EP0580721B1 - Method of cleaning painted hard surfaces with low voc cleaning compositions - Google Patents
Method of cleaning painted hard surfaces with low voc cleaning compositions Download PDFInfo
- Publication number
- EP0580721B1 EP0580721B1 EP92909867A EP92909867A EP0580721B1 EP 0580721 B1 EP0580721 B1 EP 0580721B1 EP 92909867 A EP92909867 A EP 92909867A EP 92909867 A EP92909867 A EP 92909867A EP 0580721 B1 EP0580721 B1 EP 0580721B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- surfactant
- microemulsion
- solvent
- water
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000004140 cleaning Methods 0.000 title claims description 27
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 66
- 239000004094 surface-active agent Substances 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002904 solvent Substances 0.000 claims abstract description 42
- 239000003960 organic solvent Substances 0.000 claims abstract description 29
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 13
- 239000004519 grease Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000000853 adhesive Substances 0.000 claims description 42
- 230000001070 adhesive effect Effects 0.000 claims description 42
- 239000002736 nonionic surfactant Substances 0.000 claims description 28
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 15
- 239000003093 cationic surfactant Substances 0.000 claims description 13
- 125000002091 cationic group Chemical group 0.000 claims description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 12
- 239000011707 mineral Substances 0.000 claims description 12
- 235000015096 spirit Nutrition 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 7
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 7
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 230000009965 odorless effect Effects 0.000 claims description 6
- 150000003138 primary alcohols Chemical class 0.000 claims description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- RJSZFSOFYVMDIC-UHFFFAOYSA-N tert-butyl n,n-dimethylcarbamate Chemical compound CN(C)C(=O)OC(C)(C)C RJSZFSOFYVMDIC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000003973 paint Substances 0.000 description 12
- 239000012855 volatile organic compound Substances 0.000 description 12
- 239000001993 wax Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- -1 grime Substances 0.000 description 9
- 239000004064 cosurfactant Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003599 detergent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 238000005406 washing Methods 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
- C11D17/0021—Aqueous microemulsions
-
- 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
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- 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
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- 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
- C11D1/835—Mixtures of non-ionic with cationic compounds
-
- 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
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/06—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using emulsions
-
- 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
- C11D1/02—Anionic compounds
-
- 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
- C11D1/38—Cationic compounds
-
- 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
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/75—Amino oxides
-
- 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
- C11D1/88—Ampholytes; Electroneutral compounds
Definitions
- This invention relates to methods for removing silicone wax, grease, grime, adhesives and the like from painted hard surfaces such as automobile finishes.
- VOCs Volatile Organic Compounds
- U.S. Patent No. 3,983,047 to Vinson describes a decal removal composition for loosening adhesive bonded to an airplane.
- the composition contains mostly organic solvent well above the regulated VOC limit and is a solvent mixture.
- U.S. Patent No. 4,146,499 to Rosano discloses a method of preparing microemulsions for a wide variety of applications including the use of hydrophobic substance such as hydrocarbon substances including mineral spirits for "their ability to dissolve most hydrophobic substance.”
- U.S. Patent No. 4,909,962 to Clark describes a composition used primarily for laundry pre-spotting that is a microemulsion comprising organic solvent and a selection of nonionic surfactants and cosolvents.
- Component C of this composition is a supplementary nonionic surfactant comprising an amine oxide or an alkyl phenol ethoxylate. See especially col. 2, line 59 and Examples 7 and 8 at col. 8.
- These compositions are specifically intended to be used on fabrics that will be followed by a regular washing, thereby infinitely diluting the composition with a water ratio of at least 100 parts water to 1 part composition.
- the optional use of these compositions as all-purpose cleaners for hard surfaces is disclosed at column 3, lines 21 to 30.
- U.S. Patent No. 4,370,174 to Brathwaite, Jr. discloses a method for removing adhesive residues using an emulsion cleaner.
- the composition used comprises an organic solvent, a minor amount of an inorganic solid absorbent powder, an water-in-oil surfactant and an oil-in-water surfactant sufficient to reverse the emulsion to a water external phase upon addition of water.
- the emulsion was initially provided in an oil external phase because it was believed that this was necessary to insure that the organic solvent was exposed to the adhesive residue.
- These compositions are applied to flooring surfaces as a preparation for subsequent application of adhesives.
- the compositions are poured directly on the surface to be cleaned and allowed to dissolve the adhesive for about 10 to 30 minutes.
- EP-A-0 384 715 describes a light-duty microemulsion detergent composition which is said to be useful in diluted form for hand-washing dishes and, in neat form, as a laundry pre-spotter.
- the oil-in-water microemulsion is also applied in neat form to greasy dishes, roasting pans etc. which are thereafter washed with water.
- the microemulsion liquid detergent composition includes a moderately water soluble complex of anionic and cationic surfactants, in which complex the anionic and cationic moieties are in essentially equivalent or equimolar proportions, an anionic detergent, a co-surfactant, an organic solvent and water.
- compositions to clean difficult-to-remove contaminants from hard surfaces safely while at the same time satisfying stringent VOC requirements.
- Such compositions preferably should be easily removed from the surface to be cleaned so as not to leave any residue.
- Water-based cleaners may be washed from the surface to be cleaned with excess water, but this is undesirable because this process requires an additional step and can leave water running from the interstices of joints in the structure that must be dried before painting. Water flushing is particularly undesirable when cleaning automobile surfaces for refinishing.
- the present invention provides a method of removing silicone wax, grease, grime, and adhesives from painted hard surfaces with an oil-in-water microemulsion comprising applying to such surfaces an effective amount of a composition comprising an organic solvent or solvent blend having a solubility parameter of between 6.9 and 8.9 (cal/cm 3 ) 1 ⁇ 2 , sufficient surfactant to support a stable microemulsion, and water in an amount sufficient to provide a total VOC content of less than 200 grams/liter.
- the microemulsion is allowed to soften and otherwise ease removal of the silicone wax, grease, grime, and the like from the surface.
- the microemulsion and the residue are removed from the surface by wiping with a dry wiping material.
