KR100462314B1 - Deterent compositions for industrial use and preparing method thereof - Google Patents
Deterent compositions for industrial use and preparing method thereof Download PDFInfo
- Publication number
- KR100462314B1 KR100462314B1 KR10-2001-0024510A KR20010024510A KR100462314B1 KR 100462314 B1 KR100462314 B1 KR 100462314B1 KR 20010024510 A KR20010024510 A KR 20010024510A KR 100462314 B1 KR100462314 B1 KR 100462314B1
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- KR
- South Korea
- Prior art keywords
- oil
- ether
- volume
- carbon atoms
- alcohol
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 53
- 239000003921 oil Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 14
- 239000003599 detergent Substances 0.000 claims abstract description 14
- 239000010696 ester oil Substances 0.000 claims abstract description 9
- -1 alkyl phenol ethers Chemical class 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 7
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 4
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- CNHQWLUGXFIDAT-UHFFFAOYSA-N dioctyl 2-hydroxybutanedioate Chemical compound CCCCCCCCOC(=O)CC(O)C(=O)OCCCCCCCC CNHQWLUGXFIDAT-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000005215 alkyl ethers Chemical class 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 claims description 2
- KTSVVTQTKRGWGU-UHFFFAOYSA-N 1-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOCCCC KTSVVTQTKRGWGU-UHFFFAOYSA-N 0.000 claims description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 claims description 2
- KCBPVRDDYVJQHA-UHFFFAOYSA-N 2-[2-(2-propoxyethoxy)ethoxy]ethanol Chemical compound CCCOCCOCCOCCO KCBPVRDDYVJQHA-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 claims description 2
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims description 2
- PCWGTDULNUVNBN-UHFFFAOYSA-N 4-methylpentan-1-ol Chemical compound CC(C)CCCO PCWGTDULNUVNBN-UHFFFAOYSA-N 0.000 claims description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 claims description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 2
- KWABLUYIOFEZOY-UHFFFAOYSA-N dioctyl butanedioate Chemical compound CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC KWABLUYIOFEZOY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 claims 1
- 150000003973 alkyl amines Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 15
- 238000011109 contamination Methods 0.000 abstract description 11
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 239000010730 cutting oil Substances 0.000 abstract description 5
- 239000004519 grease Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000000779 depleting effect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000010721 machine oil Substances 0.000 abstract description 4
- 239000003925 fat Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000004907 flux Effects 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 239000012459 cleaning agent Substances 0.000 description 20
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 14
- 239000004530 micro-emulsion Substances 0.000 description 14
- 150000001298 alcohols Chemical class 0.000 description 11
- 239000000356 contaminant Substances 0.000 description 11
- 239000000839 emulsion Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 235000001510 limonene Nutrition 0.000 description 7
- 229940087305 limonene Drugs 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 6
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000009965 odorless effect Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- XMGQYMWWDOXHJM-SNVBAGLBSA-N (-)-α-limonene Chemical compound CC(=C)[C@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-SNVBAGLBSA-N 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 2
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 2
- RGICCULPCWNRAB-UHFFFAOYSA-N 2-[2-(2-hexoxyethoxy)ethoxy]ethanol Chemical compound CCCCCCOCCOCCOCCO RGICCULPCWNRAB-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- LAPRIVJANDLWOK-UHFFFAOYSA-N laureth-5 Polymers CCCCCCCCCCCCOCCOCCOCCOCCOCCO LAPRIVJANDLWOK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- RSWGJHLUYNHPMX-OZNCTZQZSA-N (1r)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCC[C@@]2(C)C(O)=O RSWGJHLUYNHPMX-OZNCTZQZSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004982 mineral liquid crystal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0017—Multi-phase liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
-
- C11D2111/20—
Abstract
본 발명은 오일, 계면활성제, 물, 그리고 알코올 성분을 포함하는 산업용 세정제 및 그 제조 방법에 관한 것으로서, 본 발명에 따른 세정제 조성물은 (a) 탄소수 12~24의 탄화수소 50 ~ 70부피%, (b) 탄소수 12~22의 에스터 오일 1~20부피%, (c) HLB 4~20의 비이온 계면활성제 0.01~30부피%를 포함하고, 부피비로 (a)/(b)=99/1~70/30이며, 이 세정제 조성물은 전자부품 및 정밀부품의 표면에 묻어 있는 오일, 지방, 기계유, 절삭유, 그리스유, 액정오염, 플럭스 등과 같은 오염물에 대한 세정력이 뛰어나고, 열역학적으로 안정하며, 화재위험성이 적고, 생분해성이 뛰어나며, 오존층 파괴물질을 함유하지 않으므로 환경 안전성이 우수하고, 세정조에서 오염원을 포함한 오일성분과 세정액이 효율적으로 분리됨에 따라 세정수의 필요량이 적고, 발생 폐수의 양이 적어 경제적인 운용이 가능하다.The present invention relates to an industrial detergent comprising an oil, a surfactant, water, and an alcohol component and a method for preparing the same, wherein the detergent composition according to the present invention comprises (a) 50 to 70% by volume of a hydrocarbon having 12 to 24 carbon atoms, (b) 1 to 20% by volume of ester oil having 12 to 22 carbon atoms, and (c) 0.01 to 30% by volume of nonionic surfactant of HLB 4 to 20, in terms of volume ratio (a) / (b) = 99/1 to 70 / 30, this detergent composition has excellent cleaning power, thermodynamic stability, and fire risk for oil, fat, machine oil, cutting oil, grease oil, liquid crystal contamination, flux, etc. on the surface of electronic parts and precision parts. It is small, has excellent biodegradability, and does not contain ozone depleting substances, so it is excellent in environmental safety.The oil component including the pollutant and the cleaning liquid are efficiently separated from the washing tank, so the amount of washing water is small and the amount of waste water generated is economical. Phosphorus operation This is possible.
Description
본 발명은 오일, 계면활성제, 물, 그리고 알코올 성분을 포함하는 산업용 세정제 및 그 제조 방법에 관한 것이며, 더욱 상세하게는, 적어도 2가지 이상의 혼합 오일, 비이온 계면활성제, 물, 알코올, 그리고 기타 첨가제를 포함하며, 전자부품 및 정밀부품의 표면에 묻어 있는 기계유, 절삭유, 그리스, 광유, 또는 액정(liquid crystal) 오염 등과 같은 다양한 오염물에 대하여 높은 세정력을 가지며, 인화점이 높아 화재 위험성이 적고, 세정조 내에서 세정수와 오염성분의 분리가 효율적으로 수행 가능하므로 세정액의 재생 효율이 높아 경제적인 운용이 가능하며, 특히 오존층을 파괴하지 않는 세정제 조성물 및 그 제조 방법에 관한 것이다.FIELD OF THE INVENTION The present invention relates to industrial cleaners comprising oils, surfactants, water, and alcohol components and methods for their preparation, and more particularly, to at least two mixed oils, nonionic surfactants, water, alcohols, and other additives. It has high cleaning power against various contaminants such as machine oil, cutting oil, grease, mineral oil, or liquid crystal contamination on the surface of electronic parts and precision parts, high flash point, low fire risk, cleaning tank Since separation of the washing water and contaminants can be efficiently performed within the present invention, it is possible to economically operate the cleaning liquid due to its high regeneration efficiency, and in particular, to a cleaning composition and a method of manufacturing the same, which do not destroy the ozone layer.
