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CLEAN TECHNOLOGY, Vol. 16, No. 3, September 2010, pp. 172~181 C 5 계수소불화에테르를기반으로하는배합세정제의 CFC 대체세정제적용연구 민혜진, 배재흠, * 장윤상 * 수원대학교화학공학과, 기계공학과 445-743 경기도화성시봉담읍와우리산 2-2 (2010 년 8 월 17 일접수 ; 2010 년 9 월 2 일수정본접수 ; 2010 년 9 월 6 일채택 ) A Study on the Applicability of C 5 Hydrofluoroether-based Formulated Cleaning Agents as CFC-Alternatives Hye Jin Min, Jae Heum Bae, * and Yoonsang Chang * Dept. of Chemical Engineering and Dept. of Mechanical Engineering, The University of Suwon San 2-2 Wau-ri, bongdam-eup, Hwasung city, Gyeonggi 445-743, Korea (Received for review August 17, 2010; Revision received September 2, 2010; Accepted September 6, 2010) 요 약 CFC 세정제의제3 세대대체세정제로평가되는수소불화에테르 (hydrofluoroether; HFE) 는불소분자를함유하고있어표면장력이낮고습윤지수가커서미세입자제거와불소계오염물제거에우수하고인화점이없고건조성이뛰어난물성을가지고있지만, 유기물의용해력은떨어져유기오염물제거에는효율적이지못하다. 본연구에서는 C 5 계 HFE인 HFE-7100 [CF 3CF 2CF 2CF 2OCH 3] 와 HFE-mec-f[CF 3CHF= CF 2OCH 2CF 3] 에유기물질의용해력이비교적으로뛰어난 isopropyl alcohol (IPA), ethyleneglycol monoether (EG), propyleneglycol monoethylether (PM) 를인화점이나타나지않는최대량을각각첨가하여 C 5 계 HFE 기반의배합세정제를제조하여물성과여러종류의플럭스, 비수용성절삭유, 불소계오일에대한세정성평가를수행하였다. 실험결과 C 5 계기반의배합세정제는단일불소계세정제의여러가지물리적성질의장점을가지는것으로나타났다. 그리고 C 5 계기반의배합세정제는첨가된용제에따라약간의차이는있지만대체적으로플럭스, 비수용성절삭유, 불소계오일에우수한세정력을나타내어여러산업세정분야에적용가능성을보여주었다. 주제어 : 수소불화에테르, 세정제배합, 대체세정제, 세정성평가 Abstract : Hydrofluoroethers (HFEs) with fluoride molecules in their structure which are evaluated as the third generation replacement alternatives to chlorofluorocarbons (CFCs) are known to be excellent for removal of nanoparticles and fluoride-type soils due to their low surface tension and high wetting index. In addition, HFEs have good physical properties with no flash and excellent drying characteristics. But, HFEs also have shortcomings in that they are not effective for removal of organic soils due to their poor solubility in soil. In this study, C 5 HFE-based cleaning agents were formulated through addition of solvents such as isopropyl alcohol (IPA), ethyleneglycol monoether (EG), propyleneglycol monoethylether (PM) to HFE-7100 [CF 3CF 2CF 2CF 2OCH 3] or HFE-mec-f [CF 3CHF=CF 2OCH 2CF 3] with its maximum amount, respectively, in order to have no flash for the safety in the working environment. These solvents are known to be excellent for dissolving organics in soil. Their physical properties and cleaning abilities for fluxes, water-insoluble cutting oils, and fluoride-type oils were evaluated and compared with those of other cleaning agents with single * To whom correspondence should be addressed. E-mail : jhbae@suwon.ac.kr, yschang@suwon.ac.kr 172

Clean Tech., Vol. 16, No. 3, September 2010 173 components. The experimental results show that the HFE-based formulated cleaning agents have various good physical properties which are almost similar to those of a single type of HFE cleaner. They show excellent cleaning ability for fluxes, water-insoluble cutting oils, and fluoride-type oils. These results indicate that the HFE-based formulated cleaning agents can be applicable to various industrial cleaning fields because of their good physical properties and cleaning abilities for various soils. Keywords : Hydrofluoroether, Formulation of cleaning agents, Alternative cleaning agents, Evaluation of cleaning ability 1. 서론 CFC-113, 1,1,1-trichloroethane 등과같은성층권의오존파괴성질을갖는세정제는대부분의오염물에대한세정력과건조성이우수하며, 피세정물재질에대한영향이없고, 비독성이며인화성이없어안전하므로거의모든산업분야에서오랫동안세정제로사용되어왔다. 