- microemulsion used in the present method yields surprising cleaning power with a small amount of volatile organic solvent, and without the need for large amounts of detergent, harsh pH conditions or the like.
- the method of the present invention is specifically adapted to the particular performance requirements of the operation to be performed.
- the surface to be cleaned is soiled by oil, grease, wax or the like and is to be repainted or otherwise refinished
- Such cleaning is particularly important in the repainting of automobile surfaces.
- residues will lead to "fish eyes,” or noticeable bumps in the painted surface.
- the microemulsion when used in accordance with the present invention, may be applied to the surface to be treated and effectively wiped away using only a dry wiping material. No additional cleanup, such as a water wash, is required to remove any trace cleaner.
- the standard of desired cleaning may not need to be as high as for surfaces to be repainted, because adhesive will likely be applied to the same surface. In such applications, however, good cleaning is still important to avoid adhesive failure due to adhesive or surfactant residue remaining on the surface.
- the microemulsion is applied to the surface to be treated and effectively wiped away using only a dry wiping material without additional cleanup.
- the oil-in-water microemulsion used in the present invention provides good cleaning action while at the same time satisfying environmental standards for VOCs.
- the organic solvent also does not evaporate rapidly because it is contained within discontinuous droplets distributed in the continuous aqueous phase, and is not present in quantity at the liquid-air interphase.
- the lower evaporation rate of the organic solvent is further advantageous, because tenacious waxy or adhesive residues are allowed to soak in the solvent prior to removal.
- Environmental compatibility of the microemulsion may be further improved with the choice of nontoxic organic components and biodegradable surfactants. Judicious choice of components also may render the microemulsion nonflammable for easier compliance with shipping regulations.
- Residue may be more easily removed from the surface to be cleaned using the oil-in-water microemulsions by simple dry wiping techniques than using a solvent-based or water-in-oil based system. Ease in cleanup provides significant advantages both in labor-saving and a more acceptable final product.
- the microemulsion used in the present invention is an oil-in-water microemulsion.
- Such microemulsions typically contain dispersed droplets of oil in the range of 50-1500 ⁇ in diameter, which is visibly transparent or translucent.
- the microemulsion is formed spontaneously, i.e., without any energy input, with the proper selection of oil, water and surfactant components.
- the organic solvent component of the microemulsion is an organic solvent or solvent blend having a solubility parameter of between 6.9 and 8.9.
- the specific solvent or solvent blend and the concentration of the solvent to be used is selected on the basis of the proposed application. In case of applications of cleaning silicone wax, grease, or grime a low concentration of a mild hydrocarbon such as odorless mineral spirits is most suitable for cost concerns and minimal effect on fresh paint finishes. In case of adhesive remover applications where a more aggressive cleaning action is required, a higher concentration of a more aggressive organic solvent or solvent blend is preferred.
- the solvent selected should preferably have a solubility parameter of between 7.5 and 8.9 (cal/cm 3 ) 1 ⁇ 2 .
- Preferred aggressive solvents or solvent blends comprise at least 5% by weight of the solvent ingredient of a polar or aromatic component.
- a polar component examples include butyl acetate, acetone, glycol ether, alcohols or the like.
- the aromatic component may be toluene, xylene, naphthalene or aromatic mineral spirits.
- Suitable microemulsions typically comprise:
- the microemulsion comprises a blend of surfactants to enhance stability of the composition.
- Blends of surfactants are generally more efficient in providing stability, and thus need not be provided in as large amounts as a single surfactant.
- the surfactants typically are of diverse chemical classes, selected from cationic, zwitterionic, anionic and nonionic surfactants.
- the surfactants are selected from the nonionic surfactants, together with another surfactant selected from cationic, zwitterionic and anionic surfactants.
- the combination of cationic or zwitterionic surfactants with nonionic surfactants provides a wide range of temperature stability to the microemulsion and a low surfactant concentration.
- the surfactants serve both as emulsifiers and, to some extent, as cleaning agents.
- the surfactant combination is preferably chosen based on its removability from the surface or compatibility with subsequently applied paints and biodegradability.
- the preferred HLB of the nonionic surfactant is determined by the choice of organic solvent components and is selected to be higher than 7 to enable a spontaneously formed oil-in-water emulsion.
- Cationic or zwitterionic surfactants such as amines and their salts, quaternary ammonia salts, amine oxides, or other cationic surfactants known in the art, may be used.
- Alkylamine oxides such as cocodimethylamine oxide or lauryldimethylamine oxide, are preferred because of their low toxicity.
- Typical nonionic surfactants that may be used in the microemulsions include the polyoxyethylene surfactants, such as polyethoxylated alkyphenols and polyethoxylated linear or branched primary or secondary alcohols; the carboxylic acid esters, such as glycerol esters, polyoxyethylene esters, ethoxylated anhydrosorbitol esters, ethoxylated natural fats, oils and waxes and glycol esters of fatty acids; the carboxylic amides, such as diethanolamine condensates, monoalkanolamine condensates, polyoxyethylene fatty acid amides; and the polyalkylene oxide block copolymers, such as PluronicTM line of surfactants from BASF Corp.
- Polyethoxylated linear alcohols such as NeodolTM manufactured by Shell Chemicals and TergitolTM manufactured by Union Carbide Company, are preferred as most biodegradable.
- the microemulsion also comprises a co-surfactant to aid the solubilization of the surfactants in the solvent, to minimize gelation during phase transition, and to provide transparency and low viscosity of the microemulsion.
- the co-surfactant is chosen based on its polarity as well as low toxicity and flammability.
- Mid chain length alcohols such as n-propanol, n-butanol, pentanol, glycols; such as propylene glycol, or glycol ethers; such as dipropylene glycol methyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, ethylene glycol butyl ether can be used.
- an alcohol which also acts as a solvent is additionally advantageous especially in case of the adhesive remover application.
- the solvent or solvent blend is mixed with an amount of cosurfactant equal or slightly less than the amount of surfactant to be used in the ultimate composition.
- the cationic and nonionic surfactants are added to the solvent mixture, and the resultant mixture stirred well. Water is added in aliquots with gentle stirring after each addition until the viscosity has increased and subsequently decreased to indicate a phase transition from water-in-oil to oil-in-water. From this point on, water can be added rapidly in an amount to provide the concentration desired.