근래, 다양한 산업 분야, 즉 자동차, 전기, 전자, 정밀기계, 광학 산업 분야 등의 정밀 세정 영역에서 우수한 세정력을 갖는 물질로서 광범위하게 사용되어 오고 있는 오존층 파괴 물질(Ozone Depleting Substances, ODS)인 1,1,1-TCE 및 CFC-113의 대체하기 위한 연구가 활발히 진행되고 있다.Recently, Ozone Depleting Substances (ODS), 1, which has been widely used as a material having excellent cleaning power in various cleaning fields such as automobile, electric, electronic, precision machinery, and optical industry, 1, Research is actively in progress to replace 1,1-TCE and CFC-113.
이러한 대체 세정제 기술은 대별(大別)하면 염소계, 탄화수소계, 수계(水系), 준수계(準水系) 등으로 분류할 수 있다.Such alternative cleaning technologies can be roughly classified into chlorine, hydrocarbon, water, and semi-conductors.
이중 대체 세정제로서 첫 번째의 염소계 세정제는 현재 전체 시장의 많은 부분을 점유하고 있는 것으로 보여지고 있다. 그러나, 염소계의 경우 강한 인체 독성 및 발암성 등 안전성에 있어서의 심각한 문제가 지적되고 있고, 환경 규제 뿐만 아니라, 인체 관련 작업 환경에 대한 규제의 확산이 확실시되므로 점차적으로 그 시장 규모는 감소할 것으로 예상된다.The first chlorine-based cleaner as an alternative cleaner is currently seen to occupy a large share of the overall market. However, in the case of chlorine, serious problems in safety such as strong human toxicity and carcinogenicity have been pointed out, and the market size is expected to decrease gradually as it is confirmed that not only environmental regulations but also regulations on human-related working environment are spread. do.
두 번째 유형의 대체 세정제로서의 탄화수소계 세정제는 현재 염소계 다음 규모의 시장 규모를 가지고 있으나, 인화성과 건조 문제가 지적되고 있다. 또한, 이러한 탄화수소계 세정제 중에서, 벤젠, 자일렌 등과 같은 방향족계 용제형 세정제는 인체 독성이 높아 인체 안전성 및 환경 오염성에 있어 역시 문제가 있으므로 세정 현장에서 엄격한 규제를 받고 있다.Hydrocarbon-based cleaners as the second type of alternative cleaners now have market scale next to chlorine-based, but flammability and drying issues are pointed out. In addition, among such hydrocarbon-based cleaners, aromatic solvent-type cleaners such as benzene and xylene are highly toxic to humans, and thus have problems in human safety and environmental pollution, and thus are subject to strict regulations in the washing site.
인체 안전성 및 인화 안전성 등과 같은 작업 안전성을 고려할 때, 준수계 또는 수계 세정제 기술이 최근 주목받고 있다. 이러한 유형의 세정제는 기본적으로 물을 함유한 세정제로서 용제계 세정제에 비하여 인체 안전성과 작업 안전성이 우수하며, 다양한 계면활성제와 빌더를 첨가하여 세정력과 세정성을 높일 수 있는 장점이 있다. 그러나, 이와 같은 수계나 준수계 세정제의 경우, 기존의 상기한 다른 유형의 유기 용제와 대등한 성능을 발휘하도록 하기 위해서는 적절한 유기 용제와 계면활성제 시스템의 개발이 필요하며, USP 6,136,775, USP 5,271,773, USP 6,071,867에 있어서는 리모넨(D형 리모넨, L형 리모넨 및, 이들 이성질체의 혼합형태) 혹은 터펜을 사용한 고성능 세정제가 제안되어 있다. 이러한 세정제들은 우수한 세정력을 보여, 많은 작업 현장에서 기존의 CFCs를 대체하는 세정제로서 이용되고는 있으나, 리모넨이나 터펜의 경우 천연 유래 물질로서, 가격의 변동폭이 크고, 상대적으로 다른 유기 용제에 비하여 고가이므로, 소비자 및 공급자 모두에게 미용적 부담이 상대적으로 큰 문제점이 있다. 또한, 리모넨이나 터펜는 그 자체가 특이취가 강하여 지속적인 작업이 수반되는 현장 작업자가 고통을 호소하게 되는 문제가 다른 단점으로 지적되고 있다. 또한, 상대적으로 낮은 인화점을 가지고 있어, 작업시 수분량이 감소함에 따라 화재의 위험성이 높아져 엄격한 작업 관리가 필요하며, 또한 수생 생물에 대한 독성이 있어 세정 후 폐수처리에 특별한 시설 및 각별한 주의가 요망되는 등 사후 관리가 번거로운 문제점도 수반하고 있는 것으로 보고되어 있다.In consideration of work safety such as human safety and flammable safety, a compliance or water based cleaner technology has recently attracted attention. This type of cleaning agent is basically a water-containing cleaning agent is superior to the solvent-based cleaners and the human safety and work safety, there is an advantage that can increase the cleaning power and cleanability by adding various surfactants and builders. However, in the case of such water-based or semi-conductive cleaners, it is necessary to develop suitable organic solvents and surfactant systems in order to achieve the same performance as other types of organic solvents described above. USP 6,136,775, USP 5,271,773, USP In 6,071,867, high-performance cleaners using limonene (D-limonene, L-limonene and mixed forms of these isomers) or terpenes have been proposed. These cleaners show excellent cleaning power, and are used as a cleaner to replace conventional CFCs in many workplaces. However, limonene and terpene are naturally derived materials, and the price fluctuates largely and is relatively high compared to other organic solvents. However, the cosmetic burden is relatively large for both consumers and suppliers. In addition, limonene or terpene itself has a strong specificity, the problem that the on-site workers complain of continuous work is pointed out as another disadvantage. In addition, it has a relatively low flash point, and as the water content decreases during operation, the risk of fire increases, so strict work management is required. In addition, it is toxic to aquatic organisms, so special facilities and special care are required for wastewater treatment after cleaning. It has been reported that the aftercare is accompanied by a troublesome problem.
