KR101514370B1 - Manufacturing method of water-repellent emulsion - Google Patents
Manufacturing method of water-repellent emulsion Download PDFInfo
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- KR101514370B1 KR101514370B1 KR1020140097432A KR20140097432A KR101514370B1 KR 101514370 B1 KR101514370 B1 KR 101514370B1 KR 1020140097432 A KR1020140097432 A KR 1020140097432A KR 20140097432 A KR20140097432 A KR 20140097432A KR 101514370 B1 KR101514370 B1 KR 101514370B1
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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Abstract
Description
본 발명은 친환경적이며 인체 안전성이 높은 발수발유제의 제조방법에 관한 것이다.The present invention relates to a process for producing a water-repellent oil-repellent agent which is environmentally friendly and highly safe to human body.
발수제는 섬유뿐만 아니라, 제지, 전파, 피혁, 건축 등의 여러 산업분야에서 광범위하게 사용되고 있으며, 다양한 기능성 신소재 개발에 따라 발수제의 용도 역시 다양하게 성장하고 있다.Water repellent agents are widely used not only in fibers but also in various industrial fields such as paper, radio wave, leather, and construction, and the use of water repellent agents is also growing in accordance with the development of various functional new materials.
소수성 기능을 발현하는 발수제의 국내시장은 약 3,300억 정도의 시장을 형성하고 있으며, 세계시장은 국내 시장의 20배 이상으로 추정되고 있다. 이러한 발수제의 종류는 섬유 분야에서는 불소계발수제가 주류를 이루고 있으며, 건축 분야에서는 불소, 실리카, 왁스가 단독으로 사용되거나, 불소/실리카/왁스의 혼합 에멀젼 타입이 사용되고 있다.The domestic market of water repellent agent that expresses hydrophobic function forms about 330 billion market and the global market is estimated to be more than 20 times of domestic market. In the field of construction, fluorine, silica and wax are used singly or mixed emulsion type of fluorine / silica / wax is used in the field of construction.
그 중 퍼플루오로알킬(Perfluoroalkyl)기를 함유하는 불소화합물을 이용한 불소계발수제는 섬유 및 제지등 각종 기재표면에 발수성, 발유성, 내수성 및 방오성등 다양한 기능을 부여하는 표면개질제로 전 세계에서 널리 사용되고 있다.Among them, a fluorine-based water repellent agent using a fluorine compound containing a perfluoroalkyl group is widely used in the world as a surface modifier imparting various functions such as water repellency, oil repellency, water resistance and antifouling property to various substrate surfaces such as fiber and paper .
그러나, 퍼플루오로알킬(Perfluoroalkyl)기를 함유하는 화합물이 독성을 나타내어 인체 안정성 및 환경에 문제를 유발시킬 수 있다는 연구 결과가 보고되었다. 또한, 현재 사용되고 있는 C8 불소계발수발유제에서 인체에 유해한 미량의 PFOA(perfluorooctanoic acid: C8F15COOH) 및 PFOS(perfluorooctantanesulfonic acid : C8F17SO3H)와 같은 화학물질들이 검출되었다. PFOA 및 PFOS는 인체 내에 축적되고 분해되어 신체 밖으로 배출되는데 3.80 ~ 4.37년이 소요되는 화학 물질들로, 미국 환경보호청(EPA)에서는 C8 화합물의 확산방지를 위해 C8 화합물의 사용을 금지시켰으며, 전세계적으로 친환경적이며 인체에 안전한 발수제 개발을 위한 연구를 진행하고 있다.However, it has been reported that a compound containing a perfluoroalkyl group is toxic and can cause human stability and environmental problems. In addition, chemicals such as PFOA (perfluorooctanoic acid: C 8 F 15 COOH) and PFOS (perfluorooctanethanesulfonic acid: C 8 F 17 SO 3 H), which are harmful to human body, have been detected in the currently used C8 fluoride- PFOA and PFOS are chemicals that accumulate in the body and are decomposed and released outside the body, requiring 3.80 to 4.37 years. The US Environmental Protection Agency (EPA) has banned the use of C8 compounds to prevent the spread of C8 compounds. We are working on the development of environmentally friendly and safe water repellent in the world.
그럼에도 불구하고 현재까지는 기존의 발수제보다 친환경적이고 안전하며 기존 발수제의 성능을 나타낼 수 있는 친환경 발수발유제 개발은 이루어지고 있지 못한 실정이다. Nonetheless, the development of eco-friendly water-repellent agents that are more environmentally friendly and safe than conventional water-repellent agents and that can demonstrate the performance of conventional water-repellent agents has not been developed.
