의 함량은 1.92 내지 2.08 중량%, 바람직하게는 1.99 내지 2.01 중량%이며, 상기 실란 커플링제의 함량은 3.92 내지 4.08 중량%, 바람직하게는 3.99 내지 4.01 중량%이며, 상기 용매의 함량은 1.95 내지 2.05 중량%, 바람직하게는 1.99 내지 2.01 중량%이다. 여기서, 상기 셀룰로오스 입자의 함량이 너무 작거나, 테트라알콕시실란의 함량이 너무 많으면 코팅막의 유연성이 부족할 우려가 있고, 상기 셀룰로오스 입자의 함량이 너무 많거나, 테트라알콕시실란의 함량이 너무 작으면, 코팅막의 강도가 부족할 우려가 있다. 또한, 상기 실란 커플링제의 함량이 너무 작거나 많으면, 코팅막이 형성되지 않거나, 코팅막의 강도가 저하될 우려가 있다.The organic-inorganic hybrid coating composition according to the present invention comprises cellulose particles, tetraalkoxysilane (the number of carbon atoms of the alkoxy group is 1 to 3), a silane coupling agent and a solvent. In the coating composition of the present invention, the content of the cellulose particles is 0.35 to 0.45 wt%, preferably 0.39 to 0.41 wt%, and the content of the tetraalkoxysilane is 1.92 to 2.08 wt%, preferably 1.99 to 2.01 wt% %, And the content of the silane coupling agent is 3.92 to 4.08% by weight, preferably 3.99 to 4.01% by weight, and the content of the solvent is 1.95 to 2.05% by weight, preferably 1.99 to 2.01% by weight. If the content of the cellulose particles is too small or the content of the tetraalkoxysilane is too large, there is a possibility that the flexibility of the coating film becomes insufficient. If the content of the cellulose particles is too large or the content of the tetraalkoxysilane is too small, There is a possibility that the strength of the resin is insufficient. If the content of the silane coupling agent is too small or too large, there is a fear that the coating film is not formed or the strength of the coating film is lowered.
본 발명에 사용되는 셀룰로오스 입자는 β-D-글루코스가 β-글루코시드 결합(1-4글루코시드 결합)을 통해 중합체를 이룬 다당류로서, 화학식은 (C6H10O5)n로 표시될 수 있다(n은 수백 내지 수천의 정수). 셀룰로오스는 친수성이고 맛과 냄새가 없으며 물에 용해되지 않는다. 또한 섬유 내 인접한 글루칸의 비공유결합으로 인해 강철과 비슷한 정도의 신장력을 가지며 분해가 잘 되지 않는 특성을 가진다고 알려져 있다. 본 발명에 사용되는 셀룰로오스는 평균 입자 크기가 30㎛ 내지 50μm 인 셀룰로오스를 특별한 제한없이 사용할 수 있다. 또한, 필요에 따라서, 상기 나노 셀룰로오스의 표면을 개질하여 사용할 수 있다. 본 발명의 코팅 조성물을 이용하여 코팅막을 형성하면, 상기 나노 셀룰로오스의 표면은 상기 실란 커플링제에 의하여 개질되며, 실란 커플링제는 코팅막을 형성하는 실리카에 결합된다. 따라서, 실리카 코팅막과 나노 셀룰로오스가 실란 커플링제에 의해 결합되는 형태를 가짐으로서, 실리카 코팅막에 나노 셀룰로오스가 균일하게 분산된다.Cellulose particles used in the present invention are polysaccharides in which? -D-glucose is polymerized through a? -Glucosid bond (1-4 glucosidic bonds), and the formula can be represented by (C 6 H 10 O 5 ) n (N is an integer of hundreds to thousands). Cellulose is hydrophilic, has no taste and odor, and is not soluble in water. It is also known that it has an elongation similar to that of steel due to the non-covalent bonding of the adjacent glucan in the fiber and does not decompose well. The cellulose used in the present invention may be cellulose having an average particle size of 30 μm to 50 μm without any particular limitation. Further, if necessary, the surface of the nanocellulose may be modified and used. When a coating film is formed using the coating composition of the present invention, the surface of the nanocellulose is modified by the silane coupling agent, and the silane coupling agent is bonded to the silica forming the coating film. Therefore, the silica coating film and the nanocellulose are bonded by the silane coupling agent, so that the nanocellulose is uniformly dispersed in the silica coating film.