- the appropriate ratio of surfactants and amount of cosurfactant is determined through routine experimentation, reducing the amount of comparatively expensive ingredients as taught herein as possible for the particular solvent or solvent blend used.
- the ratio of cationic to nonionic surfactant can be adjusted to minimize the total amount of necessary surfactant. Generally, when less cationic surfactant is used, the total amount of surfactant must be increased.
- the cosurfactant is preferably added before the addition of water because it aids the solubilization of the surfactants in the solvent and minimizes gelation during the phase transition.
- the amount of cosurfactant to be used is adjusted to provide transparency and low viscosity.
- the formulation is adjusted by changing the ratios of surfactants in the formulation. Once the ratio of surfactant and cosurfactant has been established, the concentration of each component can be lowered or raised in relationship to the solvent to optimize stability and performance.
- microemulsion Once a satisfactory formulation for the microemulsion has been determined, usually no special techniques for mixing are required. All of the ingredients may be added in any order and mixed to form the microemulsion as taught herein.
- Preferred microemulsions comprise by weight:
- a milder, less expensive yet effective cleaning solution is preferably provided by a composition comprising by weight: 5-8% aliphatic organic solvent, 1-3% co-surfactant, 3-5% amine oxide surfactant, 2-4% nonionic surfactant having an HLB of between 7.5 and 10, and 80-89% deionized water to total 100%.
- a stronger cleaning solution is preferably provided by a composition comprising by weight: 12-15% organic solvent having at least 5% aromatic or polar components, 1-4% co-surfactant, 8-12% amine oxide surfactant, 5-7% nonionic surfactant having an HLB of between 7.5 and 10, and 62-74% deionized water to total 100%.
- An example of a mild cleaning solution composition 5-8% odorless mineral spirits, 1-3% n-propanol, 3-5% 30% active laurylamine oxide, 2-4% polyethoxylated linear primary alcohol, and 80-89% deionized water to total 100%.
- An example of a stronger cleaning solution composition 12-15% aromatic mineral spirits, 1-4% dipropylene glycol methyl ether, 8-12% 30% active laurylamine oxide, 5-7% polyethoxylated linear primary alcohol, and 62-74% deionized water to total 100%.
- the microemulsion can be applied with a pump spray, aerosol, or by wiping a rag, or preferably a highly absorbent, nonwoven pad, which can be rubbed onto the surface to be cleaned. Because of its low volatility, the microemulsion can be left on the surface to soak the contaminant if necessary. A clean rag or nonwoven pad can be used to wipe up the dissolved soil. Physical wiping of the substrate assures that all of the residue is actually removed and not merely redeposited on drying of the cleaner.
- the characteristics of the wiping material are chosen to act as a carrier for the application of the microemulsion to the surface to be cleaned. This material must be soft enough as not to scratch the surface, non-linting and absorbent enough to hold sufficient quantities of soil/microemulsion.
- the preferred wiping material is a surfactant-treated polypropylene nonwoven wiper.
- Adhesive can be quickly removed if its bulk has been previously removed mechanically.
- the bulk of the adhesive is removed with a 3M Striping and Molding Adhesive Removal Disc, which is a commercially available elastomeric disc that is rotatable about its axis. These disks rub off adhesive residues without harming the underlying finish by frictional contact with the peripheral surface of the disk.
- a portion of the peripheral surface of the disk is attributed to provide a renewed peripheral surface of the elastomer.
- a transparent microemulsion was prepared by combining the following ingredients and stirring. 6.1 wt% Odorless Mineral Spirits (Unocal® 1241, Union Oil Co.) Unocal Corporation. 1.5 n-propanol 4.4 Mackamine LO® 30% active (a laurylamine oxide surfactant from McIntyre Chem Co.) 2.4 Tergitol 15-S-3® (a nonionic surfactant from Union Carbide Corporation) 85.5 deionized water
- a transparent microemulsion was prepared by combining the following ingredients and stirring.
- composition of example 2 was used to remove the following adhesives baked 65.5°C (150°F) three hours onto a painted test panel that is a cold rolled steel panel painted with a base coat/clear coat paint system from DuPont, commercially available from Advanced Coating Technology, Inc. ScotchMount® 06378 ScotchMount® 06381 ScotchCal® A-1 3M Weather Stripping Adhesive 08011 3M General Trim Adhesive
- adhesives represent acrylate, styrene butadiene, and Neoprene type adhesives.
- the bulk of adhesive was removed with the SCOTCH-BRITE® Molding Adhesive and Stripe Removal Discs, deliberately leaving white smears of adhesive to better challenge the microemulsion adhesive cleaner.
- a hand size pad of nonwoven material as moistened with the microemulsion and rubbed for a maximum of five minutes or until the adhesive was removed from an approximate 2.26 x 10 -3 m 2 (3.5 square inch) area.
- microemulsions were prepared and used to remove the following adhesives after the bulk of adhesive was removed with 3M Striping and Molding Adhesive Removal Discs. Smears of adhesive were deliberately left on the surface to be cleaned to better challenge the power of the microemulsion adhesive remover.
- This example shows the variety of organic solvents that can be microemulsified with this basic formulation and their comparative efficiencies.
- microemulsions were prepared using 14.2 wt. % Unocal 75® solvent, the surfactants listed below and the balance of water. Amount of Each Component in weight % Cosurfactants Surfactant 1 Surfactant 2 a) Propylene Glycol 4.4 Triton N-57® 6.0 Mackamine LO® 7.6 b) DiPropylene Glycol 4.6 Triton N-57® 6.0 Mackamine LO® 7.6 c) Diethylene Glycol butyl ether 3.5 Triton N-57® 6.0 Mackamine LO® 6.0 d) N-propanol 3.6 Triton N-57® 6.0 Mackamine LO® 7.6
- microemulsions were prepared using several more biodegradable nonionic surfactants and balanced with water.
- compositions to clean a silicone and wax contaminated automobile panel was evaluated by the following technique.