환경 및 인체에 유해한 독성물질인 PFOA 및 PFOS를 방출하는 퍼플루오로알킬(Perfluoroalkyl)기를 함유하는 불소계 C8 발수발유제의 문제점을 해결하기 위해, 본 발명은 PFOA 동족체로 탄소수가 2개 감소된 C6의 불소화합물과 왁스 유압 에멀젼으로 제조하여 친환경적인 발수발유제를 제공하고자 한다.In order to solve the problems of fluorine-based C8 water-repellent emulsions containing perfluoroalkyl groups releasing PFOA and PFOS which are poisonous substances harmful to the environment and human body, the present invention relates to PFOA homologues of C6 And to provide an environmentally friendly water-repellent oil-repellent agent made of a fluorine compound and a wax hydraulic emulsion.
본 발명은 과불소알킬아크릴레이트 단량체 및 아크릴레이트 단량체를 계면활성제가 포함된 분산용액에 첨가한 후 교반하여 불소가 포함된 발수제를 제조하는 단계; 왁스를 계면활성제가 포함된 분산용액에 첨가하고 교반하여 왁스발수제를 제조하는 단계; 및 상기 불소가 포함된 발수제 및 왁스발수제를 혼합하는 단계를 포함하는 것을 특징으로 하는 발수발유제 제조방법을 제공한다.The present invention relates to a method for preparing a fluorine-containing water-repellent agent, comprising: adding a perfluoroalkyl acrylate monomer and an acrylate monomer to a dispersion solution containing a surfactant; Adding a wax to a dispersion solution containing a surfactant and stirring to prepare a wax water repellent agent; And a step of mixing the fluorine-containing water repellent agent and the wax water repellent agent.
본 발명에 따르면, 탄소수 6 이하의 불소 단량체 공중합체 및 왁스 에멀젼 공중합체를 혼합하여 제조된 발수발유제는 발수발유성, 내구성, 유연성 및 통기성을 나타내는 기능성 발수발유제로, 본 발명의 탄소수 6 이하의 저탄소 불소를 함유하는 아크릴계 불소화합물을 이용한 발수발유제는 기존의 C8 발수발유제에서 검출되었던 PFOA 및 PFOS가 검출되지 않았으며, 인체 내 PFOA 및 PFOS 반감기를 1/100로 감소시킬 수 있어, 인체 안전성을 10배 수준으로 향상시킬 수 있다.According to the present invention, a water and oil-repellent agent produced by mixing a fluorine monomer copolymer having a carbon number of 6 or less and a wax emulsion copolymer is a functional water and oil repellent agent exhibiting water and oil repellency, durability, flexibility and permeability, , The PFOA and PFOS detected in the conventional C8 water-based oil-and-oil emulsion were not detected and the PFOA and PFOS half-life in the human body could be reduced to 1/100, The safety can be improved to 10 times.
따라서, 본 발명에 따른 발수발유제는 C8의 불소계 발수발유제를 대신하여 사용가능한 친환경적 발수발유제로 사용될 수 있다.Therefore, the water and oil repellent agent according to the present invention can be used as an eco-friendly water and oil repellent agent which can be used instead of the C8 fluorinated water and oil repellent agent.
도 1은 본 발명에 따라 제조된 발수발유제 용액 및 발수형태를 확인한 결과이다.FIG. 1 shows the result of confirming the water and oil repellent solution and the water repellent form prepared according to the present invention.
본 발명은 과불소알킬아크릴레이트 단량체 및 아크릴레이트 단량체를 계면활성제가 포함된 분산용액에 첨가한 후 교반하여 불소가 포함된 발수제를 제조하는 단계; 왁스를 계면활성제가 포함된 분산용액에 첨가하고 교반하여 왁스발수제를 제조하는 단계; 및 상기 불소가 포함된 발수제 및 왁스발수제를 혼합하는 단계를 포함하는 것을 특징으로 하는 발수발유제 제조방법을 제공한다. The present invention relates to a method for preparing a fluorine-containing water-repellent agent, comprising: adding a perfluoroalkyl acrylate monomer and an acrylate monomer to a dispersion solution containing a surfactant; Adding a wax to a dispersion solution containing a surfactant and stirring to prepare a wax water repellent agent; And a step of mixing the fluorine-containing water repellent agent and the wax water repellent agent.