그러나이들물질들은안정적으로지구성층권까지도달하여그곳에머무르면서태양에서오는자외선을차단하여지구의생태계와인류의안전을지켜주는오존의파괴물질로알려져서몬트리올의정서에의거하여생산과사용이금지되기에이르렀다 [1]. 오존파괴물질인 CFC계세정제의제1 세대대체물질로 CFC계세정제와유사한물리화학적성질과세정력을가진 hydrofluorocarbons(hcfs) 의물질이개발되어현재여러분야에서 CFC계세정제를대체하여많이사용하고있다. 그러나이들물질도 CFC계세정제보다작지만오존파괴지수 (ODP; ozone-depletion potential) 를가지고있어국제협약에따라일정기간후에는전폐하도록되어있다 [2]. CFC계세정제의제2 세대대체물질로오존파괴지수가 0인 hydrofluorocarbons (HFCs) 과 perfluorocarbons (PFCs) 가개발되어 HFC43-10-mee [CF 3CHFCHFCF 2CF 3] 와같은일부물질이세정제로사용되고있으나이들물질들은지구온난화지수 (GWP; global-warming potential) 가매우커서교토기후변화협약에의거하여사용에규제를받고있다 [1]. CFC계세정제의제3세대대체물질로미국의 3M사와일본의 Ashai Glass사에서 hydrofluoroethers(hfes) 계세정제를개발하였다. 이들물질들은 HFCs에 ether결합을추가해서제조하여대기중의수명 (lifetime) 을줄여오존파괴지수가 0이되었고, HFCs 에비하여지구온난화지수가비교적작다. HFEs는여러가지물리화학적성질이 CFC와유사하여산업적으로세정제뿐만아니라냉매, 발포제, 소화제등에활용되고있다. HFEs를세정제로활용하는연구는국내외적으로그리많지않다. Flecher 등이발화가우려되고세정제에의한재질의영향이우려되는고농축산소환경의항공기배관연결부에서의 hydraulic oil, grease 등의오염물을제거하는데 HFE 계세정제인 HFE-7100, HFE71-DE (50% HFE-7100+50% trans-1-2-dichloroethylene) 적용한사례가있다 [4]. Middleman 등은 10-9 mbar의초진공을요구하는입자가속기진공시스템에서탄화수소오염물질을제거하는데유해물질인기존의세 정제 trichloroethylene를 HFE계세정제로대체하는사례를발표하였다 [5]. 그리고미국의 Naval Surface Warfare Center (NSWC) 에서비산소계기 (non-oxygen gauge) 세정용으로기존의 HCFC-141b[CFCl 2CH 3] 를 HFE71-DE로대체하였다는보고가있다 [6]. 국내에서는민등이단일성분의 HFE계세정제를 CFC 세정제대체가능성에대한연구를최근에실시한바있다 [7]. 이들연구에서보는바와같이 HFE계세정제는밀도가크고표면장력이극히작고 (13 dyne/cm 이하 ) 습윤지수가커서입자제거에는우수하지만 KB값 (Kauri-butanol value) 이작아불소계오염물을제외하고는유기오염물을제거하기가어려운단점이있다 [7,8]. 또한 HFE의가격이고가이기때문에단일물질로는특정정밀세정분야나난연성이요구되는방위산업분야에서제한적으로사용되고있다. 그리고그동안 HFE 배합세정제로사용되어왔던 HFE71-DE은세정성이좋고건조성이좋고난연성이우수하지만유해물질인염소계세정제와의배합이므로특수한영역에서밀폐분위기에서만사용해야하는단점이있다. 따라서본연구에서는 HFE계세정제의산업체에서의적용가능성을판단하기위하여 1차적으로탄소수가 5개인 C 5-HFE 계세정제단일성분인 HFE-7100, HFE-476mec, HFE- 449mec-f 의물성과세정력을 CFC-113, 삼염화에탄 (1,1,1-trichloroethane), HCFC-141b, 염화메틸렌 (methylene chloride, MC), 이소프로필알코올 (isopropyl alcohol, IPA), 글리콜에테르계세정제 PM (propylene glycol monomethyl ether), EG (ethylene glycol monothyl ether) 등의물질과비교평가하였다. 또한 HFE계세정제의단점인유기물용해도를향상시키기위하여 HFE-7100와 HFE-449mec-f에염소계세정제보다유해하지않아대체세정제로많이사용하지만, 인화성이있어사용에주의가필요한 IPA, EG, PM을각각인화점이측정되지않는최대배합비율로첨가하여배합세정제를제조하고물성과세정성능평가를시행하여 HFE를기반으로하는배합세정제의세정분야적용가능성을평가하였다. 2. 실험 2.1. 실험재료본연구에사용한세정제와세정대상오염물에대해서 Table 1과 Table 2에요약하여나타내었다. 세정제는한국과학기술연구원

174 청정기술, 제 16 권제 3 호, 2010 년 9 월 Table 1. Mixing ratio of HFEs to additives in the HFE-base formulated cleaning agents Classification HFEs Additives Mixing ratio Formulated cleaning agents HFE-7100 HFE-7100 HFE-7100 HFE-449mec-f HFE-449mec-f HFE-449mec-f IPA EG PM IPA EG PM 80:20 50:50 30:70 80:20 60:40 50:50 (KIST) 에서합성한 HFE-476mec [CF 3CHF= CF 2OCH 2CF 3] 와 HFE-449mec-f [CF 3CHFCF 2 OCH 2CH 3] 를공급받아사용하였다. 이들제품중에 HFE-476mec는순도가 73.3%, 75.3%, 94.2% 의 3종류였고, HFE-449mec-f 는순도 88.0% 이었으며, 나머지성분은 IPA 및여러불순물이함유되어있는것으로확인되었다. HFE-476-mec 와 HFE-449mec-f 는두물질모두 C 5 계 HFE 물질이지만 HFE-476-mec-f 가구조식에서불소원자수가 3개더많고수소원자수가 3개더적다 [9]. 이들 KIST 의합성제품들과비교대상제품으로상용화되어시판중인 HFE-7100 (CF 3CF 2CF 2CF 2OCH 3; methyl nonafluorobutyl ether; 3M Novec TM ) 을사용하였다. 그리고이들 HFE계세정제와비교대상의세정제로 CFC-113. 1,1,1,-TCE, MC, HCFC -141b, IPA, PM, EG는시중에서구입하여정제없이사용하였다. 배합세정제로는 Table 1과같이첨가제 IPA, EG, PM을 HFE- 7100과 HFE-449mec-f(88.0%) 와각각인화점이측정되지않는최대혼합비율을선정하여물성과세정성능평가를시행하였다. 세정대상오염물로는인쇄회로기관 (printed circuit board) 의조립생산과정에서납땜을원활히하기위해사용되는 4가지의플럭스를대상으로하였다. 비수용성플럭스는 DF-500 ( 두성공업화학 ), Alpha615-15(Alpha Metals) 를대상으로하였으며. 수용성플럭스는 WS609(Alpha Metals), WF6063M (Senju Metals) 을대상으로하였다. 위의 4가지 flux에대한조성을 Table 2에나타내었다. 