KR101408703B1 - Fabrication method for thin film having superhydrophobic surface and superhydrophobic thin film fabricated thereby - Google Patents
Fabrication method for thin film having superhydrophobic surface and superhydrophobic thin film fabricated thereby Download PDFInfo
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- KR101408703B1 KR101408703B1 KR1020120039651A KR20120039651A KR101408703B1 KR 101408703 B1 KR101408703 B1 KR 101408703B1 KR 1020120039651 A KR1020120039651 A KR 1020120039651A KR 20120039651 A KR20120039651 A KR 20120039651A KR 101408703 B1 KR101408703 B1 KR 101408703B1
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- triacrylate
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- 239000010409 thin film Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 20
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 20
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 7
- 230000001678 irradiating effect Effects 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 16
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical group C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
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- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ZCHGODLGROULLT-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;propane-1,2-diol Chemical compound CC(O)CO.OCC(CO)(CO)CO ZCHGODLGROULLT-UHFFFAOYSA-N 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 2
- MTPIZGPBYCHTGQ-UHFFFAOYSA-N 2-[2,2-bis(2-prop-2-enoyloxyethoxymethyl)butoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCC(CC)(COCCOC(=O)C=C)COCCOC(=O)C=C MTPIZGPBYCHTGQ-UHFFFAOYSA-N 0.000 claims description 2
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 2
- NCNNNERURUGJAB-UHFFFAOYSA-N 3-[2,2-bis(3-prop-2-enoyloxypropoxymethyl)butoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OCCCOCC(CC)(COCCCOC(=O)C=C)COCCCOC(=O)C=C NCNNNERURUGJAB-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
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- 229920000642 polymer Polymers 0.000 description 19
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- 239000002086 nanomaterial Substances 0.000 description 10
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- 238000001878 scanning electron micrograph Methods 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 4
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 125000006850 spacer group Chemical group 0.000 description 3
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- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- OYKPJMYWPYIXGG-UHFFFAOYSA-N 2,2-dimethylbutane;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(C)(C)C OYKPJMYWPYIXGG-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- FIOCEWASVZHBTK-UHFFFAOYSA-N 2-[2-(2-oxo-2-phenylacetyl)oxyethoxy]ethyl 2-oxo-2-phenylacetate Chemical compound C=1C=CC=CC=1C(=O)C(=O)OCCOCCOC(=O)C(=O)C1=CC=CC=C1 FIOCEWASVZHBTK-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 244000205754 Colocasia esculenta Species 0.000 description 1
- 235000006481 Colocasia esculenta Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
본 발명은 (A) 기판 상에 광개시제가 포함된 광중합성 모노머 용액을 가하는 단계; (B) 상기 용액 위에 PDMS(polydimethylsiloxane) 커버를 덮는 단계; 및 (C) 상기 PDMS 커버 위로 자외선을 조사하여 광중합성 모노머를 광중합하는 단계;를 포함하여 이루어지는 것을 특징으로 하는 초소수성 표면을 갖는 박막의 형성 방법및 이에 의해 제조된 초소수성 박막에 관한 것이다. (A) a photopolymerizable monomer containing a photoinitiator on a substrate Adding a solution; (B) covering a PDMS (polydimethylsiloxane) cover on the solution; And (C) photopolymerizing the photopolymerizable monomer by irradiating ultraviolet rays onto the PDMS cover. The present invention relates to a method of forming a thin film having a superhydrophobic surface and a superhydrophobic thin film produced thereby.
Description
본 발명은 초소수성 표면을 갖는 박막의 형성 방법 및 이에 의해 제조된 초소수성 박막에 관한 것이다.
The present invention relates to a method of forming a thin film having a super-hydrophobic surface and a super-hydrophobic thin film produced thereby.
초소수성(superhydrophonic) 표면은 물에 친화력을 갖지 않는 표면으로, 특히 표면에 물방울이 접촉했을 때 150° 이상의 높은 접촉각을 갖는 물질로 정의된다. 자연계에서는 연꽃잎이나 토란잎과 같은 많은 식물에서 관찰할 수 있다. 이 같은 표면은 조금만 기울여도 물방울이 미끄러지지 않고 구르면서 표면의 이물질을 제거하는 자가세정효과(self cleaning) 또는 연꽃잎효과(Lotus effect)를 나타낸다. 이와 같은 자가세정효과가 연꽃잎 표면의 10㎛의 큰 돌기 위에 100nm의 작은 돌기가 있는 마이크로/나노 구조가 표면과 물방울의 접촉면을 최소화하는 역할을 하여 초소수성을 갖기 때문임이 밝혀지면서, 이를 일상 생활 및 여러 산업 분야에 응용하고자 하는 연구들이 활발하게 진행되고 있다. 예를 들면, 유기물의 오염이 문제가 되는 냉장고, 휴대폰 등과 같은 전자제품의 외장제나, 습도나 이물질 오염 예방이 필수적인 건축자재에 폭넓게 적용할 수 있다.A superhydrophonic surface is defined as a surface that has no affinity for water, especially a material with a high contact angle of 150 ° or more when water droplets contact the surface. In nature, it can be observed in many plants such as soft petals and taro leaves. Such a surface exhibits a self cleaning or lotus effect that removes foreign matter from the surface while the water droplets do not slip even when tilted a little. It has been found that the micro / nano structure having a small protrusion of 100 nm on the large protrusion of 10 탆 on the surface of the soft petal leaf has the effect of minimizing the contact surface between the surface and the water droplet, And various applications for various industrial fields have been actively conducted. For example, it can be widely applied to exterior materials of electronic products such as refrigerators and mobile phones, where contamination of organic matter is a problem, and building materials in which prevention of humidity and foreign matter contamination is essential.