- Commercial silicone and/or wax containing polishes were applied to painted panels according to directions of the manufacturer to provide a contaminated surface.
- the microemulsion was applied to a clean, dry pad, wiped onto the contaminated surface and wiped off with a second clean, dry pad.
- the panel was then repainted and the quality of the paint finish evaluated by counting the number of "fish eye” caused by poor filming and adhesion and by the cross-hatch adhesion test (ASTM D3359).
- a control section was cleaned by Ditzler DX330®, a commercial, pure solvent prep solvent.
- Ditzler DX-330 - apply about 4 grams to Scott WypAllTM towel and apply to wax panel - wipe off with clean, dry Scott WypAll.
- Example 1 apply about 5 grams to Scott WypAll towel and apply to waxed panel - wipe off with clean, dry WypAll towel.
- DuPont Prep Solvent II apply about 5 grams with Scott WypAll towel - let stand about 2 minutes - remove with wet WypAll towel followed by dry WypAll towel.
- BASF same as DuPont Prep Solvent II, except use two wet wipes.
- the best cleaner is Ditzler DX-330, which is a standard solvent cleaner and does not comply with VOC standards.
- Example 1 compares favorably with the other low VOC cleaners, but accomplishes this cleaning in one step rather than two steps.
- Example 1 performed as well or better than other low VOC prep solvents.
- the stability of the experimental microemulsions was tested by subjecting samples to a minimum of three freeze-thaw cycles and to a minimum of one week at 50°C. Although some samples would separate into distinct phase, the transparent microemulsion could be restored with mild shaking.
- Droplet particle size was determined by dynamic light scattering using a Malvern Photon Correlation Spectrometer.
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Abstract
Description
- This invention relates to methods for removing silicone wax, grease, grime, adhesives and the like from painted hard surfaces such as automobile finishes.
- Currently, contaminants are removed from hard surfaces such as automobile finishes with cleaning fluids that are predominately organic solvents. These solvents are now being regulated because of their effect on air quality. Specifically, the South Coast Air Quality Management District and Bay Areas of California have issued rules defining the amount of Volatile Organic Compounds (VOCs) which may be present in certain materials whose vapors may be discharged into the atmosphere. Additionally, organic solvents suffer from the disadvantage that they may evaporate before there is an opportunity to wipe it off. Premature evaporation may leave soil residues on the surface to be cleaned.
- U.S. Patent No. 4,446,044 to Rutkiewic, et. al. describes a water-in-oil emulsion, used as a cleaning fluid for automotive finish surfaces. Rutkiewic, et. al. make the explicit statement at column 3, lines 23-26 that "in order for this particular emulsion to be efficacious as a cleaner, it is necessary that the water, not the organic solvent, constitute the internal phase." This suggests that the emulsion must be of the water-in-oil type for effective cleaning.
- U.S. Patent No. 3,983,047 to Vinson describes a decal removal composition for loosening adhesive bonded to an airplane. The composition contains mostly organic solvent well above the regulated VOC limit and is a solvent mixture.
- U.S. Patent No. 4,146,499 to Rosano discloses a method of preparing microemulsions for a wide variety of applications including the use of hydrophobic substance such as hydrocarbon substances including mineral spirits for "their ability to dissolve most hydrophobic substance."
- U.S. Patent No. 4,909,962 to Clark describes a composition used primarily for laundry pre-spotting that is a microemulsion comprising organic solvent and a selection of nonionic surfactants and cosolvents. Component C of this composition is a supplementary nonionic surfactant comprising an amine oxide or an alkyl phenol ethoxylate. See especially col. 2, line 59 and Examples 7 and 8 at col. 8. These compositions are specifically intended to be used on fabrics that will be followed by a regular washing, thereby infinitely diluting the composition with a water ratio of at least 100 parts water to 1 part composition. The optional use of these compositions as all-purpose cleaners for hard surfaces is disclosed at column 3, lines 21 to 30.
- U.S. Patent No. 4,370,174 to Brathwaite, Jr. discloses a method for removing adhesive residues using an emulsion cleaner. The composition used comprises an organic solvent, a minor amount of an inorganic solid absorbent powder, an water-in-oil surfactant and an oil-in-water surfactant sufficient to reverse the emulsion to a water external phase upon addition of water. The emulsion was initially provided in an oil external phase because it was believed that this was necessary to insure that the organic solvent was exposed to the adhesive residue. These compositions are applied to flooring surfaces as a preparation for subsequent application of adhesives. The compositions are poured directly on the surface to be cleaned and allowed to dissolve the adhesive for about 10 to 30 minutes.
- EP-A-0 384 715 describes a light-duty microemulsion detergent composition which is said to be useful in diluted form for hand-washing dishes and, in neat form, as a laundry pre-spotter. The oil-in-water microemulsion is also applied in neat form to greasy dishes, roasting pans etc. which are thereafter washed with water. The microemulsion liquid detergent composition includes a moderately water soluble complex of anionic and cationic surfactants, in which complex the anionic and cationic moieties are in essentially equivalent or equimolar proportions, an anionic detergent, a co-surfactant, an organic solvent and water.
- There is a need in the art for a composition to clean difficult-to-remove contaminants from hard surfaces safely while at the same time satisfying stringent VOC requirements. Such compositions preferably should be easily removed from the surface to be cleaned so as not to leave any residue. Water-based cleaners may be washed from the surface to be cleaned with excess water, but this is undesirable because this process requires an additional step and can leave water running from the interstices of joints in the structure that must be dried before painting. Water flushing is particularly undesirable when cleaning automobile surfaces for refinishing.
- The present invention provides a method of removing silicone wax, grease, grime, and adhesives from painted hard surfaces with an oil-in-water microemulsion comprising applying to such surfaces an effective amount of a composition comprising an organic solvent or solvent blend having a solubility parameter of between 6.9 and 8.9 (cal/cm3)½, sufficient surfactant to support a stable microemulsion, and water in an amount sufficient to provide a total VOC content of less than 200 grams/liter. The microemulsion is allowed to soften and otherwise ease removal of the silicone wax, grease, grime, and the like from the surface. The microemulsion and the residue are removed from the surface by wiping with a dry wiping material.