본 발명의 코팅 조성물에 사용되는 테트라알콕시실란은 가수분해 및 축합 반응을 통하여 실리카 코팅막을 형성할 수 있는 통상의 실리카 전구체로서, 알콕시기의 탄소수가 1 내직 3개인 알콕시 실란 화합물, 구체적으로, 테트라에틸 오쏘실리케이트 (Tetraethyl 0rtho silicate, TEOS, 테트라에톡시실란)를 사용할 수 있다. The tetraalkoxysilane used in the coating composition of the present invention is a conventional silica precursor capable of forming a silica coating film through hydrolysis and condensation reaction and is an alkoxysilane compound having three carbon atoms in the alkoxy group, Tetraethyl orthosilicate (TEOS, tetraethoxysilane) can be used.
본 발명의 코팅 조성물에 사용되는 실란 커플링제는 실리카 코팅막을 가교시키는 역할을 하는 것으로서, 3-메타크릴옥시프로필 트리메톡시실란 (3-Methacryloxypropyl trimethoxysilane), 3-(2,3-에폭시프로폭시) 프로필 트리메톡시실란 (3-(2,3-Epoxypropoxy) propyl trimethoxysilane), 비닐트리메톡시실란(Vinyltrimethoxysilane), 비닐트리에톡시실란, 3-트리메톡시 실릴프로필 메타크릴레이트(3-Trimethoxysilylpropyl Methacrylate, MPTMS) 등을 사용할 수 있다. The silane coupling agent used in the coating composition of the present invention has a role of crosslinking the silica coating film, and includes 3-methacryloxypropyl trimethoxysilane, 3- (2,3-epoxypropoxy) Propyl trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-trimethoxysilylpropyl methacrylate, 3-trimethoxysilylpropyl methacrylate, MPTMS) can be used.
본 발명의 코팅 조성물에 사용되는 용매로는 셀룰로오스 입자, 테트라알콕시실란 및 실란 커플링제를 용해 또는 분산시켜 균일한 코팅막을 형성할 수 있는 용매를 특별한 제한없이 사용할 수 있다. 상기 용매의 예로는, 메탄올, 에탄올 등의 알코올 용매를 예시할 수 있다. As the solvent used in the coating composition of the present invention, a solvent capable of forming a uniform coating film by dissolving or dispersing cellulose particles, tetraalkoxysilane and silane coupling agent can be used without particular limitation. Examples of the solvent include alcohol solvents such as methanol and ethanol.
또한, 본 발명에 따른 코팅 조성물은, 필요에 따라, 펄프(pulp), 투명 코팅제, 암모니아 용액 등의 각종 첨가제를 더욱 포함할 수 있다. In addition, the coating composition according to the present invention may further contain various additives such as pulp, transparent coating agent and ammonia solution, if necessary.
이와 같이, 나노 셀룰로오스가 하이브리드(분산)된 실리카 코팅막을 형성하면, 코팅막의 강도를 유지하면서, 코팅막의 유연성이 향상된다. 또한, 본 발명의 조성물로 형성된 코팅막은 유연성이 높아 잘 깨지지 않으며, 코팅막이 형성된 제품을 구부릴 경우에 코팅막이 불투명하게 변질되는 것을 억제할 수 있다. Thus, when the silica coating film in which nanocellulose is hybridized (dispersed) is formed, the flexibility of the coating film is improved while maintaining the strength of the coating film. In addition, the coating film formed from the composition of the present invention has high flexibility and is not broken easily, and it is possible to suppress opacification of the coating film when the product having the coating film is bent.
이하, 구체적인 실시예 및 비교예를 통하여 본 발명을 더욱 상세히 설명한다. 하기 실시예는 본 발명을 예시하기 위한 것으로서, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail by way of specific examples and comparative examples. The following examples illustrate the present invention and are not intended to limit the scope of the present invention.