본 발명의 구체예에서, 불소가 포함된 발수제에 사용되는 과불소알킬아크릴레이트 단량체는 1 내지 6개의 탄소원자를 갖는 것이 사용될 수 있으며, 예로는 퍼풀루오로부탄설포닉산(C4F9SO3H), 퍼풀루오르헥사노헥사노익산(C5F11CO2H), 퍼풀루오르헥산설포네이트(C6F13SO3H), 폴리헵타풀루오르부틸아크릴레이트, 폴리펜타풀루오르프로필아크릴레이트, 폴리헥사풀루오르프로필아크릴레이트 및 폴리트리풀루오르에틸아크릴레이트로 이루어진 군에서 하나 또는 둘 이상 선택되어 30 내지 70 중량부로 사용될 수 있으며, 보다 바람직하게는 폴리펜타풀루오르프로필아크릴레이트, 폴리헥사풀루오르프로필아크릴레이트, 퍼풀루오르헥사노헥사노익산, 폴리헵타풀루오르부틸아크릴레이트 및 폴리트리풀루오르에틸아크릴레이트일 수 있으나, 이에 한정되지는 않는다.In embodiments of the present invention, the perfluoroalkyl acrylate monomers used in the fluorine-containing water repellent agent may be those having 1 to 6 carbon atoms, such as perfluorobutanesulfonic acid (C 4 F 9 SO 3 H ), Perfluorooctanohexanohexanoic acid (C 5 F 11 CO 2 H), perfluorooctane sulfonate (C 6 F 13 SO 3 H), polyheptafluorobutyl acrylate, polypentafluoropropoxyacrylate And may be used in an amount of 30 to 70 parts by weight, and more preferably polypentafluoropropyl acrylate, polyhexafluoropropyl acrylate, polytetrafluoroethyl acrylate, Perfluorooctyl acrylate, perfluorooctyl acrylate, perfluorooctyl acrylate, perfluorooctyl acrylate, perfluorooctyl acrylate, perfluoro propyl acrylate, perfluoroohexanohexanoic acid, polyheptafluorobutyl acrylate and polytripuluryl ethyl acrylate. It does that.
또한 상기 아크릴레이트 단량체는 불포화 이중결합을 갖는 것이 사용될 수 있으며, 예로는 메틸아크릴레이트, 에틸아크릴레이트, 라우릴아크릴레이트 및 스테아릴아크릴레이트로 이루어진 군에서 하나 또는 둘 이상 선택되어, 10 내지 50 중량부로 사용될 수 있으며, 보다 바람직하게는 에틸아크릴레이트일 수 있으나, 이에 한정되지는 않는다. The acrylate monomer may have an unsaturated double bond. Examples of the acrylate monomer include one or more selected from the group consisting of methyl acrylate, ethyl acrylate, lauryl acrylate and stearyl acrylate, And more preferably ethyl acrylate, but is not limited thereto.
상기 불소가 포함된 발수제에 사용되는 분산용액은 물; 및 메틸알코올, 에틸알코올, 이소프로필알코올, N-부탄올 및 N-부틸알코올로 이루어진 군에서 선택된 어느 하나 또는 둘 이상의 알코올의 혼합용액으로, 보다 바람직하게는 상기 분산용액은 물 30 내지 90 중량부 및 알코올 10 내지 70 중량부가 첨가된 혼합용액일 수 있으나, 이에 한정되지는 않는다.The dispersion solution used in the fluorine-containing water repellent agent is water; And a mixed solution of any one or two or more alcohols selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, N-butanol and N-butyl alcohol, more preferably, the dispersion solution comprises 30 to 90 parts by weight of water, And 10 to 70 parts by weight of alcohol may be added, but the present invention is not limited thereto.
본 발명의 다른 구체예에서, 왁스발수제에 사용되는 왁스는 이소파라핀, 노르말파라핀, 폴리올레핀왁스, 폴리에틸렌왁스, 칸델릴라왁스, 솔루블라이저왁스, 세레신왁스 및 카나우바왁스로 이루어진 군에서 하나 또는 둘 이상 선택될 수 있으며, 보다 바람직하게는 폴리에틸렌왁스일 수 있으나, 이에 한정되지는 않는다.In another embodiment of the present invention, the wax used in the wax water repellent agent is one or two or more selected from the group consisting of isoparaffin, normal paraffin, polyolefin wax, polyethylene wax, candelilla wax, solubilized wax, ceresin wax and carnauba wax And more preferably polyethylene wax, but is not limited thereto.