상기한 바와 같은 종래 기술의 단점을 보완하기 위한 종래의 제안으로서, USP 5,350,457, USP 5,567,348 및, USP 5,725,679은 유기 용제로서 무취의 탄화수소를 사용하는 방법을 제안하고 있다. 이러한 종래의 방안은 무취의 탄화수소를 사용함에 따라 작업이 순조롭고, 세정후 세정조에서 유성 오염 성분과 세정수의 분리가 가능하여 세정수의 사용량을 감소시킬 수가 있으므로 폐수 처리비용 및 부담이감소하여 경제성이 높은 장점은 있으나, 사용되는 탄화수소의 인화점이 상대적으로 낮으므로, 작업시 수분의 함량이 감소할 경우 화재의 위험성이 증대되고, 고점성 유성 오염의 세정시 계면활성제와 오일의 라멜라 액정 구조가 형성되어 미세한 홈이나 굴곡 부분에서의 세정 효율이 열등하다는 문제점이 지적되고 있다.As a conventional proposal to supplement the disadvantages of the prior art as described above, USP 5,350,457, USP 5,567,348, and USP 5,725,679 propose a method using an odorless hydrocarbon as an organic solvent. This conventional method is easy to operate by using odorless hydrocarbons, and since it is possible to separate oily contaminants and washing water in the washing tank after washing, the amount of washing water can be reduced, thereby reducing the waste water treatment cost and burden and economical efficiency. Although there is a high advantage, the flash point of the hydrocarbon used is relatively low, so the risk of fire increases when the water content decreases during operation, and the lamellar liquid crystal structure of the surfactant and the oil is formed when the high viscosity oil contamination is cleaned. As a result, the problem of poor cleaning efficiency in minute grooves and curved portions is pointed out.
따라서, 본 발명의 첫 번째 목적은 기존의 세정력은 우수하나 오존층 파괴 물질인 1,1,1-TCE 및 CFC-113의 대체물로서, 오존 비파괴성 세정제를 제공하기 위한 것이다.Accordingly, the first object of the present invention is to provide an ozone non-destructive cleaning agent as a substitute for 1,1,1-TCE and CFC-113, which are excellent in existing cleaning power but ozone depleting substances.
본 발명의 두 번째 목적은 고점성의 유성 오염에 대해서 우수한 세정 효율을 발휘하여 정밀부품의 세정 및 전자 부품의 세정에 효율적인 고성능 세정제를 제공하기 위한 것이다.A second object of the present invention is to provide a high-performance cleaning agent that is effective for cleaning precision parts and cleaning electronic parts by exerting an excellent cleaning efficiency against high viscosity oil contamination.
본 발명의 세 번째 목적은 화재의 위험성이 저감된 세정제를 제공하기 위한 것이다.It is a third object of the present invention to provide a cleaner with reduced risk of fire.
본 발명의 네 번째 목적은 광범위한 세정 온도 범위에 걸쳐 우수한 세정력을 나타내며 열역학적으로 안정한 세정제를 제공하기 위한 것이다.A fourth object of the present invention is to provide a detergent which exhibits excellent cleaning power over a wide range of cleaning temperatures and is thermodynamically stable.
본 발명의 다섯 번째 목적은 생분해성이 뛰어나 환경 안전성이 우수하고, 세정조 내에서 오염원을 포함한 오일 성분과 물의 분리가 가능하여 폐수 발생량의 감소를 극대화 할 수 있는 환경 친화적 세정제를 제공하기 위한 것이다.The fifth object of the present invention is to provide an environmentally friendly detergent that is excellent in biodegradability and excellent in environmental safety, and is capable of separating oil components and water including pollutants in a washing tank to maximize the reduction of waste water generation.
본 발명의 여섯 번째 목적은 인체에 저독성이므로 작업 환경성이 우수한 세정제를 제공하기 위한 것이다.A sixth object of the present invention is to provide a detergent having low work environment and excellent working environment.
본 발명의 일곱 번째 목적은 상기한 본 발명의 첫 번째 내지 여섯 번째 목적에 따른 세정제의 제조 방법을 제공하기 위한 것이다.A seventh object of the present invention is to provide a method for preparing a cleaning agent according to the first to sixth objects of the present invention described above.
상기한 본 발명의 첫 번째 내지 여섯 번째 목적을 달성하기 위한 본 발명의 바람직한 일 양태(樣態)에 따르면, (a) 탄소수 12~24의 탄화수소 50 ~70부피%, (b) 탄소수 12~22의 에스터 오일 1~20부피%, (c) HLB 4~20의 비이온 계면활성제 0.01~30부피%, (d) 물 2~30부피%를 포함하고, 부피비로 (a)/(b)=99/1~70/30인 고성능 산업용 세정제가 제공된다.According to one preferred aspect of the present invention for achieving the above first to sixth objects of the present invention, (a) 50 to 70% by volume hydrocarbons having 12 to 24 carbon atoms, and (b) 12 to 22 carbon atoms Ester oil of 1-20% by volume, (c) 0.01-30% by volume of nonionic surfactant of HLB 4-20, (d) 2-30% by volume of water, and (a) / (b) = High performance industrial cleaners from 99/1 to 70/30 are provided.
상기한 본 발명의 첫 번째 내지 여섯 번째 목적을 달성하기 위한 본 발명의 바람직한 다른 일 양태(樣態)에 따르면, 상기한 첫 번째 양태의 조성물에 (e) 알코올류 0.01~30부피%를 더욱 포함하며, (d)/(c)=0.1~1.5인 고성능 산업용 세정제가 제공된다.According to another preferred aspect of the present invention for achieving the above first to sixth objects of the present invention, the composition of the above first aspect further comprises 0.01 to 30% by volume of alcohols. And, (d) / (c) = 0.1 ~ 1.5 high performance industrial cleaner is provided.
상기한 본 발명의 일곱 번째 목적을 달성하기 위한 본 발명의 바람직한 일 양태(樣態)에 따르면, 오일 성분으로서 탄소수 12~24의 포화 또는 불포화 탄화수소와 탄소수 12~22의 이염기산 에스터 오일을 99/1~70/30의 비율로 적용하여 유성계를 제공하는 단계와, 비이온성 계면활성제를 첨가하는 단계로 구성되는 고성능 산업용 세정제의 제조 방법이 제공된다.According to one preferred aspect of the present invention for achieving the seventh object of the present invention, a saturated or unsaturated hydrocarbon having 12 to 24 carbon atoms and a dibasic acid ester oil having 12 to 22 carbon atoms is used as an oil component. Provided is a method of producing a high-performance industrial cleaner comprising the step of providing an oily system by applying a ratio of 1 ~ 70/30, and the step of adding a nonionic surfactant.