또한가공성향상을위해사용되는유제인비수용성절삭유 (bath oil 70%, lard oil 15%, chlorinated paraffin 15%; KOTON 226G, 한국하우톤 ), 여러기계류의윤활제로사용되는불소계오일 (polyfluoro polyether) 을선정하여실험하였다. 오염물도포에는오염물과세정제에의한부식성이거의없는스테인레스평판 (SUS 304 plate :25 75 2) 을재질호환성평가후사용하였다. 2.2. 실험방법 본연구에서는각세정제의기본성질을알아보기위해우선 ph, 비등점, 밀도, 점도, 표면장력등을측정하였다. ph는 ph meter(istec 125PD) 를이용하여 25±1 에서 3회측정후평균하였으며. 비등점은 distillation tester(maker?, AD-6) 를이용하여플라스크에 100 ml의세정제를넣고끓기시작하는지점의온도를자동적으로측정하였다. 밀도는 density/specific Table 2. Composition of various flux tested in this work Water-insoluble flux Water-soluble flux Flux Model (Company, Country) DF-500 (Doosung, Korea) Alpha 615-15 (Alpha Metals, Korea) WS609 (Alpha Metals, Korea) Composition IPA 78%, Rosin 17%, Other 5% IPA 75%, Mineral Spirits 10%, Tail Oil Rosin 10%, Other 5% Dipropylene Glycol 20~25% Methyl ether 30~35% Nonionis Surfactant 15~20% Amine Surfactant 25~30% WF6063M Sn-Ag-Cu-In metal alloy (Senju Metals, Japan) gravity meter (KEM Kyoto Electronics, DA-110M) 를이용하여 25±1 에서 3회측정하여평균하였으며. 점도는 viscometer (Brookfield, LVDV +CP), 표면장력은 surface tensionmeter (Fisher Scientific, Surface Tensionmat 21) 를이용하여 25±1 에서 3회측정하여평균하였다. 또한세정제의세정성능을예측할수있는지수인습윤지수 (wetting index) 를구하였다. 습윤지수는밀도 (ρ), 점도 (μ), 표면장력 (γ) 의관계식으로다음식과같이무차원값으로계산된다. (1) 습윤지수가큰값을갖는세정제일수록오염물질에용이하게침투하고, 오염물질을쉽게수중으로탈착시켜세정효율을증가시키는것으로알려져있다. 인화점측정은인화점측정기 (Grabner, MINIFLASH FLPH Tester) 을사용하여 ASTM D 6450 표준시험법에따라측정하였다. 또한증기압측정은 automatic vapor pressure tester(tanaka Scientific Limeted, AVP-30D) 를사용하여 ASTM D 323의표준시험법에따라측정하였다. 그리고세정제의유기물질의용해력을판단하기위하여세정제가같은부피의아닐린과완전히용해하는최저온도인아닐린점 (aniline ) 을 KS M2053 시험법에따라측정하였다. 세정성능평가는오염물질인플럭스의경우피세정물에일정량을도포하고, 105 에서 12시간동안 baking하여용매를제거한후사용하였으며, 불소계오일, 비수용성절삭유등은시편을오염물질에침적하여도포한후 desiccator에서 24시간동안상온건조하여사용하였다. 세정성능평가는세정, 건조의 2단계로이루어졌으며, 오염물질을균일하게도포한시편을교반없이세정제에일정시간동안담금으로써단순침적세정하고, 60 의강제대류오븐 (forced convection oven) 에서잔류세정제를건조시켜중량법으로반복측정하여진행하

Clean Tech., Vol. 16, No. 3, September 2010 175 Table 3. Physical properties of cleaning agents with single component Physical properties ph Boilig Density (g/cm 3 ) Viscosity (cp, at 25 ) Surface tension (dyne/cm) Flash Vapor pressure (kpa, at 37.8 ) Wetting index Aniline CFC-113 5.01 48 1.5136 0.65 20.7 none 123.7 112 <-20 1,1,1-TCE 5.78 87 1.3105 0.86 28.7 none 29.9 53 <-20 MC 6.13 40 1.2933 0.17 31.8 none 82.4 239 <-20 HCFC-141b 5.02 30.8 1.2360 0.58 21.4 none 129.3 100 <-20 IPA 6.66 80 0.7832 2.74 23.6 18.9 20.9 12 <-20 EG 5.70 135 0.9300 1.22 28.8 44 9.2 26 <-20 PM 3.91 120 0.9201 1.58 25.8 38 3.1 23 <-20 HFE-7100 6.00 61 1.5097 0.61 13.6 none 54.2 182 <-20 HFE-476mec(73.3%) 4.08 71 1.3006 1.02 14.8 none 32.7 86 <-20 HFE-476mec(75.3%) 5.29 71 1.3105 0.98 14.3 none 31.8 94 <-20 HFE-476mec(94.2%) 5.61 70 1.4371 0.72 13.8 none 32.0 145 <-20 HFE-476mecf(88.0%) 5.32 69 1.5354 1.05 14.0 none 31.5 104 <-20 였다. 구체적인실험방법은여러문헌에자세히기록되어있다 [10,11]. 3. 실험결과및고찰 3.1. 세정제의물성측정결과각단일세정제의물성측정결과를 Table 3 에나타내었다. ph를측정한결과대부분의세정제가 3.9~6.7로약산성임을나타내었다. 비점측정결과 EG와 PM을제외한모든실험대상세정제의비점이물보다낮아쉽게상압에서기화가잘일어날것으로판단되었다. HFE-476mec는순도가높아질수록밀도는높아지고점도와표면장력이낮아짐에따라습윤지수가높아져세정성능효율이높아질것으로기대되었다. 그리고 HFE계세정제들은표면장력이 13.6~14.8 dyne/cm로타세정제보다월등히낮고습윤지수가높아오염물에대한침투력이높을것으로기대되며, 인화점이없어안전하지만증기압이높아증발손실이우려된다. 그리고아닐린점도낮아오염물질에대한큰용해력이기대된다. HFE 기반의배합세정제의물성은 Table 4에나타내었다. ph를측정한결과단일세정제와같이대부분의세정제가 3.3~ 6.2로약산성또는중성세제임을나타내었다. 비점은 53~71 로 물보다낮아쉽게상압에서기화가잘일어날것으로판단되었다. 점도측정결과배합세정제중 HFE-449mec-f 과 IPA를배합한세정제의점도가 0.42 cp로가장낮은값을나타내었으며. 습윤지수가다른배합세정제보다가장높아높은세정효율을보일것으로기대되었다. 