또한 왁스발수제에 사용되는 분산용액은 노르말핵산, 1,6-헥산디올, 1-헥산올, 메틸알코올, 에틸알코올, 노르말프로필알코올, 이소-프로필알코올, 노르말부틸알코올, 이소-부틸알코올, 에틸렌글리콜, N,N-디메틸포름아마이드, 아세틸아세톤, 케톤, 에테르, 디에틸렌글리콜 및 모노부틸에테르로 이루어진 군에서 하나 또는 둘 이상 선택되어 10 내지 30 중량부로 사용될 수 있으며, 보다 바람직하게는 노르말헥산 및 이소프로필알코올로 이루어진 혼합 분산용액일 수 있으나, 이에 한정되지는 않는다.Also, the dispersion solution used in the wax water repellent agent may be at least one selected from the group consisting of normal nucleic acids, 1,6-hexanediol, 1-hexanol, methyl alcohol, ethyl alcohol, normal propyl alcohol, iso-propyl alcohol, normal butyl alcohol, isobutyl alcohol, , N, N-dimethylformamide, acetylacetone, ketone, ether, diethylene glycol and monobutyl ether, and more preferably from 10 to 30 parts by weight, more preferably from normal hexane and iso Propyl alcohol, but is not limited thereto.
상기 분산용액에 포함되는 계면활성제는 비이온계면활성제로 폴리에틸렌글리콜메틸에테르, 폴리옥시에틸렌옥틸페닐에테르, 폴리옥시에틸렌소르비탄모노라우레이트, 소디움라우릴설페이트, 소디움도데실설페이트 및 소르비탄모노올레이트로 이루어진 군에서 하나 또는 둘 이상 선택될 수 있으며, 10 내지 50 중량부로 사용될 수 있으나, 이에 한정되지는 않는다.The surfactant contained in the dispersion solution may be selected from nonionic surfactants such as polyethylene glycol methyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene sorbitan monolaurate, sodium lauryl sulfate, sodium dodecyl sulfate and sorbitan monooleate And may be used in an amount of 10 to 50 parts by weight, but is not limited thereto.
상기 불소가 포함된 발수제 또는 왁스발수제 공중합체에 사용되는 단량체의 반응 결합을 진행시키기 위해서 단량체가 균일하게 해리되도록 사용되는 개시제는 열 개시제이며, 예로는 아조비스아이소부티로나이트릴, 벤조일 퍼옥사이드, 아세틸 퍼 옥사이드, 라우릴퍼오사이드, t-부틸 퍼옥사이드, t-부틸 하이드록시 퍼옥사이드 및 큐밀퍼옥사이드로 이루어진 군에서 하나 또는 둘 이상을 선택되어 1 내지 10 중량부로 첨가될 수 있으나, 이에 한정되지는 않는다. 또한 용액의 저장 안정성을 높이기 위해 폴리비닐 알코올, 폴리에틸렌글리콜, 폴리프로필렌글리콜 또는 폴리비닐피롤리돈를 1 내지 10 중량부로 추가로 첨가할 수 있으나, 이에 한정되지는 않는다. The initiator used to uniformly dissociate the monomer to promote the reaction of the monomer used in the fluorine-containing water repellent agent or the wax-water repellent copolymer is a thermal initiator, and examples thereof include azobisisobutyronitrile, benzoyl peroxide, One or more selected from the group consisting of acetyl peroxide, lauryl peroxide, t-butyl peroxide, t-butyl hydroxy peroxide and cumyl peroxide may be added and added in an amount of 1 to 10 parts by weight, . In order to improve the storage stability of the solution, polyvinyl alcohol, polyethylene glycol, polypropylene glycol or polyvinylpyrrolidone may be added in an amount of 1 to 10 parts by weight, but not limited thereto.
본 발명의 또 다른 구체예에서, 상기 불소가 포함된 발수제를 제조하는 단계는 65 내지 80℃에서 4 내지 5시간 동안 교반하는 단계를 포함할 수 있다.In another embodiment of the present invention, the step of preparing the fluorine-containing water repellent agent may include stirring at 65 to 80 DEG C for 4 to 5 hours.
또한 상기 왁스발수제를 제조하는 단계는 60 내지 70℃에서 4 내지 5시간 동안 교반하는 단계를 포함할 수 있다.The step of preparing the wax water repellent agent may include stirring at 60 to 70 DEG C for 4 to 5 hours.
또한 상기 불소가 포함된 발수제 및 왁스발수제를 혼합하는 단계는 불소가 포함된 발수제 100 중량부에 대하여 왁스발수제를 20 내지 40 중량부로 혼합할 수있다.The step of mixing the fluorine-containing water repellent agent and the wax water repellent agent may include mixing the wax water repellent agent in an amount of 20 to 40 parts by weight with respect to 100 parts by weight of the fluorine-containing water repellent agent.