상기한 본 발명의 일곱 번째 목적을 달성하기 위한 본 발명의 바람직한 다른일 양태(樣態)에 따르면, 보조 계면활성제로서 알코올을 알코올/비이온성 계면활성제=0.1~1.5의 비율로 혼합하는 단계, 및/또는 물을 전조성물 기준으로 0~30부피%가 되도록 첨가하는 단계를 더욱 포함하는 고성능 산업용 세정제의 제조 방법이 제공된다.According to another preferred aspect of the present invention for achieving the seventh object of the present invention, the step of mixing the alcohol as an auxiliary surfactant in the ratio of alcohol / nonionic surfactant = 0.1 ~ 1.5, and And / or further comprising adding water to 0-30% by volume based on the precursor composition.
도 1은 본 발명의 바람직한 W/O 타입 마이크로에멀젼이 형성되는 오일/비이온 계면활성제/물 시스템의 상평형도이다.1 is a phase diagram of an oil / nonionic surfactant / water system in which a preferred W / O type microemulsion of the present invention is formed.
도 2는 알코올의 첨가에 따른 도 1의 W/O 타입 마이크로에멀젼의 형성 온도 영역을 나타내는 도면이다.FIG. 2 is a view showing a temperature range of formation of the W / O type microemulsion of FIG. 1 with the addition of alcohol.
이하, 본 발명에 대하여 구체적으로 설명하기로 한다.Hereinafter, the present invention will be described in detail.
먼저, 본 발명의 세정제를 구성하는 오일 성분에 대하여 설명하면, 무색 무취의 탄화수소 오일로서 비점이 높고 인화성이 상대적으로 낮으며, 환경 안전성과 인체 안전성이 우수한 오일을 선택하는 것이 바람직하다.First, the oil component constituting the cleaning agent of the present invention will be described. It is preferable to select an oil having a high boiling point, relatively low flammability, and excellent environmental safety and human safety as a colorless odorless hydrocarbon oil.
직쇄 파라핀의 경우에는 탄소수가 증가됨에 따라서 비점이 상승하고 화재의 위험성은 감소하나, 유동성이 감소하고, 계면활성제와 강고한 액정을 형성하여 세정 시간이 증가될 우려가 있으므로, 파라핀보다는 직쇄 올레핀이 본 발명에 있어 더욱 바람직하나, 본 발명은 직쇄 파라핀의 경우를 배제하는 것은 아니다.In the case of linear paraffin, as the carbon number increases, the boiling point increases and the risk of fire decreases, but since the fluidity decreases and the cleaning time may be increased by forming a strong liquid crystal with a surfactant, a linear olefin rather than paraffin is seen. Although more preferred in the invention, the invention does not exclude the case of straight-chain paraffins.
올레핀의 경우 불포화기가 존재하므로 탄소수 증가에도 상온에서 유동성이 있고, 탄소수가 18인 경우에도 매우 낮은 점성과 상대적으로 낮은 화재 위험성을 부여한다. 본 발명의 세정제에 사용되는 올레핀은 탄소수 12~24의 범위이며, 바람직하게는 탄소수 12~20의 범위, 가장 바람직하게는 탄소수 14~18의 범위이나, 이는 본 발명에 있어서 제한적인 것은 아니다.In the case of olefins, an unsaturated group is present, so it has fluidity at room temperature even when the carbon number is increased, and even at 18 carbon atoms, it gives very low viscosity and a relatively low fire risk. The olefin used in the cleaning agent of the present invention is in the range of 12 to 24 carbon atoms, preferably in the range of 12 to 20 carbon atoms, most preferably in the range of 14 to 18 carbon atoms, but this is not limitative in the present invention.
본 발명의 세정제에 사용될 수 있는 다른 오일 성분으로서는, 이염기산의 에스터형 오일을 들 수 있다. 상대적으로 올레핀이나 파라핀에 비하여 생분해도가 높고, 인화점이 높아 화재의 위험성이 낮으며, 올레핀이나 파라핀에 혼합되어 전체적인 유성분과 물과의 계면에 위치하여 좀더 안정한 에멀젼을 형성하게 한다. 본 발명에 바람직하게 사용될 수 있는 이염기산의 에스터 오일로서는 디옥틸 말레이트, 디옥틸 아디페이트, 디옥틸 숙시네이트 등을 들 수 있으며, 탄화수소와 혼합시 높은 유동성과 친수성 오염에 대한 제거율이 증가되는 효과를 나타낸다.As another oil component which can be used for the washing | cleaning agent of this invention, the ester type oil of dibasic acid is mentioned. Compared to olefins and paraffins, biodegradability is high, flash point is high, and the risk of fire is low. When mixed with olefins and paraffins, they are located at the interface between the whole oil and water to form a more stable emulsion. Examples of ester oils of dibasic acids which can be preferably used in the present invention include dioctyl malate, dioctyl adipate, and dioctyl succinate, and the effect of increasing the removal rate against high fluidity and hydrophilic contamination when mixed with hydrocarbons. Indicates.
본 발명의 세정제에 사용되는 오일 성분으로서의 상기한 혼합 오일은 무취이며, 인화점이 높아 상대적으로 화재의 위험성이 적고, 상온에서 유동성이 높아 오염 성분의 빠른 제거가 가능한 오일로서, 상기한 탄화수소와 이염기산 에스터의 혼합 비율은 비용적 측면 및 상 안정성 측면에서 99:1~70:30의 범위가 바람직하다. 상기한 혼합 오일은 전조성 기준으로 50부피%~90부피%의 범위, 바람직하게는 60부피%~85부피%의 범위, 더욱 바람직하게는 65부피%~80부피%의 범위이다.The above-mentioned mixed oils as oil components used in the cleaning agent of the present invention are odorless, have a high flash point, have a relatively low risk of fire, have high fluidity at room temperature, and enable fast removal of contaminants. The mixing ratio of the ester is preferably in the range of 99: 1 to 70:30 in terms of cost and phase stability. The mixed oil is in the range of 50% by volume to 90% by volume, preferably in the range of 60% by volume to 85% by volume, more preferably in the range of 65% by volume to 80% by volume.
이어서, 본 발명의 세정제를 구성하는 계면활성제에 대하여 설명하면, 생분해도가 우수하며, 전자 부품 등에의 이온성 물질의 잔류는 바람직하지 못할 수 있으므로 비이온 계면활성제가 바람직하게 사용될 수 있다.Next, the surfactant constituting the cleaning agent of the present invention will be described. Since the degree of biodegradation is excellent and the residual of the ionic substance in the electronic component or the like may be undesirable, a nonionic surfactant may be preferably used.