표면장력은 HFE-7100과 IPA를배합한세정제가 13.6 dyne/cm로가장낮은표면장력을보였다. HFE-7100과 HFE-449mec-f 에배합세정제중 PM과배합된세정제가다른배합세정제보다점도 (1.15, 1.05 cp) 와표면장력 (16.4, 17.5 dyne/cm) 이가장높음을알수있었다. HFE 계세정제가인화점이없는점을활용하여 HFE계세정제를기반으로하여배합한세정제들도인화점이없어사용하고취급하기에안전하며 IPA, EG 및 PM가함유되어있어 HFE계세정제가취약한유기물질세정에적합할것으로기대된다. 또한이들배합세정제들은증기압도높아건조에용이하지만세정제의증발손실에유의할필요가있을것으로판단된다. 3.2. 세정제의세정성평가 3.2.1. 단일세정제의비교평가각단일세정제의세정성평가결과를 Table 5~10에나타내었다. 각단일세정제의세정성평가결과모든오염물에대해서 HFE-476mec 는순도가높아짐에따라높은세정효율을보 Table 4. Physical properties of formulated cleaning agents Formulated cleaning agents Physical properties ph Boiling Density (g/cm 3 ) Viscosity (cp, at 25 ) Surface tension (dyne/cm) Flash Vapor pressure (kpa, at 37.8, ) Wetting index Aniline HFE-7100:IPA 8:2 5.50 53.3 1.3409 0.56 13.6 none 59.4 176 <-20 HFE-7100:EG 5:5 6.23 58.1 1.2101 0.86 14.8 none 43.2 95 <-20 HFE-7100:PM 3:7 4.11 56.6 1.0901 1.15 16.4 none 44.7 58 <-20 HFE-449mec-f:IPA 8:2 4.74 64.8 1.3709 0.42 14.7 none 42.9 222 <-20 HFE-449mec-f: EG 6:4 4.13 67.8 1.2705 0.95 16.3 none 30.8 84 <-20 HFE-449mec-f:PM 5:5 3.34 70.7 1.2100 1.05 17.5 none 29.4 66 <-20

176 청정기술, 제 16 권제 3 호, 2010 년 9 월 Table 5. Cleaning efficiency of water-insoluble DF500 flux by single cleaning agents 1,1,1-TCE 36.00 36.00 36.00 36.00 36.00 42.00 42.00 48.00 MC 99.04 99.04 99.04 99.24 99.27 99.27 99.19 99.33 HCFC-141b 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 IPA 29.17 52.78 52.78 55.56 55.56 55.56 55.94 55.94 EG 28.57 28.57 38.10 38.10 47.62 61.90 61.00 80.94 PM 14.29 17.86 42.86 71.43 71.43 71.43 71.43 71.43 HFE-7100 0.00 0.00 0.00 0.00 0.00 12.31 40.00 40.00 HFE-476mec(73.3%) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 HFE-476mec(75.3%) 34.38 40.63 46.88 46.88 56.25 62.50 68.75 68.75 HFE-476mec(94.2%) 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HFE-449mec-f(88.0%) 50.00 73.33 73.33 73.33 73.33 80.00 86.67 86.67 Table 6. Cleaning efficiency of water-insoluble Alpha 615-15 flux by single cleaning agents 1,1,1-TCE 97.71 100.00 100.00 100.00 100.00 100.00 100.00 100.00 MC 93.13 96.95 96.95 100.00 100.00 100.00 100.00 100.00 HCFC-141b 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 IPA 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 PM 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HFE-7100 12.50 16.67 16.67 19.17 22.50 24.17 24.17 25.00 HFE-476mec(73.3%) 8.80 16.00 24.80 24.80 28.00 32.80 36.80 37.60 HFE-476mec(75.3%) 74.62 88.46 93.08 95.38 99.23 100.00 100.00 100.00 HFE-476mec(94.2%) 73.96 89.58 96.88 100.00 100.00 100.00 100.00 100.00 HFE-449mec-f(88.0%) 5.47 14.84 22.66 28.13 32.81 35.94 97.50 44.53 Table 7. Cleaning efficiency of water-soluble WS609 flux by single cleaning agents 1,1,1-TCE 77.51 86.60 88.04 88.04 93.78 94.26 97.13 97.13 MC 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HCFC-141b 76.77 82.26 83.87 83.87 83.87 84.84 88.39 88.39 IPA 98.42 100.00 100.00 100.00 100.00 100.00 100.00 100.00 PM 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HFE-7100 11.68 12.18 14.59 14.59 17.39 17.39 18.65 18.65 HFE-476mec(73.3%) 23.26 52.56 59.07 60.93 61.40 61.40 64.19 64.65 HFE-476mec(75.3%) 69.05 85.71 92.86 96.03 96.03 99.21 100.00 100.00 HFE-476mec(94.2%) 63.60 88.00 94.80 96.80 96.80 100.00 100.00 100.00 HFE-449mec-f(88.0%) 0.00 15.52 17.24 23.28 23.28 30.17 31.03 37.93 여주었다. 이는순도가높아짐에따라표면장력이낮고습윤지수가높아오염물에더잘침투하여세정효율이높게나타난것으로판단된다. 그리고일반적으로비수계오염물인경우불소함유량이적은 HFE-476mec가불소함유량이많은 HFE- 476mec-f보다특히세정성이우수하였으며수계오염물인 WF6063M flux의경우는 HFE-476mec-f세정제의세정성이 MC, EG와같이아주우수하였다. 오염물이불소계오일인경우 HFE계세정제와불소를함유하고있는 CFC-113과 HCFC-141b 세정제는모두 100% 의세정효율을보였다. 반면에 MC, 1,1,1-TCE를포함한불소를함유하고있지않은나머지세정제는저조한세정효율을보여주었다. 이와같은세정실험결과는이전의 Trifluoroethanol 등과같은불소계세정제