상기 불소가 포함된 발수제 및 왁스발수제의 혼합 범위를 벗어나게 되면 발수도가 약해지는 문제점이 야기될 수 있다.
If the mixing range of the fluorine-containing water-repellent agent and the wax water-repellent agent is out of the range, the water-repellency may become weak.
이하, 본 발명의 이해를 돕기 위하여 실시예를 들어 상세하게 설명하기로 한다. 다만 하기의 실시예는 본 발명의 내용을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다. 본 발명의 실시예는 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해 제공되는 것이다.BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are intended to illustrate the contents of the present invention, but the scope of the present invention is not limited to the following examples. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.
<< 실시예Example 1> 1> 실시예Example 1 제조 1 Manufacturing
반응용기에 이소프로필알콜올 45g, 증류수 135g 및 계면활성제인 폴리옥시에틸렌소르비탄모노라우레이트 20g을 가한 후 교반하면서 에틸아크릴레이트 30g 및 폴리펜타풀루오르프로필아크릴레이트 45g을 서서히 첨가하였다.45 g of isopropyl alcohol, 135 g of distilled water and 20 g of polyoxyethylene sorbitan monolaurate as a surfactant were added to the reaction vessel, and then 30 g of ethyl acrylate and 45 g of polypentafluoropropylacrylate were gradually added while stirring.
그 다음 개시제로 벤조일 퍼옥사이드 4g을 가하고 65 내지 80℃ 온도에서 4 내지 5시간 동안 충분하게 교반하여 공중합체한 1차 발수제를 제조하였다.Next, 4 g of benzoyl peroxide was added as an initiator and the mixture was thoroughly stirred at a temperature of 65 to 80 ° C for 4 to 5 hours to prepare a copolymerized primary water repellent.
다른 반응용기에 폴리에틸렌왁스 25g, 노르말헥산 35g 및 이소프로필알코올 65g을 가하고 계면활성제로 폴리옥시에틸렌소르비탄모노라우레이트 25g, 증류수 70g 및 소포제 3g을 첨가하여 60 내지 75℃ 온도에서 4 내지 5시간 동안 충분하게 교반하여 2차 왁스 발수제를 제조하였다.To another reaction vessel, 25 g of polyethylene wax, 35 g of n-hexane and 65 g of isopropyl alcohol were added, and 25 g of polyoxyethylene sorbitan monolaurate as a surfactant, 70 g of distilled water and 3 g of defoamer were added and heated at 60 to 75 ° C for 4 to 5 hours And sufficiently stirred to prepare a secondary wax water repellent agent.
그 후 1차 발수제 반응용기에 2차 왁스 발수제를 70:30 (1차 발수제:2차 왁스 발수제) 중량비로 서서히 첨가하면서 3 내지 4시간 동안 교반한 후 분산제 및 결합제를 각각 3g씩 첨가하여 최종적으로 균일한 친환경 발수제를 제조하였다.Thereafter, a second water-repellent agent was added to the reaction vessel of the first water-repellent agent gradually at a weight ratio of 70:30 (primary water-repellent agent: second water-repellent agent) to the reaction vessel for 3 to 4 hours and then 3 g of dispersant and binder were added thereto A uniform environmentally friendly water repellent agent was prepared.
<< 실시예Example 2> 2> 실시예Example 2 제조 2 Manufacturing
반응용기에 이소프로필알코올 45g, 증류수 135g 및 계면활성제인 폴리옥시에틸렌소르비탄모노라우레이트 20g을 가한 후 교반하면서 에틸아크릴레이트 30g 및 폴리헥사풀루오르프로필아크릴레이트 45g을 서서히 첨가하였다.45 g of isopropyl alcohol, 135 g of distilled water and 20 g of polyoxyethylene sorbitan monolaurate as a surfactant were added to the reaction vessel, and 30 g of ethyl acrylate and 45 g of polyhexafluoropropylacrylate were gradually added while stirring.
그 다음 개시제로 벤조일 퍼옥사이드 4g을 가하고 65 내지 80℃ 온도에서 4 내지 5시간 동안 충분하게 교반하여 공중합체한 1차 발수제를 제조하였다.Next, 4 g of benzoyl peroxide was added as an initiator and the mixture was thoroughly stirred at a temperature of 65 to 80 ° C for 4 to 5 hours to prepare a copolymerized primary water repellent.