소수성 표면을 구현하는 방법은 크게 낮은 표면에너지를 가진 재료를 코팅하는 방법과 표면의 기하학적 구조를 변화시켜 표면을 거칠게 만드는 방법으로 나눌 수 있다. 그러나 낮은 표면에너지를 가진 물질을 코팅한다고 하여도 구현할 수 있는 접촉각은 약 120° 정도로 초소수성 표면을 구현하는 데는 한계가 있다. 거친 표면을 갖도록 하는 방법은 높은 접촉각을 얻을 수 있어 많은 연구가 집중되고 있으며, 대표적인 종래의 기술로는 물리적인 구조를 이용하는 소프트리소그래피(softlithography) 기술과 용매의 증발 현상에 따른 고분자의 응집(aggregation) 현상을 응용한 기술이 있다. The hydrophobic surface can be divided into two ways: coating a material with a low surface energy and changing the geometry of the surface to roughen the surface. However, even when a material having a low surface energy is coated, the contact angle that can be realized is about 120 °, which is a limit to realize a superhydrophobic surface. As a result, a high contact angle can be obtained and many researches have been concentrated. Typical conventional techniques include a soft lithography technique using a physical structure and an aggregation of a polymer due to a solvent evaporation phenomenon. There is a technology applying the phenomenon.
소프트리소그래피 기술에 의하면 자연적으로 초소수성 성질을 가지고 있는 표면의 역의 구조를 가지는 고분자 몰드를 형성한다. 다음으로 그 고분자 몰드를 사용하여 연꽃잎과 같은 마이크로/나노 표면 구조를 가지는 고분자 표면을 제조하여 자연을 모방하는 기술이다. 최근에는 이보다 더 발전하여 포토리소그래피(photolithography)를 통하여 원하는 디자인(예를 들어 일정 간격을 가지는 기둥 구조)을 고분자 표면에 구현하여 초소수성의 성질을 나타내도록 하였다. 그러나 이러한 물리적 방법은 표면 처리 과정이 번잡하고, 비용이 높으며, 대면적 처리에는 적합하지 않다는 문제가 있다.According to the soft lithography technique, a polymer mold having an inverse structure of a surface having naturally hydrophobic properties is formed. Next, by using the polymer mold, it is a technology to mimic nature by preparing a polymer surface having micro / nano surface structure such as soft petal leaf. In recent years, it has been further developed to realize a desired design (for example, a columnar structure having a constant interval) through photolithography on the surface of a polymer to exhibit super-hydrophobic properties. However, such a physical method has a problem that the surface treatment process is troublesome, the cost is high, and it is not suitable for large-area treatment.
고분자의 응집을 응용한 기술은 고분자를 용매에 녹인 용액 안에 기판을 침지하여 기판 표면에 용액을 흡착 시킨 후, 용매를 증발시킴으로써 고분자의 석출 과정에서 고분자들끼리 응집이 일어나 초소수성 성질을 갖는 구조를 갖도록 하는 것이다. 하지만 이와 같은 방법들은 다단계의 공정을 필요로 한다. 또한 고분자의 응집현상을 통해 초소수성의 성질을 얻기 위해서는 고분자 용액과 기판과의 젖음성이 좋은 경우로만 국한되므로 적용분야에 한계가 있다.The technique of applying polymer flocculation is to immerse a substrate in a solution in which a polymer is dissolved in a solvent to adsorb a solution on the substrate surface and then evaporate the solvent so that the polymer aggregates between the polymers during the precipitation of the polymer, Respectively. However, these methods require a multi-step process. In addition, in order to obtain super-hydrophobic properties through the agglomeration phenomenon of the polymer, the wettability between the polymer solution and the substrate is limited to only a limited range.