Clean Tech., Vol. 16, No. 3, September 2010 177 Table 8. Cleaning efficiency of water-soluble WF6063M flux by single cleaning agents 1,1,1-TCE 89.35 93.23 96.13 95.16 96.13 97.10 100.00 100.00 MC 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HCFC-141b 76.89 86.67 94.22 94.22 94.22 94.22 98.22 98.22 IPA 16.17 27.17 31.13 34.78 36.35 40.87 94.96 96.52 PM 94.58 98.52 100.00 100.00 100.00 100.00 100.00 100.00 HFE-7100 5.44 38.77 40.88 40.88 40.88 44.21 48.25 49.85 HFE-476mec(73.3%) 18.60 27.27 30.17 32.23 32.23 32.23 35.12 35.54 HFE-476mec(75.3%) 42.55 59.57 76.60 80.85 85.11 85.11 87.23 91.49 HFE-476mec(94.2%) 72.73 84.21 88.04 91.87 91.87 92.34 92.34 92.34 HFE-449mec-f(88.0%) 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Table 9. Cleaning efficiency of water-insoluble cutting oil by single cleaning agents 1 min 2 min 3 min 4 min 6 min 8 min 10 min CFC-113 100.00 100.00 100.00 100.00 100.00 100.00 100.00 1,1,1-TCE 99.62 100.00 100.00 100.00 100.00 100.00 100.00 MC 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HCFC-141b 100.00 100.00 100.00 100.00 100.00 100.00 100.00 IPA 98.84 100.00 100.00 100.00 100.00 100.00 100.00 EG 100.00 100.00 100.00 100.00 100.00 100.00 100.00 PM 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HFE-7100 41.20 51.80 69.50 76.30 87.60 92.80 95.90 HFE-476mec(73.3%) 57.19 71.88 78.13 78.13 78.13 78.13 78.75 HFE-476mec(75.3%) 76.14 100.00 100.00 100.00 100.00 100.00 100.00 HFE-476mec(94.2%) 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HFE-449mec-f(88.0%) 55.63 69.72 76.06 79.58 86.62 90.14 94.37 Table 10. Cleaning efficiency of polyfluoropolyether lubricating oil by single cleaning agents 1 min 2 min 3 min 4 min 6 min 8 min 10 min CFC-113 100.00 100.00 100.00 100.00 100.00 100.00 100.00 1,1,1-TCE 71.01 71.01 71.43 71.43 71.43 71.43 71.43 MC 16.79 19.08 22.52 25.19 32.06 32.06 33.97 HCFC-141b 44.28 73.19 94.58 100.00 100.00 100.00 100.00 IPA 46.34 46.88 47.97 49.59 52.30 52.30 52.30 EG 13.21 18.93 24.29 25.71 25.71 25.71 25.71 PM 37.87 40.83 47.04 48.52 50.89 50.89 50.89 HFE-7100 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HFE-476mec(73.3%) 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HFE-476mec(75.3%) 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HFE-476mec(94.2%) 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HFE-449mec-f(88.0%) 100.00 100.00 100.00 100.00 100.00 100.00 100.00 의세정성평가결과와일치하였다 [7]. 또한비수용성 flux인 DF500과불소계오일을제외하고는 HFE계단일세정제보다 EG, PM의세정성이뛰어나이들물질을적절히배합하면좋은배합세정제가기대된다. 3.2.2. HFE 계배합세정제의비교평가 HFE계세정제인 HFE-7100과 HFE-mec-f(88.0%) 에각각인화점이나타나지않도록 IPA, EG, PM을최대로첨가하여제조한 HFE계배합세정제의세정성평가결과를 Table

178 청정기술, 제 16 권제 3 호, 2010 년 9 월 Table 11. Cleaning efficiency for water-insoluble DF500 flux by formulated cleaning agents IPA 29.17 52.78 52.78 55.56 55.56 55.56 55.94 55.94 EG 28.57 28.57 38.10 38.10 47.62 61.90 61.90 80.95 PM 14.29 17.86 42.86 71.43 71.43 71.43 71.43 71.43 HFE-7100[H1] 0.00 0.00 0.00 0.00 0.00 12.31 40.00 40.00 HFE-449mec-f(88.8%)[H4] 50.00 73.33 73.33 73.33 73.33 80.00 86.67 86.67 H1:IPA = 80:20 13.64 22.73 25.76 28.79 28.79 29.39 48.48 50.00 H1:EG = 50:50 30.95 42.86 52.38 61.09 71.43 71.43 71.43 71.43 H1:PM = 30:70 0.00 9.09 63.64 70.45 