본 발명의 세정제에 바람직하게 사용될 수 있는 비이온 계면활성제는 평균 HLB가 4~20의 범위인 것이 바람직하다. 계면활성제는 오일 성분의 유화 및 세정성을 높이고 물에 의한 세정성 및 제품의 상 안전성을 양호하게 하기 위하여 사용된다. 상기한 비이온 계면활성제의 예로서는, 폴리옥시알킬렌 알킬 에테르, 폴리옥시알킬렌 알킬 페놀 에테르, 폴리옥시알킬렌 아릴 페놀 에테르, 폴리옥시알킬렌 지방산 에스터, 폴리옥시알킬렌 솔비탄 지방산 에스터, 폴리옥시알킬렌 알킬 아민, 솔비탄 지방산 에스터, 알킬 알코올 아민, 아릴 알코올 아민, 또는 이들의 임의의 혼합물을 들 수 있으며, 생분해도 및 성능을 고려시 폴리옥시알킬렌 알킬 에테르가 바람직하게 사용될 수 있다. 이들 비이온 계면활성제는 전조성 기준으로 0.01부피%~30부피%의 범위, 바람직하게는 5부피%~25부피%의 범위, 더욱 바람직하게는 10부피%~20부피%의 범위이다.Nonionic surfactants which can be preferably used in the cleaning agent of the present invention preferably have an average HLB in the range of 4 to 20. Surfactants are used to enhance the emulsification and detergency of the oil component, and to improve the detergency by water and the phase safety of the product. Examples of the above nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenol ethers, polyoxyalkylene aryl phenol ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, and polyoxy Alkylene alkyl amines, sorbitan fatty acid esters, alkyl alcohol amines, aryl alcohol amines, or any mixtures thereof, and polyoxyalkylene alkyl ethers may be preferably used in view of biodegradability and performance. These nonionic surfactants are in the range of 0.01 vol% to 30 vol%, preferably in the range of 5 vol% to 25 vol%, and more preferably in the range of 10 vol% to 20 vol%, on the basis of preforming properties.
전술한 세가지 성분과 물이 혼합되는 본 발명에 따른 시스템에서의 최적의 조성비를 도 1에 도시한다.The optimum composition ratio in the system according to the invention in which the three components mentioned above and water are mixed is shown in FIG. 1.
통상적으로는, 오일성분/계면활성제/물의 혼합시스템에서는, 1) O/W 타입 마이크로에멀젼, 2) 바이컨틴뉴어스(bicontinous) 타입 마이크로에멀젼, 3) W/O 타입 마이크로에멀젼의 3가지 타입의 유화물의 제조가 가능하나, 바이컨틴뉴어스 타입 에멀젼의 경우 비극성 및 극성 오염원에 대한 세정력은 우수하나 상안정성에 문제가 있어 장기 보존시 상분리가 일어나게 되므로 제품화하기 어렵다는 단점이 있고, O/W 타입의 에멀젼의 경우 극성 오염원에 대한 세정력은 우수하나, 비극성 오염원에 대한 세정력은 약한 단점이 있다. 따라서, 지방 및 오일, 기계유, 절삭유, 그리스, 광유, 액정(liquid crystal) 오염 등 다양한 비극성 오염원에 대한 세정제 시스템으로서는 W/O 타입의 에멀젼 시스템이 바람직할 수 있으며, 오염원에 대한 우수한 세정력, 열역학적 안정성으로 인한 장기 보관성, 특히 세정 과정에서 용수 절감성을 얻을 수 있는 조성 영역의 결정이 필요하다. 세정성이 우수하고, 열역학적으로 안정한 마이크로에멀젼을 형성하기 위해서는 형성 온도에 따른 오일/비이온계면활성제/물 시스템에 대한 상평형 (phase equilibrium) 의 예측이 필수적이다. 따라서, 물과 오일, 그리고 비이온 계면활성제의 부피 변화에 따른 상의 변화를 관찰한 후 이로부터 도 1에 나타낸 바와 같은 상의 마이크로에멀젼이 형성되는 영역을 확인한 후, 이 영역 주위의 성분 용액을 만들어서 온도 변화에 따른 상 변화를 관찰하여 도 1에 나타낸 상의 W/O타입 마이크로에멀젼이 형성되는 오일/비이온계면활성제/물 시스템의 상평형도를 도시하였다.Typically, in oil / surfactant / water mixing systems, there are three types of: 1) O / W type microemulsions, 2) bicontinous type microemulsions, and 3) W / O type microemulsions. Although emulsifiers can be manufactured, bicontinental type emulsions have excellent cleaning power against nonpolar and polar contaminants, but have phase defects due to phase stability, which makes it difficult to commercialize them. In the case of emulsion, the cleaning power for the polar pollutant is excellent, but the cleaning power for the nonpolar pollutant is weak. Therefore, W / O type emulsion system may be preferable as a cleaning system for various nonpolar contaminants such as fat and oil, machine oil, cutting oil, grease, mineral oil, liquid crystal contamination, and the like. It is necessary to determine the compositional area that can provide long-term storage, especially water savings during cleaning. Prediction of phase equilibrium for oil / nonionic surfactant / water systems with forming temperature is essential to form microemulsions with good cleanability and thermodynamic stability. Therefore, after observing the change of the phase according to the volume change of water, oil, and nonionic surfactant, and confirming the region where the microemulsion of the phase is formed therefrom as shown in FIG. The phase change with the change was observed to show the phase equilibrium of the oil / nonionic surfactant / water system in which the W / O type microemulsion of the phase shown in FIG. 1 was formed.
친수성 부분과 소수성 부분으로 이루어진 비이온 계면활성제는 온도가 증가함에 따라 소수성이 증가하게 된다. 따라서, 저온에서는 물과의 친화성이 크고, 고온에서는 오일과의 친화성이 커지게 된다. 세정 온도가 상승되면, 비이온 계면활성제의 소수성이 증가하게 되므로 계면활성제의 세정력을 높이기 위해서는 도 1의 B 영역과 같은 조성비를 고려하는 것이 유리하며, 온도가 낮은 세정 조건에서는 이와 반대로 A 영역과 같은 조성비를 로 조성물을 디자인하는 것이 유리하다. 또한, 사용하는 비이온 계면활성제의 HLB(hydrophilic lipophilic balance)에 있어서는, 높은 HLB를 가진 계면활성제의 경우에는 B 영역의 조성비에서도 안정한 상의 마이크로에멀젼이 형성되며, 상대적으로 HLB가 낮은 비이온 계면활성제를 사용하는 경우에는 A 영역에서 또한 안정한 상의 마이크로에멀젼이 형성되는 것으로 나타났다. 상기한 결과로부터 W/O 타입의 세정제를 제조함에 있어서 물의 첨가량은, 전조성물 기준으로 0부피%~30부피%의 범위, 바람직하게는 2부피%~25부피%의 범위, 더욱 바람직하게는 5부피%~15부피%의 범위일 수 있다.Nonionic surfactants, consisting of hydrophilic and hydrophobic moieties, increase in hydrophobicity with increasing temperature. Therefore, the affinity with water is large at low temperature, and the affinity with oil is high at high temperature. When the cleaning temperature is increased, the hydrophobicity of the nonionic surfactant is increased, so to increase the cleaning power of the surfactant, it is advantageous to consider the composition ratio as shown in the region B of FIG. 1. It is advantageous to design the composition with a composition ratio. In addition, in the hydrophilic lipophilic balance (HLB) of the nonionic surfactant to be used, in the case of the surfactant having a high HLB, a microemulsion of a stable phase is formed even at a composition ratio of the B region, and a nonionic surfactant having a relatively low HLB is formed. In the case of use, microemulsions of stable phases were also formed in the A region. From the above results, the amount of water added in the preparation of the W / O type cleaning agent is in the range of 0% to 30% by volume, preferably in the range of 2% to 25% by volume, more preferably 5 It may range from volume% to 15 volume%.