본 발명은 종래기술의 문제점을 해결하기 위하여, 다양한 종류의 기판에 보다 간단한 공정으로 초소수성 표면을 갖는 박막을 형성하는 방법을 제공하고자 하는 것을 목적으로 한다. SUMMARY OF THE INVENTION It is an object of the present invention to provide a method of forming a thin film having a superhydrophobic surface in a simple process on various types of substrates in order to solve the problems of the prior art.
또한 본 발명은 기판의 대면적 처리가 가능한 초소수성 표면을 갖는 박막 형성방법을 제공하는 것을 다른 목적으로 한다.Another object of the present invention is to provide a method of forming a thin film having a super-hydrophobic surface capable of processing a large area of a substrate.
본 발명의 또 다른 목적은 상기 방법에 의해 제조된 초소수성 박막을 제공하는 것이다.
It is still another object of the present invention to provide a superhydrophobic thin film produced by the above method.
전술한 목적을 달성하기 위한 본 발명은 (A) 기판 상에 광개시제가 포함된 광중합성 모노머 용액을 가하는 단계; (B) 상기 용액 위에 PDMS(polydimethylsiloxane) 커버를 덮는 단계; 및 (C) 상기 PDMS 커버 위로 자외선을 조사하여 광중합성 모노머를 광중합하는 단계;를 포함하여 이루어지는 것을 특징으로 하는 초소수성 표면을 갖는 박막의 형성 방법에 관한 것이다.In order to accomplish the above object, the present invention provides a photoresist composition comprising (A) a photopolymerizable monomer Adding a solution; (B) covering a PDMS (polydimethylsiloxane) cover on the solution; And (C) photopolymerizing the photopolymerizable monomer by irradiating UV light onto the PDMS cover. The present invention also relates to a method of forming a thin film having a superhydrophobic surface.
본 발명에서 기판이라 함은 표면에 초소수성 박막을 형성하려는 대상물질로 그 재질에 제한을 받지 않는다. 하기 실시예에서 예시하였듯이, 유리, 고분자, 종이 등과 같은 다양한 물질을 기판으로 사용할 수 있다.The term " substrate " in the present invention is intended to form a super-hydrophobic thin film on the surface of the substrate. As illustrated in the following examples, various materials such as glass, polymer, paper and the like can be used as a substrate.
본 발명에서 광중합성 모노머는 빛의 조사에 의해 광중합이 일어나 고분자를 형성할 수 있는 단량체로서, 하기 실시예에서는 trimethylpropane triacrylate에 대한 데이터만을 구체적으로 기재하였으나, 사전 실험에 의하면 다양한 종류의 광중합성 모노머를 사용하여 초소수성 박막을 형성할 수 있었다. 특히, 모노머 중 아크릴 기를 세 개 이상을 포함하는 Trimethylolpropane triacrylate, Pentaerythritol triacrylate, Trimethylolpropane ethoxylate triacrylate, Glycerol propoxylate (1PO/OH) triacrylate, Trimethylolpropane propoxylate triacrylate, Pentaerythritol propoxylate triacrylate, Di(trimethylolpropane) tetraacrylate, Pentaerythritol tetraacrylate, Dipentaerythritol tetraacrylate, Dipentaerythritol pentaacrylate, Sorbitol pentaacrylate, Dipentaerthritol hexaacrylate, Tripentaerythritol hexacrylate 및 Tripentaerythritol heptaacrylate로 이루어진 군으로부터 선택된 하나 이상의 모노머들은 다른 광중합성 모노머에 비해 더욱 효과적으로 초소수성 박막을 형성하였다.In the present invention, the photopolymerizable monomer is photopolymerized by light irradiation to form a polymer. In the following examples, only data on trimethylpropane triacrylate are specifically described. However, according to a preliminary experiment, various kinds of photopolymerizable monomers A superhydrophobic thin film could be formed. Particularly, it is preferable to use a monomer having three or more acryl groups such as trimethylolpropane triacrylate, Pentaerythritol triacrylate, Trimethylolpropane ethoxylate triacrylate, Glycerol propoxylate (1PO / OH) triacrylate, Trimethylolpropane propoxylate triacrylate, Pentaerythritol propoxylate triacrylate, Di (trimethylolpropane) tetraacrylate, Pentaerythritol tetraacrylate, , Dipentaerythritol pentaacrylate, Sorbitol pentaacrylate, Dipentaerthritol hexaacrylate, Tripentaerythritol hexacrylate and Tripentaerythritol heptaacrylate formed a super-hydrophobic thin film more effectively than other photopolymerizable monomers.