- The microemulsion used in the present method yields surprising cleaning power with a small amount of volatile organic solvent, and without the need for large amounts of detergent, harsh pH conditions or the like.
- The method of the present invention is specifically adapted to the particular performance requirements of the operation to be performed. Thus, where the surface to be cleaned is soiled by oil, grease, wax or the like and is to be repainted or otherwise refinished, it is particularly important to provide cleaning that will leave no trace of residue of either the soil or the cleaning agent itself. Such cleaning is particularly important in the repainting of automobile surfaces. Such residues will lead to "fish eyes," or noticeable bumps in the painted surface. The microemulsion, when used in accordance with the present invention, may be applied to the surface to be treated and effectively wiped away using only a dry wiping material. No additional cleanup, such as a water wash, is required to remove any trace cleaner. When a surface that is soiled with adhesive is to be cleaned, the standard of desired cleaning may not need to be as high as for surfaces to be repainted, because adhesive will likely be applied to the same surface. In such applications, however, good cleaning is still important to avoid adhesive failure due to adhesive or surfactant residue remaining on the surface. Here again, the microemulsion is applied to the surface to be treated and effectively wiped away using only a dry wiping material without additional cleanup.
- The oil-in-water microemulsion used in the present invention provides good cleaning action while at the same time satisfying environmental standards for VOCs. The organic solvent also does not evaporate rapidly because it is contained within discontinuous droplets distributed in the continuous aqueous phase, and is not present in quantity at the liquid-air interphase. The lower evaporation rate of the organic solvent is further advantageous, because tenacious waxy or adhesive residues are allowed to soak in the solvent prior to removal. Environmental compatibility of the microemulsion may be further improved with the choice of nontoxic organic components and biodegradable surfactants. Judicious choice of components also may render the microemulsion nonflammable for easier compliance with shipping regulations.
- Residue may be more easily removed from the surface to be cleaned using the oil-in-water microemulsions by simple dry wiping techniques than using a solvent-based or water-in-oil based system. Ease in cleanup provides significant advantages both in labor-saving and a more acceptable final product.
- The microemulsion used in the present invention is an oil-in-water microemulsion. Such microemulsions typically contain dispersed droplets of oil in the range of 50-1500Å in diameter, which is visibly transparent or translucent. The microemulsion is formed spontaneously, i.e., without any energy input, with the proper selection of oil, water and surfactant components.
- The organic solvent component of the microemulsion is an organic solvent or solvent blend having a solubility parameter of between 6.9 and 8.9. The specific solvent or solvent blend and the concentration of the solvent to be used is selected on the basis of the proposed application. In case of applications of cleaning silicone wax, grease, or grime a low concentration of a mild hydrocarbon such as odorless mineral spirits is most suitable for cost concerns and minimal effect on fresh paint finishes. In case of adhesive remover applications where a more aggressive cleaning action is required, a higher concentration of a more aggressive organic solvent or solvent blend is preferred. The solvent selected should preferably have a solubility parameter of between 7.5 and 8.9 (cal/cm3)½. Preferred aggressive solvents or solvent blends comprise at least 5% by weight of the solvent ingredient of a polar or aromatic component. Examples of such a polar component include butyl acetate, acetone, glycol ether, alcohols or the like. The aromatic component may be toluene, xylene, naphthalene or aromatic mineral spirits.
- Suitable microemulsions typically comprise:
- a) an organic solvent or solvent blend having a solubility parameter of between 6.9 and 8.9 (cal/cm3)½,
- b) sufficient nonionic surfactant or nonionic surfactant blend to maintain a microemulsion, and
- c) water in an amount sufficient to provide a total VOC content of less than 200 grams/liter.
- More typically, the microemulsion comprises a blend of surfactants to enhance stability of the composition. Blends of surfactants are generally more efficient in providing stability, and thus need not be provided in as large amounts as a single surfactant. The surfactants typically are of diverse chemical classes, selected from cationic, zwitterionic, anionic and nonionic surfactants. Preferably, the surfactants are selected from the nonionic surfactants, together with another surfactant selected from cationic, zwitterionic and anionic surfactants.
- The combination of cationic or zwitterionic surfactants with nonionic surfactants provides a wide range of temperature stability to the microemulsion and a low surfactant concentration.
- The surfactants serve both as emulsifiers and, to some extent, as cleaning agents. The surfactant combination is preferably chosen based on its removability from the surface or compatibility with subsequently applied paints and biodegradability. The preferred HLB of the nonionic surfactant is determined by the choice of organic solvent components and is selected to be higher than 7 to enable a spontaneously formed oil-in-water emulsion.
- Cationic or zwitterionic surfactants, such as amines and their salts, quaternary ammonia salts, amine oxides, or other cationic surfactants known in the art, may be used. Alkylamine oxides, such as cocodimethylamine oxide or lauryldimethylamine oxide, are preferred because of their low toxicity.
- Typical nonionic surfactants that may be used in the microemulsions include the polyoxyethylene surfactants, such as polyethoxylated alkyphenols and polyethoxylated linear or branched primary or secondary alcohols; the carboxylic acid esters, such as glycerol esters, polyoxyethylene esters, ethoxylated anhydrosorbitol esters, ethoxylated natural fats, oils and waxes and glycol esters of fatty acids; the carboxylic amides, such as diethanolamine condensates, monoalkanolamine condensates, polyoxyethylene fatty acid amides; and the polyalkylene oxide block copolymers, such as Pluronic™ line of surfactants from BASF Corp. Polyethoxylated linear alcohols, such as Neodol™ manufactured by Shell Chemicals and Tergitol™ manufactured by Union Carbide Company, are preferred as most biodegradable.
- Most preferably, the microemulsion also comprises a co-surfactant to aid the solubilization of the surfactants in the solvent, to minimize gelation during phase transition, and to provide transparency and low viscosity of the microemulsion. The co-surfactant is chosen based on its polarity as well as low toxicity and flammability. Mid chain length alcohols; such as n-propanol, n-butanol, pentanol, glycols; such as propylene glycol, or glycol ethers; such as dipropylene glycol methyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, ethylene glycol butyl ether can be used. The use of an alcohol which also acts as a solvent is additionally advantageous especially in case of the adhesive remover application. An inflammable, low toxic glycol ether, such as dipropylene monoethyl ether, is preferred especially in the adhesive remover formulation which has a higher concentration of organic components.