이어서, 본 발명의 세정제에 사용될 수 있는 또 다른 성분으로서의 알코올류에 대하여 설명하기로 한다. 알코올류는 오일과 비이온 계면활성제 그리고 물 3성분 시스템에서 생성되는 에멀젼의 상안전성을 증가시키기 위해서 첨가되는데, 이는 또한 넓은 온도 범위에서 안정한 에멀젼이 유지되도록 도와줌으로써 다양한 세정 온도 범위에서 원활한 세정이 가능하도록 도와주며, 또한 세정력 향상에 있어서도 중요한 역할을 한다. 일반적으로, 오일/비이온계면활성제/물로 이루어진 3 성분 시스템에 알코올과 같은 보조 계면활성제가 첨가될 경우, 상 변화는 알코올의 친수 및 소수적인 성질에 의존하게 되는데, 일반적으로 부탄올 또는 펜탄올 등과 같은 탄소수가 적은 알코올이 첨가되면 시스템은 친수성이 증가하게 되어 마이크로에멀젼을 형성하는 온도가 높아지게 되며, 헵탄올 또는 옥탄올 등과 같은 탄소수가 많은 알코올이 첨가되면 시스템의 소수성이 증가하여 마이크로에멀젼을 형성하는 온도가 낮아지게 된다[J.C. Lim, C.A. Miller, and C. Yang, Colloids and Surfaces, 66, 45~53(1992), R. Stray and M. Jonstromer, J. Phys. Chem. 96, 4537~4542 (1992) 참조].Next, alcohols as another component that can be used in the cleaning agent of the present invention will be described. Alcohols are added to increase the phase safety of emulsions produced in oils, nonionic surfactants, and water three-component systems, which also help to maintain stable emulsions over a wide temperature range, allowing smooth cleaning over a wide range of cleaning temperatures. In addition, it also plays an important role in improving cleaning power. Generally, when a co-surfactant such as alcohol is added to a three component system of oil / nonionic surfactants / water, the phase change will depend on the hydrophilic and hydrophobic nature of the alcohol, generally butanol or pentanol The addition of alcohols of low carbon number increases the hydrophilicity of the system and increases the temperature of forming the microemulsion. The addition of alcohols of high carbon number such as heptanol or octanol increases the hydrophobicity of the system to form the microemulsion. Becomes lower [JC Lim, C. A. Miller, and C. Yang, Colloids and Surfaces, 66, 45-53 (1992), R. Stray and M. Jonstromer, J. Phys. Chem. 96, 4537-4542 (1992).
본 발명에 사용될 수 있는 상기한 알코올류의 예로서는 에탄올, 프로판올, 부탄올, 헥산올, 이소프로판올, 헵탄올, 옥탄올, 데칸올, 이소헥산올, 이소옥탄올, 이소데칸올, 에틸렌 글리콜, 디에틸렌 글리콜, 트리에틸렌 글리콜, 에틸렌 글리콜 메틸 에테르, 디에틸렌 글리콜 메틸 에테르, 트리에틸렌 글리콜 메틸 에테르, 에틸렌 글리콜 에틸 에테르, 디에틸렌 글리콜 에틸 에테르, 트리에틸렌 글리콜 에틸 에테르, 에틸렌 글리콜 모노프로필 에테르, 디에틸렌 글리콜 모노프로필 에테르, 트리에틸렌 글리콜 모노프로필 에테르, 에틸렌 글리콜 모노부틸 에테르, 디에틸렌 글리콜 모노부틸 에테르, 트리에틸렌 모노부틸 에테르, 에틸렌 글리콜 디부틸 에테르, 디에틸렌 글리콜 디부틸 에테르, 트리에틸렌 글리콜 디부틸 에테르, 에틸렌 글리콜 모노헥실 에테르, 디에틸렌 글리콜 모노헥실 에테르, 트리에틸렌 글리콜 모노헥실 에테르, 또는 이들의 임의의 혼합물이 사용될 수 있으나, 짧은 탄소수의 알코올은 화재의 위험성이 높고, 세정후 폐액에 잔류하는 경우가 많아 방출수의 COD를 증가시킬 우려가 있다. 따라서, 세정제의 상안정성을 높이고, 알코올 자체의 인화점이 높아 화재의 위험성이 적은 알코올이 특히 적합하다. 이러한 바람직한 알코올의 예로서는, 디에틸렌 글리콜, 트리에틸렌 글리콜, 에틸렌 글리콜 모노부틸 에테르, 디에틸렌 글리콜 모노부틸 에테르, 트리에틸렌 모노부틸 에테르, 에틸렌 글리콜 모노헥실 에테르, 트리에틸렌 글리콜 모노헥실 에테르 또는 이들의 임의의 혼합물을 들 수 있으며, 가장 바람직하게는 디에틸렌 글리콜 모노부틸 에테르, 트리에틸렌 모노부틸 에테르, 또는 이들의 혼합물이다. 이들 알코올의 혼합 비율 결정은 다른 성분을 고정시키고, 계면활성제 성분과 알코올간의 비를 변화시키면서 단상의 에멀젼이 형성되는 영역을 관찰함으로서 결정하게 된다.Examples of the above alcohols that can be used in the present invention include ethanol, propanol, butanol, hexanol, isopropanol, heptanol, octanol, decanol, isohexanol, isooctanol, isodecanol, ethylene glycol, diethylene glycol, Triethylene glycol, ethylene glycol methyl ether, diethylene glycol methyl ether, triethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, triethylene glycol ethyl ether, ethylene glycol monopropyl ether, diethylene glycol monopropyl ether , Triethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol dibutyl ether, triethylene glycol dibutyl ether, ethylene glycol mono Hexyl ether, Diethylene glycol monohexyl ether, triethylene glycol monohexyl ether, or any mixtures thereof may be used, but short carbon alcohols are a high risk of fire and often remain in the waste liquid after cleaning, thus reducing the COD of the discharged water. There is a risk of increasing. Therefore, alcohols which improve the phase stability of the cleaning agent, and which have a high flash point of the alcohol itself, have a low risk of fire, are particularly suitable. Examples of such preferred alcohols include diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene monobutyl ether, ethylene glycol monohexyl ether, triethylene glycol monohexyl ether or any thereof Mixtures, most preferably diethylene glycol monobutyl ether, triethylene monobutyl ether, or mixtures thereof. Determination of the mixing ratio of these alcohols is made by fixing the other components and observing the region in which the single phase emulsion is formed while changing the ratio between the surfactant component and the alcohol.