본 발명에서 광개시제란 빛의 조사에 의해 라디칼을 형성하여 광중합을 일으킬 수 있는 물질로서, 통상의 광중합에 사용될 수 있는 광개시제라면 어떤 것이라도 사용할 수 있다. 사전실험에 의하면 광개시제의 종류는 박막의 성질에 영향을 미치지 않았다. 광개시제는 통상의 사용 범위인 1~5 %(v/v)를 사용하는 것이 바람직하나 이에 한정되는 것은 아니며 광개시제의 종류에 따라 적절히 선택할 수 있을 것이다. 광개시제의 예로서는 RGACURE 184, IRGACURE 2959, IRGACURE 500, IRGACURE 754, IRGACURE 651, IRGACURE 369, IRGACURE 907, IRGACURE 1300, IRGACURE 819, IRGACURE 819 DW, IRGACURE 2022, IRGACURE 2100, IRGACURE 784, IRGACURE 250, DAROCUR 1173, DAROCUR MBF, DAROCUR TPO, DAROCUR 4265 등을 들 수 있으나, 이에 한정되는 것이 아님은 당연하다.In the present invention, the photoinitiator is a material capable of forming a radical by irradiation of light to cause photopolymerization, and any photoinitiator that can be used for ordinary photopolymerization can be used. According to the preliminary experiments, the type of photoinitiator did not affect the properties of the thin film. The photoinitiator is preferably used in a usual use range of 1 to 5% (v / v), but is not limited thereto and may be appropriately selected depending on the type of photoinitiator. Examples of photoinitiators include RGACURE 184, IRGACURE 2959, IRGACURE 500, IRGACURE 754, IRGACURE 651, IRGACURE 369, IRGACURE 907, IRGACURE 1300, IRGACURE 819, IRGACURE 819 DW, IRGACURE 2022, IRGACURE 2100, IRGACURE 784, IRGACURE 250, DAROCUR 1173, MBF, DAROCUR TPO, DAROCUR 4265, and the like, but it is not limited thereto.
상기 광중합성 모노머는 용액 중 10~60%(v/v)가 함유되어 있는 것이 바람직하다. 모노머의 함량이 너무 적거나 너무 많은 경우에는, 생성되는 박막이 초소수성을 나타내지 않았다.The photopolymerizable monomer preferably contains 10 to 60% (v / v) of the solution. When the monomer content was too small or too large, the resulting film did not show superhydrophobicity.
상기 광중합성 모노머의 용매로는 모노머를 용해시킬 수 있으면서 끓는점이 120℃이하인 유기용매라면 어떤 것이라도 사용할 수 있다. 대표적인 예로는 C1~C4의 알콜, 아세톤, 아세토니트릴, 벤젠, 2-부타논, 클로로벤젠, 클로로폼, 사이클로핵산, 톨루엔, 1,2-디클로로메탄(DCM), 헵탄 및 헥산을 들 수 있으며 이들 중 광중합 모노머의 종류에 따라 모노머를 용해시킬 수 있는 것을 선택하여 사용할 수 있다. 실시예에는 알콜의 데이터만을 제시하였으나, 사전실험에 의하면 광중합성 모노머를 용해시킬 수 있다면 상기 용매를 사용하는 경우에도 동일하게 초소수석 표면을 갖는 박막이 형성되었다. 본 발명에서 박막 표면의 나노구조는 광중합 과정 시 용매의 증발에 영향을 받기 때문에 용매의 끓는점이 너무 높은 경우에는 나노구조 형성에 영향을 미치므로 초소수성 표면을 갖는 박막이 형성되지 않는다.
As the solvent of the photopolymerizable monomer, any organic solvent which can dissolve the monomer and has a boiling point of 120 ° C or less can be used. Representative examples include C1 to C4 alcohols, acetone, acetonitrile, benzene, 2-butanone, chlorobenzene, chloroform, cyclic nucleic acid, toluene, 1,2-dichloromethane (DCM), heptane and hexane Depending on the kind of the intermediate photopolymerizable monomer, those capable of dissolving the monomer can be selected and used. In the examples, only alcohol data was presented. However, if the photopolymerizable monomer can be dissolved according to a preliminary experiment, a thin film having a superfine surface can be formed even when the solvent is used. In the present invention, since the nanostructure of the thin film surface is affected by the evaporation of the solvent during the photopolymerization process, when the boiling point of the solvent is too high, the thin film having a superhydrophobic surface is not formed because it affects nanostructure formation.
상기 PDMS 커버는 모노머 용액을 사이에 두고 기판과 밀착시키거나 혹은 기판에 스페이서(spacer)를 형성하여 기판과 소정의 간격을 갖도록 하여 덮을 수 있다. 기판과 PDMS 커버를 밀착시킨다고 하여도 기판과 PDMS 커버 사이에는 수십㎛ 두께의 고분자 모노머 용액이 존재하게 되므로 광중합을 통해 박막이 형성되게 된다. 혹은 스페이서를 사용하는 경우에는 보다 정밀하게 고분자 모노머 용액의 두께를 제어할 수 있는 장점이 있다. The PDMS cover may be in close contact with the substrate with a monomer solution therebetween, or may be covered with a spacer at a predetermined interval from the substrate by forming a spacer thereon. Even when the substrate and the PDMS cover are closely contacted, a polymer monomer solution having a thickness of several tens of μm is present between the substrate and the PDMS cover, so that a thin film is formed through photopolymerization. Or when the spacer is used, the thickness of the polymer monomer solution can be controlled more precisely.