- To formulate experimental microemulsions, the solvent or solvent blend is mixed with an amount of cosurfactant equal or slightly less than the amount of surfactant to be used in the ultimate composition. The cationic and nonionic surfactants are added to the solvent mixture, and the resultant mixture stirred well. Water is added in aliquots with gentle stirring after each addition until the viscosity has increased and subsequently decreased to indicate a phase transition from water-in-oil to oil-in-water. From this point on, water can be added rapidly in an amount to provide the concentration desired.
- The appropriate ratio of surfactants and amount of cosurfactant is determined through routine experimentation, reducing the amount of comparatively expensive ingredients as taught herein as possible for the particular solvent or solvent blend used. The ratio of cationic to nonionic surfactant can be adjusted to minimize the total amount of necessary surfactant. Generally, when less cationic surfactant is used, the total amount of surfactant must be increased. The cosurfactant is preferably added before the addition of water because it aids the solubilization of the surfactants in the solvent and minimizes gelation during the phase transition. The amount of cosurfactant to be used is adjusted to provide transparency and low viscosity. If the amount of necessary cosurfactant exceeds the desired VOC, the formulation is adjusted by changing the ratios of surfactants in the formulation. Once the ratio of surfactant and cosurfactant has been established, the concentration of each component can be lowered or raised in relationship to the solvent to optimize stability and performance.
- Once a satisfactory formulation for the microemulsion has been determined, usually no special techniques for mixing are required. All of the ingredients may be added in any order and mixed to form the microemulsion as taught herein.
- Preferred microemulsions comprise by weight:
- a) 5-15% of an organic solvent or solvent blend having a solubility parameter of between 6.9 and 8.9 (cal/cm3)½,
- b) 8-12% of a cationic or zwitterionic surfactant,
- c) 4-8% of a nonionic surfactant or nonionic surfactant blend having an HLB of between 7.5 and 10,
- d) 1-5% of a co-surfactant, and
- e) 50-82% of water, such that the total VOC content of the microemulsion is less than 200 grams/liter.
- Where the microemulsion is to be used for cleaning silicone wax, grease, and grime from hard surfaces to be repainted, a milder, less expensive yet effective cleaning solution is preferably provided by a composition comprising by weight:
5-8% aliphatic organic solvent, 1-3% co-surfactant, 3-5% amine oxide surfactant, 2-4% nonionic surfactant having an HLB of between 7.5 and 10, and 80-89% deionized water to total 100%. - Where the microemulsion is to be used for cleaning adhesives from hard surfaces, a stronger cleaning solution is preferably provided by a composition comprising by weight:
12-15% organic solvent having at least 5% aromatic or polar components, 1-4% co-surfactant, 8-12% amine oxide surfactant, 5-7% nonionic surfactant having an HLB of between 7.5 and 10, and 62-74% deionized water to total 100%. - An example of a mild cleaning solution composition:
5-8% odorless mineral spirits, 1-3% n-propanol, 3-5% 30% active laurylamine oxide, 2-4% polyethoxylated linear primary alcohol, and 80-89% deionized water to total 100%. - An example of a stronger cleaning solution composition:
12-15% aromatic mineral spirits, 1-4% dipropylene glycol methyl ether, 8-12% 30% active laurylamine oxide, 5-7% polyethoxylated linear primary alcohol, and 62-74% deionized water to total 100%. - The microemulsion can be applied with a pump spray, aerosol, or by wiping a rag, or preferably a highly absorbent, nonwoven pad, which can be rubbed onto the surface to be cleaned. Because of its low volatility, the microemulsion can be left on the surface to soak the contaminant if necessary. A clean rag or nonwoven pad can be used to wipe up the dissolved soil. Physical wiping of the substrate assures that all of the residue is actually removed and not merely redeposited on drying of the cleaner. The characteristics of the wiping material are chosen to act as a carrier for the application of the microemulsion to the surface to be cleaned. This material must be soft enough as not to scratch the surface, non-linting and absorbent enough to hold sufficient quantities of soil/microemulsion. The preferred wiping material is a surfactant-treated polypropylene nonwoven wiper.
- Adhesive can be quickly removed if its bulk has been previously removed mechanically. Preferably, the bulk of the adhesive is removed with a 3M Striping and Molding Adhesive Removal Disc, which is a commercially available elastomeric disc that is rotatable about its axis. These disks rub off adhesive residues without harming the underlying finish by frictional contact with the peripheral surface of the disk. During the removal of adhesive step, a portion of the peripheral surface of the disk is attributed to provide a renewed peripheral surface of the elastomer. After cleaning with the emulsion according to the method of the present invention, the surface is surprisingly clean and requires no further cleaning step before repainting or reapplying decals, molding, striping, etc.
- The following non-limiting examples are provided to illustrate the present invention.
- A transparent microemulsion was prepared by combining the following ingredients and stirring.
6.1 wt% Odorless Mineral Spirits (Unocal® 1241, Union Oil Co.) Unocal Corporation. 1.5 n-propanol 4.4 Mackamine LO® 30% active (a laurylamine oxide surfactant from McIntyre Chem Co.) 2.4 Tergitol 15-S-3® (a nonionic surfactant from Union Carbide Corporation) 85.5 deionized water -
- The composition of example 2 was used to remove the following adhesives baked 65.5°C (150°F) three hours onto a painted test panel that is a cold rolled steel panel painted with a base coat/clear coat paint system from DuPont, commercially available from Advanced Coating Technology, Inc.
ScotchMount® 06378 ScotchMount® 06381 ScotchCal® A-1 3M Weather Stripping Adhesive 08011 3M General Trim Adhesive - These adhesives represent acrylate, styrene butadiene, and Neoprene type adhesives. The bulk of adhesive was removed with the SCOTCH-BRITE® Molding Adhesive and Stripe Removal Discs, deliberately leaving white smears of adhesive to better challenge the microemulsion adhesive cleaner. A hand size pad of nonwoven material as moistened with the microemulsion and rubbed for a maximum of five minutes or until the adhesive was removed from an approximate 2.26 x 10-3 m2 (3.5 square inch) area.