다른 반응용기에 폴리에틸렌왁스 25g, 노르말헥산 35g 및 이소프로필알코올 65g을 가하고 계면활성제로 폴리옥시에틸렌소르비탄모노라우레이트 25g, 증류수 70g 및 소포제 3g을 첨가하여 60 내지 75℃ 온도에서 4 내지 5시간 동안 충분하게 교반하여 2차 왁스 발수제를 제조하였다.To another reaction vessel, 25 g of polyethylene wax, 35 g of n-hexane and 65 g of isopropyl alcohol were added, and 25 g of polyoxyethylene sorbitan monolaurate as a surfactant, 70 g of distilled water and 3 g of defoamer were added and heated at 60 to 75 ° C for 4 to 5 hours And sufficiently stirred to prepare a secondary wax water repellent agent.
그 후 1차 발수제 반응용기에 2차 왁스 발수제를 70:30 (1차 발수제:2차 왁스 발수제) 중량비로 서서히 첨가하면서 3 내지 4시간 동안 교반한 후 분산제 및 결합제를 각각 3g씩 첨가하여 최종적으로 균일한 친환경 발수제를 제조하였다.Thereafter, a second water-repellent agent was added to the reaction vessel of the first water-repellent agent gradually at a weight ratio of 70:30 (primary water-repellent agent: second water-repellent agent) to the reaction vessel for 3 to 4 hours and then 3 g of dispersant and binder were added thereto A uniform environmentally friendly water repellent agent was prepared.
<< 실시예Example 3> 3> 실시예Example 3 제조 3 Manufacturing
반응용기에 이소프로필알코올 45g, 증류수 135g 및 계면활성제인 폴리옥시에틸렌소르비탄모노라우레이트 20g을 가한 후 교반하면서 에틸아크릴레이트 30g 및 퍼풀루오르헥사노헥사노익산 45g을 서서히 첨가하였다.45 g of isopropyl alcohol, 135 g of distilled water and 20 g of polyoxyethylene sorbitan monolaurate as a surfactant were added to the reaction vessel, and then 30 g of ethyl acrylate and 45 g of perfluoroohexanohexanoic acid were gradually added while stirring.
그 다음 개시제로 벤조일 퍼옥사이드 4g을 가하고 65 내지 80℃ 온도에서 4 내지 5시간 동안 충분하게 교반하여 공중합체한 1차 발수제를 제조하였다.Next, 4 g of benzoyl peroxide was added as an initiator and the mixture was thoroughly stirred at a temperature of 65 to 80 ° C for 4 to 5 hours to prepare a copolymerized primary water repellent.
다른 반응용기에 폴리에틸렌왁스 25g, 노르말헥산 35g 및 이소프로필알코올 65g을 가하고 계면활성제로 폴리옥시에틸렌소르비탄모노라우레이트 25g, 증류수 70g 및 소포제 3g을 첨가하여 60 내지 75℃ 온도에서 4 내지 5시간 동안 충분하게 교반하여 2차 왁스 발수제를 제조하였다.To another reaction vessel, 25 g of polyethylene wax, 35 g of n-hexane and 65 g of isopropyl alcohol were added, and 25 g of polyoxyethylene sorbitan monolaurate as a surfactant, 70 g of distilled water and 3 g of defoamer were added and heated at 60 to 75 ° C for 4 to 5 hours And sufficiently stirred to prepare a secondary wax water repellent agent.
그 후 1차 발수제 반응용기에 2차 왁스 발수제를 70:30 (1차 발수제:2차 왁스 발수제) 중량비로 서서히 첨가하면서 3 내지 4시간 동안 교반한 후 분산제 및 결합제를 각각 3g씩 첨가하여 최종적으로 균일한 친환경 발수제를 제조하였다.Thereafter, a second water-repellent agent was added to the reaction vessel of the first water-repellent agent gradually at a weight ratio of 70:30 (primary water-repellent agent: second water-repellent agent) to the reaction vessel for 3 to 4 hours and then 3 g of dispersant and binder were added thereto A uniform environmentally friendly water repellent agent was prepared.
<< 실시예Example 4> 4> 실시예Example 4 제조 4 Manufacturing
반응용기에 이소프로필알코올 45g, 증류수 135g 및 계면활성제인 폴리옥시에틸렌소르비탄모노라우레이트 20g을 가한 후 교반하면서 에틸아크릴레이트 30g 및 폴리헵타풀루오르부틸아크릴레이트 45g을 서서히 첨가하였다.45 g of isopropyl alcohol, 135 g of distilled water and 20 g of polyoxyethylene sorbitan monolaurate as a surfactant were added to the reaction vessel, and 30 g of ethyl acrylate and 45 g of polyheptafluorobutyl acrylate were gradually added while stirring.