PDMS 커버를 덮지 않거나 유리와 같은 기밀성 기판을 커버로 덮고 자외선을 조사하는 경우에는 초소수성 표면이 형성되지 않았다. 이는 광중합 시 PDMS 커버가 용매의 증발을 제어하기 때문인 것으로 판단된다.
When the PDMS cover is not covered or an airtight substrate such as glass is covered with a cover and ultraviolet rays are irradiated, a superhydrophobic surface is not formed. It is considered that PDMS cover controls the evaporation of the solvent during the photopolymerization.
이때 생성되는 박막의 두께는 1~100㎛가 되도록 하는 것이 바람직하다. 박막의 두께가 100㎛ 이상인 경우에는 박막의 표면이 초소수성을 나타내지 않았다.
At this time, the thickness of the thin film to be formed is preferably 1 to 100 mu m. When the thickness of the thin film was 100 mu m or more, the surface of the thin film did not show superhydrophobicity.
본 발명은 또한 상기 방법에 의해 형성된 초소수성 박막에 관한 것이다. 본 발명의 초소수성 박막은 가전제품, 자동차, 건축 내외장재 등 다양한 분야에 적용이 가능하다.
The present invention also relates to a superhydrophobic thin film formed by the above method. The ultra-hydrophobic thin film of the present invention can be applied to various fields such as home appliances, automobiles, interior and exterior materials for buildings.
이상과 같이 본 발명에 의하면 다양한 종류의 기판에 대면적 처리가 가능한 보다 간단한 공정에 의해 초소수성 표면을 갖는 박막을 형성할 수 있다. As described above, according to the present invention, a thin film having a superhydrophobic surface can be formed by a simpler process capable of large-area processing on various kinds of substrates.
상기 방법에 의해 제조된 초소수성 물질은 전자부품 산업, 포장재, 건축 등 다양한 산업 분야에 응용이 가능하다.
The ultra-hydrophobic material produced by the above method can be applied to various industrial fields such as an electronic parts industry, a packaging material, and an architecture.
도 1은 본 발명의 일실시예에 의해 형성된 초소수성 표면을 갖는 박막의 사진.
도 2는 여러 가지 기판 상에 형성된 초소수성 표면을 갖는 박막과 물방울의 접촉 이미지 사진.
도 3은 여러 가지 용매를 사용하여 형성된 초소수성 표면을 갖는 박막의 SEM 이미지 및 물방울과의 접촉 이미지 사진.
도 4는 광중합성 모노머의 농도에 따라 형성된 초소수성 표면을 갖는 박막의 SEM 이미지 사진.
도 5는 광중합성 모노머의 농도에 따라 형성된 초소수성 표면을 갖는 박막의 물방울과의 접촉 이미지 사진.
도 6은 광중합성 모노머 용액 중 에탄올의 함량과 접촉각의 관계를 나타내는 그래프.
도 7은 광중합성 모노머의 농도에 따라 형성된 초소수성 표면을 갖는 박막의 SEM 이미지 및 형광 이미지 사진.
도 8은 광중합성 모노머 용액 중 에탄올 함량과 형광 강도의 관계를 나타내는 그래프.
도 9는 본 발명의 일실시예에 의한 박막의 자가세정효과를 보여주는 사진.1 is a photograph of a thin film having a superhydrophobic surface formed according to an embodiment of the present invention.
FIG. 2 is a contact image of a thin film and a water droplet having a super-hydrophobic surface formed on various substrates. FIG.
FIG. 3 is a SEM image of a thin film having a superhydrophobic surface formed using various solvents, and a contact image photograph with water droplets. FIG.
Figure 4 is a SEM image of a thin film having a superhydrophobic surface formed according to the concentration of the photopolymerizable monomer.
5 is a photograph of a contact image of a thin film having a super-hydrophobic surface formed according to the concentration of the photopolymerizable monomer with water droplets.
6 is a graph showing the relationship between the content of ethanol and the contact angle in the photopolymerizable monomer solution.
7 is an SEM image and a fluorescence image of a thin film having a superhydrophobic surface formed according to the concentration of the photopolymerizable monomer.
8 is a graph showing the relationship between the ethanol content and the fluorescence intensity in the photopolymerizable monomer solution.
9 is a photograph showing a self-cleaning effect of a thin film according to an embodiment of the present invention.