- The following microemulsions were prepared and used to remove the following adhesives after the bulk of adhesive was removed with 3M Striping and Molding Adhesive Removal Discs. Smears of adhesive were deliberately left on the surface to be cleaned to better challenge the power of the microemulsion adhesive remover.
- This example shows the variety of organic solvents that can be microemulsified with this basic formulation and their comparative efficiencies.
- The following microemulsions were prepared using 14.2 wt. % Unocal 75® solvent, the surfactants listed below and the balance of water.
Amount of Each Component in weight % Cosurfactants Surfactant 1 Surfactant 2 a) Propylene Glycol 4.4 Triton N-57® 6.0 Mackamine LO® 7.6 b) DiPropylene Glycol 4.6 Triton N-57® 6.0 Mackamine LO® 7.6 c) Diethylene Glycol butyl ether 3.5 Triton N-57® 6.0 Mackamine LO® 6.0 d) N-propanol 3.6 Triton N-57® 6.0 Mackamine LO® 7.6 - The following microemulsions were prepared using several more biodegradable nonionic surfactants and balanced with water.
- In the table below, the abbreviations are:
- U75 =
- Unocal 75®, 7.5% aromatic mineral spirits commercially available from Unocal Corporation.
- U1241 =
- Unocal 1241®, odorless mineral spirits commercially available from Unocal Corporation.
- DPM =
- dipropylene glycol methyl ether.
- n-pro =
- n-propanol.
- T15-S-3 =
- Triton 15-S-3®, a nonionic surfactant from Union Carbide Corporation.
- Neo 91-6 =
- Neodol 91-6®, a nonionic surfactant from Shell Oil Co.
- T15-S-5 =
- Triton 15-S-5®, a nonionic surfactant from Union Carbide Corporation.
- Neo 23-3 =
- Neodol 23-3®, a nonionic surfactant from Shell Oil Co.
- The ability of compositions to clean a silicone and wax contaminated automobile panel was evaluated by the following technique. Commercial silicone and/or wax containing polishes were applied to painted panels according to directions of the manufacturer to provide a contaminated surface. The microemulsion was applied to a clean, dry pad, wiped onto the contaminated surface and wiped off with a second clean, dry pad. The panel was then repainted and the quality of the paint finish evaluated by counting the number of "fish eye" caused by poor filming and adhesion and by the cross-hatch adhesion test (ASTM D3359). A control section was cleaned by Ditzler DX330®, a commercial, pure solvent prep solvent.
- Painted steel panels, 25.4 cm x 122 cm, were waxed with either DuPont Rain Dance™ paste wax or 3M Liquid Polish, PN 05993. The waxed panels were conditioned at room temperature for 7 days. Panels were then taped off with 2.54 cm wide plastic tape into separate 22 cm x 28 cm sections, and each section was cleaned as according to manufacturer's specification.
- Ditzler DX-330 - apply about 4 grams to Scott WypAll™ towel and apply to wax panel - wipe off with clean, dry Scott WypAll.
- Example 1 - apply about 5 grams to Scott WypAll towel and apply to waxed panel - wipe off with clean, dry WypAll towel.
- ACME Aqua Klix™ - same as Example 1.
- DuPont Prep Solvent II - apply about 5 grams with Scott WypAll towel - let stand about 2 minutes - remove with wet WypAll towel followed by dry WypAll towel.
- BASF - same as DuPont Prep Solvent II, except use two wet wipes.
-
"Fish Eyes" Per 28 cm x 22 cm Panel Rain Dance Liquid Polish Example 1 26.5 27 DuPont 24.3 29.7 BASF 26.7 29.7 ACME 25.0 37.3 Ditzler 4.7 11.7 - The best cleaner is Ditzler DX-330, which is a standard solvent cleaner and does not comply with VOC standards. Example 1 compares favorably with the other low VOC cleaners, but accomplishes this cleaning in one step rather than two steps.
- Two cross hatch sections performed, one with a light scratch and one with a deep scratch in accordance with ASTM D3359. The performance evaluation used the following criteria:
- Good -
- No top paint removed from paint directly covered
- either scratch. - Fair -
- Some top coat removed from deep scratch only.
- Poor -
- Some top coat paint removed from both scratch areas.
- V. Poor -
- total top coat paint removed over all taped area.
- Using this test, the composition of Example 1 performed as well or better than other low VOC prep solvents.
- 24 hour old DuPont Centari Acrylic Enamel painted panels were used to test solvent attack by prep solvents.
Example 1 - no attack after 1 minute.
3M General Purpose Adhesive Cleaner - swells paint 5-10 seconds.
DuPont Prep Sol II 39295 - attacks, swells paint.
ACME Aqua Klix - very slight attack.
BASF 905 - attacks, swells paint . - The stability of the experimental microemulsions was tested by subjecting samples to a minimum of three freeze-thaw cycles and to a minimum of one week at 50°C. Although some samples would separate into distinct phase, the transparent microemulsion could be restored with mild shaking.
- Droplet particle size was determined by dynamic light scattering using a Malvern Photon Correlation Spectrometer.
- Flash point measurements were made according to the Tag closed cup method in accordance with ASTM D 56.