도 2는 오일/비이온계면활성제/물 시스템에 보조 계면활성제로서 디에틸렌 글리콜 모노부틸 에테르(BDG)와 같은 에틸렌 글리콜계 보조제를 첨가했을 경우, 단상의 W/O 타입 에멀젼이 형성되는 온도의 영역이 넓어지는 것을 보여주고 있다.FIG. 2 shows the range of temperatures at which a single phase W / O type emulsion is formed when an ethylene glycol based adjuvant such as diethylene glycol monobutyl ether (BDG) is added as an auxiliary surfactant to an oil / nonionic surfactant / water system. It is showing this widening.
상기와 같은 결과로부터, 결론적으로 알코올/비이온 계면활성제의 비율이 0.50~1.50일 때 약 0℃~80 또는 90℃까지의 넓은 온도 영역에서 열역학적으로 안정한 에멀젼의 형성됨을 확인할 수 있다. 이들 알코올은 전조성 중 기준으로 0.01부피%~30부피%의 범위, 바람직하게는 3부피%~25부피%의 범위, 더욱 바람직하게는 5부피%~17부피%의 범위이다.From the above results, it can be concluded that when the ratio of alcohol / nonionic surfactant is 0.50 to 1.50, a thermodynamically stable emulsion is formed at a wide temperature range of about 0 ° C to 80 or 90 ° C. These alcohols are in the range of 0.01% to 30% by volume, preferably in the range of 3% to 25% by volume, more preferably in the range of 5% to 17% by volume in the preforming composition.
본 발명에 따른 세정제의 기본 조성에 세정제의 안정성 향상이나 세정제에 심각한 물성 변화를 주지 않는 범위 내에서의 소량의 기타 첨가제를 포함할 수 있다. 대표적인 첨가제로서는, 세정제의 방청 효과를 위한 방청제 및 산화방지제, 금속 세정을 위한 킬레이트제, 그리고 거품을 제거하기 위한 소포제 등을 적절한 양으로 배합 가능하며, 이 또한 본 발명의 영역 내이다. 전조성 기준으로 0.01중량%~5중량%의 범위, 바람직하게는 0.1중량%~1중량%의 범위, 더욱 바람직하게는 0.1중량%~0.5중량%의 범위로 배합될 수 있으나, 피세정물의 종류 및 목적, 그리고 세정 방식 등에 따라 그 배합량은 변화될 수 있다.The basic composition of the cleaning agent according to the present invention may include a small amount of other additives within the range of improving stability of the cleaning agent or not causing serious change in physical properties of the cleaning agent. Representative additives include rust inhibitors and antioxidants for the rust inhibiting effect of the detergents, chelating agents for metal cleaning, and antifoaming agents for removing foam, and the like, in an appropriate amount, which is also within the scope of the present invention. Although it can be formulated in the range of 0.01% to 5% by weight, preferably in the range of 0.1% to 1% by weight, more preferably in the range of 0.1% to 0.5% by weight based on the rollability, And the compounding amount may be changed depending on the purpose and the cleaning method.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하기로 하나, 하기한 실시예는 본 발명을 예증하기 위한 것일 뿐, 본 발명을 제한하는 것은 아님을 이해하여야만 할 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are only to illustrate the present invention, it should be understood that it does not limit the present invention.
실시예 1∼12 및 비교예 1∼4Examples 1-12 and Comparative Examples 1-4
테스트 시편(試片)의 준비: Preparation of test specimens :
아비에틴산(abietic acid) 4g을 10ml의 IPA(Isopropyl alcohol)에 용해시킨 후, 7.5×2.4×0.2cm3크기의 스테인레스 시편(SUS plate)에 얇게 도포하였다. 2시간~4시간 정도 실온에 방치한 후, 70℃~90℃의 오븐에서 12시간 정도 방치하였다.4 g of abienic acid was dissolved in 10 ml of Isopropyl alcohol (IPA), and then thinly coated on a stainless steel plate (7.5 plate) having a size of 7.5 × 2.4 × 0.2 cm 3 . After leaving at room temperature for 2 hours-4 hours, it was left to stand in 70 degreeC-90 degreeC oven for about 12 hours.
세정력 평가: Detergency rating :
세정 온도는 보편적으로 사용되는 온도인 40℃로 결정하였으며, 상기의 조성으로 제조된 마이크로에멀젼형 세정제 50ml에, 위의 방법으로 제작된 오염 시편을 침적시키고 각각 2분 간격으로 시간이 경과한 후, 상온의 증류수(전기전도도: 약 18㎲/cm)를 사용한 세정액 중에서 다시 각각 2분간 오염 시편을 침적시켰다. 그 다음, 약 2분간 온풍 건조시킨 후, 시편으로부터 제거된 오염원의 무게를 측정하여 세정력을 평가하였다.The cleaning temperature was determined to be 40 ° C., which is a commonly used temperature, and 50 ml of the microemulsion type detergent prepared in the above composition was dipped into the contaminated specimens prepared by the above method, and then each time was elapsed at 2 minute intervals. Contaminated specimens were further deposited for 2 minutes in a washing solution using distilled water (electric conductivity: about 18 mA / cm) at room temperature. Then, after drying for 2 minutes in warm air, the cleaning power was evaluated by measuring the weight of the contaminant removed from the specimen.
세정력 평가방법 및 평가기준: Detergency Evaluation Method and Criteria :
제거율(%)=(A-B)/A×100(식 중에서, A는 테스트 전에 부착된 오염원의 무게, B는 세정력 테스트 후에 부착된 오염원의 무게이다)% Removal = (A-B) / A x 100 (where A is the weight of the source attached before the test and B is the weight of the source attached after the cleaning test)
유수분리성 평가: Oil separability rating :
세정조에서의 유수분리성의 평가는 10g의 세정제와 0.3g의 플럭스, 절삭유 및, 그리스유를 혼합하여 오염액을 만든 후 증류수로 3%, 5%, 10%의 비율로 희석하여 세정수를 제조한 후, 각각을 25℃, 40℃, 60℃에서 25분 동안 정치시켜 물 층과 오염원 층을 분리 한 후 물층의 COD를 측정, 유수분리성을 평가하였다.Evaluation of oil separability in the washing tank was made by mixing 10 g of detergent, 0.3 g of flux, cutting oil, and grease oil to make a contaminated liquid, and then diluting it with distilled water at a ratio of 3%, 5%, and 10%. Then, each was allowed to stand at 25 ° C., 40 ° C., 60 ° C. for 25 minutes to separate the water layer and the contaminant layer, and the COD of the water layer was measured to evaluate oil / water separation.