이하 첨부된 실시예를 들어 본 발명을 보다 상세히 설명한다. 그러나 이러한 실시예는 본 발명의 기술적 사상의 내용과 범위를 쉽게 설명하기 위한 예시일 뿐, 이에 의해 본 발명의 기술적 범위가 한정되거나 변경되는 것은 아니다. 또한 이러한 예시에 기초하여 본 발명의 기술적 사상의 범위 안에서 다양한 변형과 변경이 가능함은 당업자에게는 당연할 것이다.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these embodiments are merely examples for explaining the content and scope of the technical idea of the present invention, and thus the technical scope of the present invention is not limited or changed. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea of the present invention based on these examples.
실시예 1 : 초소수성 표면을 갖는 박막의 형성Example 1: Formation of a thin film having a superhydrophobic surface
5% (v/v) Darocur 1173을 광개시제로 함유한 30% (v/v) TMPTA(Trimethylolpropane triacrylate) 용액 200㎕를 기판위에 떨어뜨린 후 PDMS 커버로 덮어주었다. 상기 용액의 용매로는 에탄올, 메탄올 또는 이소프로판올을 사용하였다. 이후, 365nm의 자외선을 PDMS 커버 상에서 30분간 조사하여 TMPTA의 광중합에 의해 형성된 초소수성 필름을 얻었다. 도 1의 상기 방법에 의해 형성된 초소수성 필름의 사진이다.
200 μl of a 30% (v / v) TMPTA (Trimethylolpropane triacrylate) solution containing 5% (v / v) Darocur 1173 as a photoinitiator was dropped onto the substrate and covered with a PDMS cover. As the solvent of the solution, Ethanol, methanol or isopropanol was used. Ultraviolet rays of 365 nm were then irradiated on the PDMS cover for 30 minutes to obtain a superhydrophobic film formed by photopolymerization of TMPTA. 1 is a photograph of a superhydrophobic film formed by the method of FIG.
실시예 2 : 박막의 표면 특성의 관측Example 2: Observation of surface properties of thin films
1) 기판 종류에 따른 박막의 표면 특성1) Surface properties of thin films according to substrate type
에탄올을 용매로 사용한 TMPTA 용액을 사용하여 실시예 1의 방법에 의해 다양한 기판(유리, PDMS 고분자, PET 필름, 종이 (A4 용지), 페트리 디쉬)에 박막을 형성하였다. 형성된 박막이 초소수성 표면을 갖는 지 확인하기 위하여 상기 표면위에 물 4㎕를 떨어뜨려 물방울을 형성시킨 후, pendant drop method(optical tensiometer, KSV Instruments, Finland)를 사용하여 접촉각을 측정하였다. 도 2는 각 기판에 형성된 박막과 물방울의 접촉 이미지 사진이다. 도 2에서 확인할 수 있듯이, 모든 기판에 형성된 박막에 대해 물방울과의 접촉각은 153~168ㅀ로 상기 박막의 표면들은 초소수성을 나타내었다.
A thin film was formed on various substrates (glass, PDMS polymer, PET film, paper (A4 paper), Petri dish) by the method of Example 1 using a TMPTA solution using ethanol as a solvent. To confirm that the formed thin film had a super-hydrophobic surface, 4 물 of water was dropped on the surface to form water droplets, and contact angle was measured using a pendant drop method (optical tensiometer, KSV Instruments, Finland). 2 is a contact image of a thin film formed on each substrate and water droplets. As can be seen from FIG. 2, the contact angle of water droplets with respect to the thin film formed on all the substrates was From 153 to 168 ㅀ, the surfaces of the films showed superhydrophobicity.
2) TMPTA 용액의 용매 종류에 따른 박막의 표면 특성2) Surface properties of thin films depending on solvent type of TMPTA solution
TMPTA의 용매로 에탄올, 이소프로판올 또는 메탄올을 사용하여 실시예 1의 방법에 따라 유리기판 상에 박막을 형성하고, 1)의 방법에 의해 물방울에 대한 표면 접촉각을 측정하였다. 상기 방법에 의해 형성된 박막의 물방울 접촉 이미지 사진과 SEM 이미지 사진을 도 3에 도시하였다. 에탄올 뿐 아니라 이소프로판올이나 메탄올을 사용한 경우 역시 접촉각이 150° 이상으로 초소수성 표면 특성을 나타내며, SEM 이미지로부터 상기표면에 나노 구조물이 형성되어 있음을 알 수 있다. 용매에 따라서는 끓는 점이 높을수록, 표면에 형성된 나노구조물의 크기가 더 작았다.
A thin film was formed on a glass substrate according to the method of Example 1 using ethanol, isopropanol or methanol as a solvent of TMPTA, and the surface contact angle with respect to water droplets was measured by the method 1). A water droplet contact image and a SEM image of the thin film formed by the above method are shown in FIG. In the case of using isopropanol or methanol as well as ethanol, the contact angle was also 150 ° or more, indicating superhydrophobic surface characteristics. From the SEM image, it can be seen that nanostructures were formed on the surface. The higher the boiling point, the smaller the size of the nanostructures formed on the surface, depending on the solvent.