84.09 84.09 95.45 95.45 H4:IPA = 80: 20 40.74 48.15 74.07 74.07 74.07 74.07 74.07 74.07 H4:EG = 60:40 81.25 96.88 100.00 100.00 100.00 100.00 100.00 100.00 H4:PM = 50:50 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Table 12. Cleaning efficiency of water-insoluble Alpha 615-15 flux by formulated cleaning agents Cleaning Agent IPA 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 PM 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HFE-7100[H1] 12.50 16.67 16.67 19.17 22.50 24.17 24.17 25.00 HFE-449mec-f(88.8%)[H4] 5.47 14.84 22.66 28.13 32.81 35.94 37.50 44.53 H1 : IPA = 80 : 20 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H1 : EG = 50 : 50 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H1 : PM = 30 : 70 87.50 98.08 100.00 100.00 100.00 100.00 100.00 100.00 H4 : IPA = 80 : 20 97.56 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H4 : EG = 60 : 40 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H4 : PM = 50 : 50 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Table 13. Cleaning efficiency of water-soluble WS609 flux by formulated cleaning agents IPA 98.42 100.00 100.00 100.00 100.00 100.00 100.00 100.00 PM 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HFE-7100[H1] 11.68 12.18 14.59 14.59 17.39 18.65 18.65 18.65 HFE-449mec-f(88.8%)[H4] 0.00 15.52 17.24 23.28 23.28 30.17 31.03 37.93 H1:IPA = 80:20 39.37 58.95 69.63 76.66 88.53 93.37 95.75 97.63 H1:EG = 50:50 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H1:PM = 30:70 93.37 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H4:IPA = 80: 20 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H4:EG = 60:40 97.54 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H4:PM = 50:50 61.88 100.00 100.00 100.00 100.00 100.00 100.00 100.00 11~16 에나타내었다. Table 11에는비수계 flux인 DF-500 의세정효율을나타내었는데 HFE-7100는단일로사용한경우 40% 의세정효율을나타냈지만, IPA, EG, PM과각각배합한경우단일로사용하였을때보다세정효율이상승되었으며, PM과배합한세정제가가장높은효율을보여주었다. 그리고 HFE-449mec-f에 IPA, EG, PM을각각배합한세정제는단 일로사용한세정제들보다우수한세정효율을보여주었다. 특히 EG와 PM과배합한세정제는 10분이내에 100% 세정효율을보여주었으며 EG, PM 단일세정제보다세정효율이훨씬높아두세정제의배합에따른상승 (synergy) 효과가있음을나타내었다. Table12에서는비수용성플럭스 Alpha 615-15 에대한배합세정제의우수한세정효율을보여주고있다.

Clean Tech., Vol. 16, No. 3, September 2010 179 Table 14. Cleaning efficiency of water-soluble WF6063M flux by formulated cleaning agents Cleaning Time IPA 16.17 27.17 31.13 34.78 36.35 40.87 94.96 96.52 PM 94.58 98.52 100.00 100.00 100.00 100.00 100.00 100.00 HFE-7100[H1] 5.44 38.77 40.88 40.88 40.88 44.21 48.25 49.82 HFE-449mec-f(88.8%)[H4] 42.55 59.57 76.60 80.85 85.11 85.11 87.23 91.49 H1:IPA = 80:20 9.62 15.95 52.38 55.54 81.56 85.07 87.10 84.39 H1:EG = 50:50 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H1:PM = 30:70 91.49 98.58 100.00 100.00 100.00 100.00 100.00 100.00 H4:IPA = 80: 20 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H4:EG = 60:40 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H4:PM = 50:50 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Table 15. Cleaning efficiency of water-insoluble cutting oil by formulated cleaning agents Cleaning Time 1 min 2 min 3 min 4 min 6 min 8 min 10 min IPA 98.84 100.00 100.00 100.00 100.00 100.00 100.00 EG 100.00 100.00 100.00 100.00 100.00 100.00 100.00 PM 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HFE-7100[H1] 41.20 51.80 69.50 76.30 87.60 92.80 95.90 HFE-449mec-f(88.8%)[H4] 55.63 69.72 76.06 79.58 86.62 90.14 94.37 H1:IPA = 80:20 