그 다음 개시제로 벤조일 퍼옥사이드 4g을 가하고 65 내지 80℃ 온도에서 4 내지 5시간 동안 충분하게 교반하여 공중합체한 1차 발수제를 제조하였다.Next, 4 g of benzoyl peroxide was added as an initiator and the mixture was thoroughly stirred at a temperature of 65 to 80 ° C for 4 to 5 hours to prepare a copolymerized primary water repellent.
다른 반응용기에 폴리에틸렌왁스 25g, 노르말헥산 35g 및 이소프로필알코올 65g을 가하고 계면활성제로 폴리옥시에틸렌소르비탄모노라우레이트 25g, 증류수 70g 및 소포제 3g을 첨가하여 60 내지 75℃ 온도에서 4 내지 5시간 동안 충분하게 교반하여 2차 왁스 발수제를 제조하였다.To another reaction vessel, 25 g of polyethylene wax, 35 g of n-hexane and 65 g of isopropyl alcohol were added, and 25 g of polyoxyethylene sorbitan monolaurate as a surfactant, 70 g of distilled water and 3 g of defoamer were added and heated at 60 to 75 ° C for 4 to 5 hours And sufficiently stirred to prepare a secondary wax water repellent agent.
그 후 1차 발수제 반응용기에 2차 왁스 발수제를 70:30 (1차 발수제:2차 왁스 발수제) 중량비로 서서히 첨가하면서 3 내지 4시간 동안 교반한 후 분산제 및 결합제를 각각 3g씩 첨가하여 최종적으로 균일한 친환경 발수제를 제조하였다.Thereafter, a second water-repellent agent was added to the reaction vessel of the first water-repellent agent gradually at a weight ratio of 70:30 (primary water-repellent agent: second water-repellent agent) to the reaction vessel for 3 to 4 hours and 3 g of dispersant and binder were added thereto A uniform environmentally friendly water repellent agent was prepared.
<< 실시예Example 5> 5> 실시예Example 5 제조 5 Manufacturing
반응용기에 이소프로필알코올 45g, 증류수 135g 및 계면활성제인 폴리옥시에틸렌소르비탄모노라우레이트 20g을 가한 후 교반하면서 에틸아크릴레이트 30g 및 폴리트리풀루오르에틸아크릴레이트 45g을 서서히 첨가하였다.45 g of isopropyl alcohol, 135 g of distilled water and 20 g of polyoxyethylene sorbitan monolaurate as a surfactant were added to the reaction vessel, and then 30 g of ethyl acrylate and 45 g of polytrifluoroethyl acrylate were gradually added while stirring.
그 다음 개시제로 벤조일 퍼옥사이드 4g을 가하고 65 내지 80℃ 온도에서 4 내지 5시간 동안 충분하게 교반하여 공중합체한 1차 발수제를 제조하였다.Next, 4 g of benzoyl peroxide was added as an initiator and the mixture was thoroughly stirred at a temperature of 65 to 80 ° C for 4 to 5 hours to prepare a copolymerized primary water repellent.
다른 반응용기에 폴리에틸렌왁스 25g, 노르말헥산 35g 및 이소프로필알코올 65g을 가하고 계면활성제로 폴리옥시에틸렌소르비탄모노라우레이트 25g, 증류수 70g 및 소포제 3g을 첨가하여 60 내지 75℃ 온도에서 4 내지 5시간 동안 충분하게 교반하여 2차 왁스 발수제를 제조하였다.To another reaction vessel, 25 g of polyethylene wax, 35 g of n-hexane and 65 g of isopropyl alcohol were added, and 25 g of polyoxyethylene sorbitan monolaurate as a surfactant, 70 g of distilled water and 3 g of defoamer were added and heated at 60 to 75 ° C for 4 to 5 hours And sufficiently stirred to prepare a secondary wax water repellent agent.
그 후 1차 발수제 반응용기에 2차 왁스 발수제를 70:30 (1차 발수제:2차 왁스 발수제) 중량비로 서서히 첨가하면서 3 내지 4시간 동안 교반한 후 분산제 및 결합제를 각각 3g씩 첨가하여 최종적으로 균일한 친환경 발수제를 제조하였다.Thereafter, a second water-repellent agent was added to the reaction vessel of the first water-repellent agent gradually at a weight ratio of 70:30 (primary water-repellent agent: second water-repellent agent) to the reaction vessel for 3 to 4 hours and then 3 g of dispersant and binder were added thereto A uniform environmentally friendly water repellent agent was prepared.