3) 용액 중 TMPTA 농도에 따른 박막의 표면 특성3) Surface properties of thin films with TMPTA concentration in solution
에탄올을 용매로 사용하여 여러 가지 농도의 TMPTA 용액에 대해 역시 실시예 1의 방법에 따라 유리기판 상에 박막을 형성하고, 2)의 방법에 의해 물방울에 대한 SEM 이미지와 표면 접촉각을 측정하여 그 결과를 도 4와 5에 각각 도시하였다. 또한 TMPTA 용액 중 에탄올의 함량과 접촉각의 관계를 그래프로 도시하여 도 6에 나타내었다. 도 4 내지 도 6에서 에탄올의 농도는 용액 중 에탄올과 TMPTA 부피의 합에 대한 에탄올의 부피 비를 나타내는 것이다. 도 4의 SEM 이미지에 의하면 10% 에탄올 용액의 경우에는 표면이 매끄럽고 평탄하였으나, 에탄올 함량이 증가하면 표면이 거칠어져 30~40% 에탄올의 경우 표면에 구조물이 형성되기 시작하였다. 에탄올 함량이 50% 이상이 되면 마이크로 및 나노 구조물이 형성되는 것을 뚜렷히 확인할 수 있었다. 이를 도 5 및 도 6의 접촉각과 매칭시키면, 표면이 거칠어질수록 접촉각이 증가하며, 마이크로 및 나노 구조물 형성이 뚜렷한 40%~90% 에탄올에서 박막의 표면이 초소수성을 나타내었다. 이로부터, 자연계 초소수성 물질과 마찬가지로 박막 표면의 마이크로 및 나노 구조물이 초소수성의 원인이 되며, 광중합성 모노머의 농도에 따라 표면 구조가 영향을 받음을 알 수 있었다.
Ethanol was used as a solvent to form a thin film on a glass substrate according to the method of Example 1 for various concentrations of TMPTA solution and the SEM image and surface contact angle of the water droplet were measured by the method 2) 4 and 5, respectively. FIG. 6 is a graph showing the relationship between the content of ethanol and the contact angle in the TMPTA solution. In FIGS. 4 to 6, the concentration of ethanol represents the volume ratio of ethanol to the sum of the ethanol and the TMPTA volume in the solution. According to the SEM image of FIG. 4, the surface was smooth and flat in the case of the 10% ethanol solution, but the surface became rough when the ethanol content was increased, and the structure started to form on the surface in the case of 30 ~ 40% ethanol. When the ethanol content was more than 50%, it was confirmed that micro and nanostructures were formed. When this was matched with the contact angles of FIGS. 5 and 6, the contact angle increased as the surface became coarse, and the surface of the thin film showed superhydrophobicity at 40% to 90% ethanol where micro and nano structure formation was remarkable. From these results, it can be seen that micro- and nano-structures on the surface of the thin film cause superficial hydrophobicity, and the surface structure is influenced by the concentration of the photopolymerizable monomer.
박막 표면에 형성된 나노 구조물을 형광에 의해 간접적으로 측정하였다. 먼저 포토리소그래피(photolithography)를 통해 기판 상에 10㎛ 깊이의 line pattern을 형성한 후, 기판 위에 PDMS 고분자를 부어 line pattern을 갖는 PDMS 몰드를 제조하였다. line pattern이 형성된 면 위에 유리를 올려놓고 압력을 가하여 부착시켜 유리와 PDMS 고분자 사이에 직사각형의 채널이 형성되도록 하였다. 상기 채널의 한쪽 끝부분에 5% (v/v) Darocur 1173을 광개시제로 함유한 TMPTA(Trimethylolpropane triacrylate)의 에탄올 용액을 떨어뜨리면 모세관 현상에 의해 상기 용액이 채널 안으로 빨려 들어간다. 채널이 상기 용액으로 채워지면 365nm 자외선을 30분간 조사하여 line pattern의 박막을 제조하였다. 제조된 박막을 형광 현미경(NIKON, TE2000, Japan)을 사용하여 형광 이미지를 측정하고 SEM 이미지와 함께 도 7에 도시하였으며, 도 8에 그래프로 나타내었다. 도 7로부터 에탄올 함량이 증가함에 따라 형광 강도가 증가하여 나노 구조물이 증가함을 알 수 있다.