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H1:EG = 50:50 74.79 98.35 100.00 100.00 100.00 100.00 100.00 H1:PM = 30:70 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H4:IPA = 80: 20 45.17 61.39 72.97 80.31 89.19 98.07 100.00 H4:EG = 60:40 64.36 88.83 94.68 100.00 100.00 100.00 100.00 H4:PM = 50:50 50.13 64.00 74.13 82.93 92.00 94.93 99.47 Table 16. Cleaning efficiency of polyfluoropolyether lubricating oil by formulated cleaning agents Cleaning Time 1 min 2 min 3 min 4 min 6 min 8 min 10 min IPA 46.34 46.88 47.97 49.59 52.30 52.30 52.30 EG 13.21 18.93 24.29 25.71 25.71 25.71 25.71 PM 37.87 40.83 47.04 48.52 50.89 50.89 50.89 HFE-7100[H1] 100.00 100.00 100.00 100.00 100.00 100.00 100.00 HFE-449mec-f(88.8%)[H4] 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H1:IPA = 80:20 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H1:EG = 50:50 5.46 6.26 6.40 6.60 6.69 6.69 6.69 H1:PM = 30:70 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H4:IPA = 80: 20 100.00 100.00 100.00 100.00 100.00 100.00 100.00 H4:EG = 60:40 75.88 91.87 100.00 100.00 100.00 100.00 100.00 H4:PM = 50:50 30.21 59.38 91.67 100.00 100.00 100.00 100.00 HFE계세정제에단일세정제로는세정효율이극히저조하지만 IPA, EG, PM을배합하여세정효율이 IPA, EG, PM 세정효율과같아짐을볼수있다. Table 13에는수용성플럭스 WS609의세정효율을나타내었다. Table에서보는바와같이 HFE-7100와 HFE-449mec-f 모두단일로사용하였을경우보다 IPA, EG, PM을배합하였 을경우매우우수한세정효율을나타내었다. Table 14에는수용성플럭스 WF 6063M에대한세정효율을나타내었다. 수용성플럭스 WS609DML 세정결과가마찬가지로 HFE계세정제인 HFE-7100와 HFE-449mec-f 는세정효율이저조하였지만 IPA, EG, PM을배합할경우세정효율이상승함을알수있다.

180 청정기술, 제 16 권제 3 호, 2010 년 9 월 Table 15에는비수용성절삭유에대한세정효율을나타내었다. 모든배합세정제모두단일의 HFE계세정제보다세정시간이단축되었고, 세정효율이상승함을볼수있었다. 비수용성절삭유역시앞의플럭스와마찬가지로 IPA, PM, EG을배합할경우세정력을상승시킴으로 HFE 세정제와타세정제와적절히배합하여각세정제의단점을보완할수있을것으로예상된다. Table 16은불소계오일에대한세정효율을나타내었다. 불소계오일에서는 HFE-7100 과각각 IPA, PM 을배합한세정제는 100% 의매우높은세정효율을보인반면 EG 배합한세정제는 10% 미만의매우저조한세정효율을보여주었다. 이것은 EG가저조한세정력을가지고있어세정력이우수한 HFE-7100의세정효율에영향을끼쳐세정력이낮추기때문인것으로판단되어진다. 그러나 HFE-449mec-f 와 EG와배합한세정제는이러한현상이나타나지않았는데이것은 HFE-449mec-f 중에 IPA 등의불순물이영향을주었기때문인것으로판단된다. 그리고 Table 16에서보는바와같이 HFE-449mec-f와배합한모든세정제는 4분이내 100% 의세정효율을나타내어불소계오염물에대하여 HFE 세정제에적절히타세정제를혼합하여세정효율을유지하면서고가의 HFE 세정제사용량을줄일수있음을알수있다. Figure 1~3은앞의결과들중에서 HFE-449-mec-f[H4] 에 PM, EG, IPA에첨가하여각각비수용성 flux, 수용성 flux, 비수용성절삭유및불소계오일을세정한결과를구체적으로도시한그래프이다. Figure 1는 H4, PM, 그리고이들의배합물세정제의비수용성 flux인 DF 500와 Alpha 615-15에대한세정결과를요약한것이다. 그림에서보는바와같이 H4, PM는단일세정제로사용할경우 DF500에대하여저조한세정효율을보여주었지만두물질을 5:5로배합한세정제가훨씬세정력이좋게나타났다. 그리고비수용성 flux인 Alpha 615-15에대해서는 PM은아주좋은세정효율을보여주었지만불소계세정제는아주저조한세정효율을나타내었고이들두물질을배합하였을경우 PM과같은우수한세정효율을보여주었다. Figure 2는 H4, IPA, 그리고이들의배합물세정제의수용성 Figure 2. Comparison of cleaning efficiency for two types of water-soluble flux by single and formulated cleaning agents. flux인 WS609와 WF6063M에대한세정결과를요약한것이다. 그림에서보는바와같이수용성 flux인 WS609 에대해서 IPA는탁월한세정력을보여주지만불소계세정제인 H4는극히저조한세정력을보여주었고이들을 8:2로배합한세정제는 IPA만큼우수한세정력을보여주었다. 그러나또다른타입의수용성 flux인 WF6063M는반대로 IPA에대해서는세정력이떨어지고불소계세정제가초기에더높은세정력을보여주었는데이들물질을 8:2로배합하였을때개별세정제보다세정력이월등하게향상됨을보여주고있다. Figure 3은 H4, EG, 그리고이들의배합세정제의비수용성절삭유와불소계오일에대한세정결과를나타낸것이다. 불소계세정제인 H4의비수용성절삭유에대한세정력은그리나쁘지는않지만 EG의세정력은이보다좋고이들물질을 6:4로배합하였을경우더욱좋아지는것으로나타났다. 그리고 H4의불소계오일에대한세정력은탁월하였고 IPA의불소계오염물에대한세정력은저조하였으며이들물질을 6:4로배합하였을경우인화점이없으면서불소계오염물에대한우수한세정력을보여주었다. Figure 1. Comparison of cleaning efficiency for two types of water-insoluble flux by single and formulated cleaning agents. Figure 3. Comparison of cleaning efficiency for two types of water-insoluble and fluoride-type oils by single and formulated cleaning agents.