[실시예] 코팅조성물의제조및이를이용한코팅막의형성 [Examples] Preparation of Coating Composition and Formation of Coating Film Using It
평균 입자 크기가 30μm인 셀룰로오스 입자 0.4 중량%, 테트라에톡시실란 (TEOS) 4.0 중량%, 실란 커플링제로서 3-트리메톡시 실릴프로필 메타크릴레이트 4.0 중량%및 용매로서 메탄올 2.0 중량%를 혼합하여, 유-무기 하이브리드 코팅 조성물을 제조하였다. 상기 코팅 조성물을 플라스틱 기판에 코팅하고 가열하여, 두께 0.5 mm의 코팅막을 형성하였다. 코팅막이 형성된 플라스틱 기판을 90도 각도로 구부린 결과 백탁 현상이 발생하지 않아 코팅막의 유연성이 우수함을 확인할 수 있었다. 또한, 형성된 코팅막의 연필 경도를 측정한 결과 4H로서 경도가 우수함을 확인할 수 있었다.0.4 wt% of cellulose particles having an average particle size of 30 μm, 4.0 wt% of tetraethoxysilane (TEOS), 4.0 wt% of 3-trimethoxysilylpropyl methacrylate as a silane coupling agent and 2.0 wt% of methanol as a solvent were mixed To prepare an organic-inorganic hybrid coating composition. The coating composition was coated on a plastic substrate and heated to form a coating film having a thickness of 0.5 mm. The plastic substrate with the coated film bent at an angle of 90 degrees showed no whitening phenomenon, indicating that the flexibility of the coated film was excellent. As a result of measuring the pencil hardness of the formed coating film, it was confirmed that the hardness was excellent as 4H.
[비교예] 코팅조성물의제조및이를이용한코팅막의형성 [Comparative Example] Preparation of Coating Composition and Formation of Coating Film Using It
셀룰로오스 입자를 사용하지 않은 것을 제외하고는, 실시예와 동일한 방법으로 코팅 조성물을 제조하고, 코팅막을 형성하였다. 코팅막이 형성된 플라스틱 기판을 90도 각도로 구부린 결과 백탁 현상이 발생하여 코팅막의 유연성이 부족함을 확인할 수 있었다. 또한, 형성된 코팅막의 연필 경도를 측정한 결과 2H로서 경도가 부족함을 확인할 수 있었다.A coating composition was prepared and coating films were formed in the same manner as in Example except that cellulose particles were not used. The plastic substrate with the coating film formed thereon was bent at an angle of 90 degrees, resulting in whitening, indicating that the flexibility of the coating film was insufficient. Further, the pencil hardness of the formed coating film was measured, and it was confirmed that the hardness was insufficient as 2H.
Claims (3)
테트라알콕시실란(알콕시기의 탄소수는 1 내지 3개임);
실란 커플링제; 및
용매를 포함하는 유-무기 하이브리드 코팅 조성물.Cellulosic particles having an average particle size of 30 탆 to 50 탆;
Tetraalkoxysilane (the number of carbon atoms of the alkoxy group is 1 to 3);
Silane coupling agents; And
Organic hybrid coating composition comprising a solvent.
The method of claim 1, wherein the tetraalkoxysilane is tetraethylorthosilicate and the silane coupling agent is 3-methacryloxypropyltrimethoxysilane, 3- (2,3-epoxypropoxy) propyltrimethoxysilane, Vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-trimethoxysilylpropyl methacrylate. 2. The oil-in-water hybrid coating composition according to claim 1,
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| KR20210062757A (en) * | 2019-11-21 | 2021-06-01 | 한국생산기술연구원 | Cellulose nano fiber surface ceramic modifing method for and ceramic coating solution manufactring method using thereof |
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|---|---|---|---|---|
| KR101015385B1 (en) | 2008-10-31 | 2011-02-22 | 한국생산기술연구원 | Solution for Thin Film Coating of Organic/Inorganic hybrid complex and Method of Produce for the Same and Method of Coating Using the Same |
| KR20130048744A (en) | 2013-04-08 | 2013-05-10 | 이재환 | Liquid curable composition |
| KR20140022798A (en) | 2011-01-12 | 2014-02-25 | 어쿠스틱 그룹 오와이 | Coating and its manufacturing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101015385B1 (en) | 2008-10-31 | 2011-02-22 | 한국생산기술연구원 | Solution for Thin Film Coating of Organic/Inorganic hybrid complex and Method of Produce for the Same and Method of Coating Using the Same |
| KR20140022798A (en) | 2011-01-12 | 2014-02-25 | 어쿠스틱 그룹 오와이 | Coating and its manufacturing process |
| KR20130048744A (en) | 2013-04-08 | 2013-05-10 | 이재환 | Liquid curable composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20210062757A (en) * | 2019-11-21 | 2021-06-01 | 한국생산기술연구원 | Cellulose nano fiber surface ceramic modifing method for and ceramic coating solution manufactring method using thereof |
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