The nanostructures formed on the thin film surface were indirectly measured by fluorescence. First, a 10 μm depth line pattern was formed on the substrate by photolithography. PDMS molds with a line pattern were prepared by pouring the PDMS polymer onto the substrate. The glass plate was placed on the surface where the line pattern was formed and pressure was applied to form a rectangular channel between the glass and the PDMS polymer. When the ethanol solution of TMPTA (Trimethylolpropane triacrylate) containing 5% (v / v) Darocur 1173 as a photoinitiator is dropped on one end of the channel, the solution is sucked into the channel by capillary phenomenon. When the channel was filled with the solution, a line pattern thin film was prepared by irradiating with ultraviolet rays of 365 nm for 30 minutes. The prepared thin film was measured for fluorescence image using a fluorescence microscope (NIKON, TE2000, Japan) and is shown in Fig. 7 together with SEM image, and is shown graphically in Fig. From FIG. 7, it can be seen that as the ethanol content increases, the fluorescence intensity increases and the number of nanostructures increases.
3) 자가세정효과 관측3) Self-cleaning effect observation
에탄올을 용매로 실시예 1의 방법에 의해 유리기판 상에 형성된 초소소성 표면을 갖는 박막이 자가세정효과를 나타내는 지 다음 실험에 의해 확인하고 그 과정 사진을 도 9에 도시하였다.Ethanol was used as a solvent to confirm that the thin film having the micro-plastic surface formed on the glass substrate by the method of Example 1 exhibits self-cleaning effect, and a photograph of the process is shown in Fig.
먼저 상기 박막 위에 커피 믹스를 뿌리고 물방울을 떨어뜨렸다. 물방울은 박막 표면과는 상호작용 없이 커피믹스의 알갱이만을 용해하여 커피 방울이 형성되어 자가세정효과를 나타냄을 확인할 수 있었다.First, a coffee mix was sprinkled on the thin film and water drops were dropped. It was confirmed that the water droplets dissolve only the particles of the coffee mix without interaction with the thin film surface, forming coffee bubbles and exhibiting self-cleaning effect.
Claims (6)
(B) 상기 용액 위에 PDMS(polydimethylsiloxane) 커버를 덮는 단계; 및
(C) 상기 PDMS 커버 위로 자외선을 조사하여 광중합성 모노머를 광중합하는 단계;
를 포함하여 이루어지는 것을 특징으로 하는 초소수성 표면을 갖는 박막의 형성 방법.
(A) a method for preparing a photoresist composition comprising a substrate and a photoinitiator, wherein the photoinitiator is selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane ethoxylate triacrylate, glycerol propoxylate (1PO / OH) triacrylate, trimethylolpropane propoxylate triacrylate, pentaerythritol propoxylate triacrylate, Adding a solution of at least one photopolymerizable monomer selected from the group consisting of Dipentaerythritol pentaacrylate, Sorbitol pentaacrylate, Dipentaerthritol hexaacrylate, Tripentaerythritol hexacrylate and Tripentaerythritol heptaacrylate;
(B) covering a PDMS (polydimethylsiloxane) cover on the solution; And
(C) photopolymerizing the photopolymerizable monomer by irradiating UV light onto the PDMS cover;
Wherein the thin film has a superhydrophobic surface.
상기 광중합성 모노머 용액 중 광중합성 모노머의 함량은 10~60%(v/v)인 것을 특징으로 하는 초소수성 표면을 갖는 박막의 형성 방법.
The method according to claim 1,
Wherein the content of the photopolymerizable monomer in the photopolymerizable monomer solution is 10 to 60% (v / v).
상기 광중합성 모노머 용액의 용매는 C1~C4의 알콜, 아세톤, 아세토니트릴, 벤젠, 2-부타논, 클로로벤젠, 클로로폼, 사이클로핵산, 톨루엔, 1,2-디클로로메탄(DCM), 헵탄 및 헥산으로 구성된 군으로부터 선택된 하나 이상인 것을 특징으로 하는 초소수성 표면을 갖는 박막의 형성 방법.
The method according to claim 1,
The solvent of the photopolymerizable monomer solution may be selected from the group consisting of C1 to C4 alcohols, acetone, acetonitrile, benzene, 2-butanone, chlorobenzene, chloroform, cyclic nucleic acid, toluene, 1,2-dichloromethane (DCM) Wherein the hydrophobic surface is at least one selected from the group consisting of:
상기 박막의 두께는 1~100 ㎛인 것을 특징으로 하는 초소수성 표면을 갖는 박막의 형성 방법.The method according to claim 1,
The thickness of the thin film is 1 to 100 m. ≪ / RTI >
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| US4224398A (en) | 1979-05-29 | 1980-09-23 | Richardson Graphics Company | Photopolymerizable latex systems |
| US20070238051A1 (en) | 2006-04-10 | 2007-10-11 | Lg Philips Lcd Co., Ltd | Blanket for a printing roll, method of manufacturing the same, patterning method using the same, and method of manufacturing liquid crystal display device |
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