유수분리성 평가방법 및 평가기준: Oil separability evaluation method and evaluation criteria :
유수분리성(%)=(A-B)/A×100(식 중에서, A는 유수분리 전의 COD, B는 유수분리후의 물층의 COD이다)Oily Water Separation (%) = (A-B) / A × 100 (wherein A is COD before oil separation and B is COD of water layer after oil separation)
상기한 표 3의 비교예 2~4의 경우 실시예 들과 비슷한 알코올/비이온 계면활성제의 비율을 나타내고 있으나, 비교예 2∼4는 리모넨 만을 사용한 경우로서 세정성은 우수하나 리모넨의 특이취로 작업성이 열등하다. 비교예 1의 경우에는 리모넨을 대체하여 탄화수소를 사용한 것으로서 리모넨의 냄새가 없고 따라서 작업성은 향상되나, 올레핀 계통의 탄화수소만으로 오일성분을 구성할 경우에는 오일 성분인아비에틴산을 세정시, 세정 초기 계면활성제와 오염원 간에 액정이 형성되고, 이후 어느 정도 시간이 경과한 이후에 세정이 되는 현상을 나타내므로 전체적으로 세정 효율이 저감되는 현상을 나타낸다. 본 발명의 실시예 1∼12의 조성물들은 올레핀계의 탄화수소와 이염기산 에스터의 혼합 오일을 사용한 경우이며, 이들 모두 초기 오염원과 계면활성제 간에 강고한 액정의 형성없이 세정이 진행되므로 빠른 세정 효율을 보여주고 있다. 또한, 세정조에서 세정수와 오염 성분의 분리가 우수하여 세정수의 사용량이 줄고, 전체적으로 운용비용이 감소하는 효과를 보여준다.In the case of Comparative Examples 2 to 4 of Table 3, the ratio of alcohol / nonionic surfactant similar to those of Examples is shown, but Comparative Examples 2 to 4 use only limonene, which is excellent in cleanability but workability due to the specific odor of limonene. This is inferior. In case of Comparative Example 1, hydrocarbon was used as a substitute for limonene, and the smell of limonene is improved, and thus workability is improved. However, when the oil component is composed of only olefinic hydrocarbons, when cleaning the oil component abietinic acid, A liquid crystal is formed between the activator and the contaminant, and since the cleaning is performed after a certain time has elapsed, the cleaning efficiency is reduced as a whole. The compositions of Examples 1 to 12 of the present invention are a case where a mixed oil of an olefin hydrocarbon and a dibasic acid ester is used, and all of them show fast cleaning efficiency because the cleaning proceeds without formation of a strong liquid crystal between the initial pollutant and the surfactant. Giving. In addition, the separation of the washing water and contaminants in the washing tank is excellent, reducing the amount of washing water used and reducing the overall operating cost.
전술한 바와 같이, 오일, 비이온 계면활성제, 물, 그리고 알코올 성분을 포함하는 열역학적으로 안정한 W/O 타입 마이크로에멀젼 타입의 본 발명에 따른 세정제는, 전자 부품 및/또는 정밀 부품 등의 표면에 묻어 있는 지방 및 오일, 기계유, 절삭유, 그리스, 광유, 액정(liquid crystal) 오염 등과 같은 다양한 오염물에 대한 넓은 세정 온도 범위에 걸쳐 세정력과 세정성(헹굼성)이 우수하며, 생분해성이 뛰어나 환경 안전성이 높고, 인체에 대하여 저독성이므로 작업 환경성도 양호하며, 특히, 세정조에서 오염원을 포함한 오일 성분과 물의 분리가 가능하여 폐수의 절감을 극대화할 수 있는 효과가 있으며, 초음파 세정, 침적 세정, 진동 세정, 그리고 스프레이 세정과 같은 다양한 세정 방법으로 세정이 가능한 세정제로서, 오존층 파괴물질인 CFCs를 대체할 수 있는 고성능 세정제이다.As described above, the cleaning agent according to the present invention of the thermodynamically stable W / O type microemulsion type containing an oil, a nonionic surfactant, water, and an alcohol component is applied to the surface of an electronic part and / or a precision part. Excellent cleaning power and rinsability over a wide cleaning temperature range for various contaminants such as fat and oil, machine oil, cutting oil, grease, mineral oil, liquid crystal contamination, etc. It is high and low toxicity to human body, so it has good working environment. In particular, it is possible to separate oil components and water including pollutants in the cleaning tank to maximize the reduction of waste water. Ultrasonic cleaning, deposition cleaning, vibration cleaning, In addition, the cleaning agent can be cleaned by various cleaning methods such as spray cleaning, and it can replace CFCs, which are ozone depleting substances. Is a high performance cleaner.
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| KR102183624B1 (en) | 2020-04-28 | 2020-11-27 | 주식회사 세이프코어 | Insulating detergent composition for cleaning current flowing equipment and industrial equipment, cleaning method and equipment using same |
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| KR100427759B1 (en) * | 2001-11-13 | 2004-04-28 | 주식회사 아담스테크놀로지 | Microemulsion typed detergent aqueous composition for liquid crystal display panel |
| JP2005162780A (en) * | 2003-11-28 | 2005-06-23 | Ibm Japan Ltd | Detergent composition and detergent for liquid crystal cell |
| CN101565831B (en) * | 2009-04-30 | 2012-01-18 | 深圳市科玺化工有限公司 | Cyclic renewable water-based cleaning agent and cyclic renewing technology |
| KR101366211B1 (en) * | 2011-10-13 | 2014-02-25 | 에이치플러스에코 주식회사 | Environmental friendly cleaning agents using vegetable oil |
| CN102994290A (en) * | 2012-12-06 | 2013-03-27 | 南通市华东润滑设备有限公司 | Washing agent for refrigerator |
| CN107130255A (en) * | 2017-06-08 | 2017-09-05 | 苏州龙腾万里化工科技有限公司 | A kind of circulation type cleaning agent for metal parts |
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| KR20020085156A (en) | 2002-11-16 |
| CN1384179A (en) | 2002-12-11 |
| CN1198914C (en) | 2005-04-27 |
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