<< 실험예Experimental Example 1> 1> 발수발유제의Water-repellent 발수도Water repellency 확인 Confirm
실험예 1 내지 5에서 제조된 발유발수제에 물을 첨가하여 각각 2% 농도의 최종 발유발수제 용액을 제조하였다. 제조된 친환경 발유발수제 용액을 각각 폴리에스테르섬유 및 각종섬유에 170℃ 온도에서 10분간 열처리하여 침적시킨 후 발수도를 측정하였다.Water was added to the foot-drop hand made in Experimental Examples 1 to 5 to prepare a final foot-drop hand made solution having a concentration of 2%. The fabricated environmentally-evolved handmade solution was heat-treated for 10 minutes at 170 ° C on polyester fibers and various fibers, and then dipped in water to measure the water content.
발수도는 스프레이 시험법으로 측정하였다. 각각의 발유발수제가 열처리된 섬유를 가로 20cm×세로 20cm로 자른 후 표면을 수평에 대하여 기울기가 45°각도가 되도록 고정면에 부착하였다. 그 후 고정된 섬유표면에 직경이 15cm인 링을 고정시켰다. 클램프에 깔대기를 고정시킨 후 노즐에 직경 0.9mm인 구멍이 19개가 있는 분사구를 섬유쪽으로 고정시키고, 상부 깔대기를 통해 증류수를 15cm 높이에서 각각의 섬유 표면에 25 내지 30초간 뿌려준 후 섬유를 떼어내어 물방울을 털어낸 다음, 발수도 최고 양호 점수인 5를 기준으로 하여 각각의 발수발유제의 발수도를 확인하였다.Foot water was measured by spray test method. Each of the footsteps was heat treated and cut into 20 cm × 20 cm lengths, and then the surface was attached to the fixing surface at an angle of 45 ° with respect to the horizontal. Thereafter, a ring with a diameter of 15 cm was fixed on the surface of the fixed fiber. After fixing the funnel in the clamp, the injection nozzle having 19 holes with a diameter of 0.9 mm is fixed to the fiber and the distilled water is sprayed on the surface of each fiber at a height of 15 cm for 25 to 30 seconds through the upper funnel, And the water-repellency of each water-repellent emulsion was checked based on the water-repellency-rated best score of 5.
그 결과, 표 1과 같은 발수도를 나타내었다.The results are shown in Table 1.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.
While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.
Claims (9)
왁스를 계면활성제가 포함된 분산용액에 첨가하고 60 내지 70℃에서 4 내지 5시간 동안 교반하여 왁스발수제를 제조하는 단계; 및
상기 불소가 포함된 발수제 100 중량부에 대하여 왁스발수제를 20 내지 30 중량부로 혼합하는 단계를 포함하는 것을 특징으로 하는 발수발유제 제조방법Adding an acrylate monomer having a perfluoroalkyl acrylate monomer and an unsaturated double bond to a dispersion solution containing a surfactant and then stirring at 65 to 80 ° C for 4 to 5 hours to prepare a fluorine-containing water repellent agent;
Adding a wax to a dispersion solution containing a surfactant and stirring at 60 to 70 DEG C for 4 to 5 hours to prepare a wax water repellent agent; And
And mixing the wax water repellent agent in an amount of 20 to 30 parts by weight with respect to 100 parts by weight of the fluorine-containing water repellent agent.
[Claim 2] The method according to claim 1, wherein the dispersion solution used in the wax water repellent agent is selected from the group consisting of normal nucleic acid, 1,6-hexanediol, 1-hexanol, methyl alcohol, ethyl alcohol, normal propyl alcohol, iso-propyl alcohol, Wherein the solvent is selected from the group consisting of butyl alcohol, ethylene glycol, N, N-dimethylformamide, acetylacetone, ketone, ether, diethylene glycol and monobutyl ether.
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| RU2676644C1 (en) * | 2018-04-11 | 2019-01-09 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") | Hydrophobic polymer coating |
| KR20200005422A (en) | 2018-07-06 | 2020-01-15 | 한국화학연구원 | Lipophilic agent by modifying starch particles |
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| KR102278339B1 (en) | 2020-07-31 | 2021-07-16 | 진호염직주식회사 | Water repellent composite and manufacturing method thereof, water repellent processing apparatus and method |
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