Clean Tech., Vol. 16, No. 3, September 2010 181 4. 결론본연구에서는단일 C 5 계 HFE계세정제, 그리고이들세정제에최근 CFC 대체세정제로널리사용되는 IPA, EG, PM를첨가하여제조한배합세정제의물성과이들세정제에대한물성및세정성능평가를진행하였다. 단일세정제의물성측정결과 HFE 계세정제는표면장력이낮고습윤지수가커서오염물질에대한침투력에의하여세정력이지배될것으로추정되었다. 또한불연성이므로안전하지만증기압이커서건조성이우수하지만증발손실이우려되었다. HFE-476-mec의경우순도가높아짐에따라표면장력이작아지고습윤지수가커져서오염물질에대한침투력이높아세정력이우수할것으로기대되었다. 단일세정제의세정성능실험결과불소계세정제는유기성오염물에대한세정력이떨어지지만 IPA, EG, PM등은유기물세정력이우수함을확인할수있었다. 또한불소계세정제는유사한구조를가진물질은서로잘녹는다 (like dissolves like) 는원리에따라불소계오염물질에대하여세정효율이매우뛰어남을확인할수가있었다. HFE-476-mec은순도가높아짐에따라세정효율이증가함을볼수있었으며, DF500, alpha615-15, WS609, WF6063M 등의 flux 세정결과매우우수한세정효율을보여주었다. 배합세정제의물성측정결과 IPA, EG, PM의영향으로단일 HFE계세정제의표면장력보다배합한세정제모두표면장력이소폭증가하였으며. IPA와 HFE-449-mec-f를배합한세정제를제외한나머지배합세정제모두습윤지수가감소하여오염물질에대한침투력이떨어질것으로추정되었다. 그러나 IPA, EG, PM은인화점이있지만 HFE계세정제와적절히배합한세정제는인화점이없음을확인할수있었다. 각배합세정제의대부분의오염물질에대한세정성능결과낮은표면장력, 높은오염물질침투력, 극성의증가등의물리화학적성질의향상으로더우수한세정력을나타내었다. 이로써고가인 HFE계세정제에오염물질에종류에따른적절한용제및첨가제를배합함으로써 HFE계세정제를효율적으로활용가능함을확인할수있었다. 감사본연구는지식경제부의 CFC 대체실용화기술개발사업의일환으로수행되었으며이에감사드립니다. 참고문헌 Hydrofluororethers (HFEs)," J Hazard. Mater., A119, 69-78 (2005). 2. Lim, S. Y., Montreol Protocol and Status of Supply and Demand of Ozone Destruction Material in Domestic Market, Seminar and Workshop for Environmental-friendly Industrial Cleaning, Korea Testing and Research Institute/The University of Suwon, 2-22 (2010). 3. Seika, A., and Misaki, S., "The Potential of Hydrofluoroethers to Replace CFCs, HCFCs and PFCs, J Fluorine Chem., 101(2), 215-221 (2000). 4. Flecher, L. E., Zugno, R., and Dimas, J., "Pipe Cleaning Using HFE Solvents and Assesment of Particle Contamination Found during Pipe Connection," Flammability and Sensitivity of Materials in Oxygen-Enriched Atmospheres: Tenth Volume ASTM STP 1454, Steinberg, T. A. Beeson, H. D. and Newton, B. E., Eds., ASTM International, West Conshhocken, PA, 2003. 5. Middleman, K. J., Herbert, J. D. and Reid, R. J., "Cleaning Stainless Steel for Use in Accelerators - Phase 1" Vacuum, 81, 793-798 (2007). 6. Bishop, M., "Cautions on Using HFE-71DE for Gauge Cleaning," Currents (3M Corp.), 56-58 (2006). 7. Min, H. J., Shin, J. H., Bae, J. H. Kim, H. G., and Lee, H. J., "A Syudy on Applicability of Hydrofluoroethers as CFC- Aternative Cleaning Agents, Clean Tech., 14(3), 184-192 (2008). 8. Robins Air Force Base, "Process and Alternative Evaluation Report - BLDG 169 Vapor Degreasing," WR-ALC/EMP Robins Air Force Base, Georgia, January 2000. 9. Lee, H. J., "A Study on the Development of C 5 Hydrofluoroethers," Final Report, UCM2199-8649-6, Korea Institute of Science and Technology, September, 2009. 10. Min, H. J., "Studies on Applicability of Hydrofluoroether- based Cleaning Agents as CFC-alternative Ones and Evaluation of Cleaning Ability of Ionic Reductive Water and Investigation of its Emulsification Effect in Formulated Lotion," Master Thesis of Chemical Engineering, the University of Suwon 2009. 11. Yoon, H. J., and Lim, C. S., "A Study on Evaluation of Cleaning Ability of Hydrofluoroethers as Alternative Cleaning Agents," Bachelor Thesis of Chemical Engineering, the University of Suwon 2008. 1. Tsai, W. T., "Environmental Risk Assessment of