Amount in weight % | |||||||
Oil | cosurfactant | Mackamine LO | surfactant A | surfactant B | |||
U75 | 14.2 | DPM | 5.6 | 13.6 | T15-S-3 | 7.2 | 0 |
U75 | 14.2 | DPM | 4.5 | 10.0 | T15-S-5 | 12 | 0 |
U75 | 14.2 | DPM | 5.6 | 10.2 | Neo91-6 | 0.5 | Neo23-2 |
5.5 | |||||||
U75 | 14.2 | DPM | 5.6 | 13.0 | Neo23-3 | 6.0 | 0 |
U1241 | 6.2 | n-pro | 1.5 | 4.4 | T15-S-3 | 2.4 | 0 |
U1241 | 6.2 | n-pro | 1.5 | 4.4 | Neo23-3 | 2.4 | 0 |
Cleaner | Liquid Polish | Rain Dance |
Example 1 | 3 Good | 3 Good; 1 Fair-Poor |
Ditzler | 3 Good | 3 Good |
DuPont | 3 Good; 1 Poor | 1 Good; 1 Poor, |
1 Very Poor | ||
BASF | 2 Good; 1 Poor | 1 Poor; 2 Very Poor |
ACME | 2 Good; 1 Fair | 2 Good; 1 Fair |
Claims (19)
- A method of cleaning silicone wax, grease, grime or adhesives from a painted hard surface in need of cleaning comprisingi) applying to said painted surface an oil-in-water microemulsion composition comprisinga) an organic solvent or solvent blend having a solubility parameter of between 6.9 and 8.9 (cal/cm3)½,b) sufficient surfactant to support a stable microemulsion, andc) water in an amount sufficient to provide a total VOC content of less than 200 grams/literin an amount sufficient to soften and otherwise ease removal of said silicone wax, grease, grime or adhesive from the painted surface;ii) allowing said composition to soften and otherwise ease removal of said silicone wax, grease, grime or adhesive from the painted surface; andiii) wiping said composition and silicone wax, grease, grime or adhesive from the painted surface with a dry wiping material.
- The method of claim 1, wherein said solvent or solvent blend has a solubility parameter of between 7.5 and 8.9.
- The method of claim 1, wherein said solvent or solvent blend is at least 5% by weight polar or aromatic components.
- The method of claim 1, wherein said microemulsion comprises:a) an organic solvent or solvent blend having a solubility parameter of between 6.9 and 8.9 (cal/cm3)½,b) sufficient nonionic surfactant or nonionic surfactant blend to maintain a microemulsion, andc) water in an amount sufficient to provide a total VOC content of less than 200 grams/liter.
- The method of claim 4, wherein said microemulsion further comprises an additional surfactant selected from cationic, zwitterionic and anionic surfactants.
- The method of claim 5, wherein said microemulsion further comprises a co-surfactant.
- The method of claim 1, wherein said microemulsion comprises by weight:a) 5-15% of an organic solvent or solvent blend having a solubility parameter of between 6.9 and 8.9,b) 8-12% of a cationic or zwitterionic surfactant,c) 4-8% of a nonionic surfactant or nonionic surfactant blend having an HLB of between 7.5 and 10,d) 1-5% of a co-surfactant, ande) 50-82% of water, such that the total VOC content of the microemulsion is less than 200 grams/liter.
- A method of cleaning silicone wax, grease or grime according to claim 1, wherein said microemulsion comprises by weight:
5-8% aliphatic organic solvent, 1-3% co-surfactant, 3-5% amine oxide surfactant, 2-4% nonionic surfactant having an HLB of between 7.5 and 10, and 80-89% deionized water to total 100%. - A method of cleaning adhesives according to claim 1, wherein said microemulsion comprises by weight:
12-15% organic solvent having at least 5% aromatic or polar components, 1-4% co-surfactant, 8-12% amine oxide surfactant, 5-7% nonionic surfactant having an HLB of between 7.5 and 10, and 62-74% deionized water to total 100%. - The method of claim 1, wherein said organic solvent or solvent blend is selected from the group consisting of odorless mineral spirits.
- The method of claim 1, wherein said organic solvent or solvent blend is selected from the group consisting of aromatic mineral spirits, toluene, xylene and mixtures thereof.
- The method of claim 7, wherein said cationic or zwitterionic surfactant is selected from the group consisting of alkylamine oxides.
- The method of claim 7, wherein said cationic or zwitterionic surfactant is selected from the group consisting of cocodimethylamine oxide and lauryldimethylamine oxide.
- The method of claim 4, wherein said nonionic surfactant is selected from the group consisting of polyethoxylated linear, primary alcohols.
- The method of claim 6, wherein said co-surfactant is selected from the group consisting of n-propanol, n-butanol, pentanol, propylene glycol, dipropylene glycol methyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, ethylene glycol butyl ether and dipropylene monoethyl ether.
- The method of claim 15, wherein said co-surfactant is selected from the group consisting of n-propanol and dipropylene glycol methyl ether.
- The method of claim 1, further comprising the step of previously removing the bulk of the residue to be removed by rubbing off said bulk with elastomeric disks.
- The method of claim 1, wherein said microemulsion comprises by weight:
5-8% odorless mineral spirits, 1-3% n-propanol, 3-5% 30% active laurylamine oxide, 2-4% polyethoxylated linear primary alcohol, and 80-89% deionized water to total 100%. - The method of claim 1, wherein said microemulsion comprises by weight:
12-15% aromatic mineral spirits, 1-4% dipropylene glycol methyl ether, 8-12% 30% active laurylamine oxide, 5-7% polyethoxylated linear primary alcohol, and 62-74% deionized water to total 100%.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US68324091A | 1991-04-10 | 1991-04-10 | |
US683240 | 1991-04-10 | ||
PCT/US1992/002760 WO1992018600A1 (en) | 1991-04-10 | 1992-04-06 | Low voc cleaning compositions and methods |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0580721A1 EP0580721A1 (en) | 1994-02-02 |
EP0580721B1 true EP0580721B1 (en) | 1997-02-12 |
Family
ID=24743151
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92909867A Expired - Lifetime EP0580721B1 (en) | 1991-04-10 | 1992-04-06 | Method of cleaning painted hard surfaces with low voc cleaning compositions |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0580721B1 (en) |
JP (1) | JPH06506496A (en) |
CA (1) | CA2107579A1 (en) |
DE (1) | DE69217486T2 (en) |
WO (1) | WO1992018600A1 (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994023012A1 (en) * | 1993-04-02 | 1994-10-13 | The Dow Chemical Company | Microemulsion and emulsion cleaning compositions |
DE4406753A1 (en) * | 1994-03-02 | 1995-09-07 | Basf Lacke & Farben | Detergent, process for the preparation of the detergent and its use |
FR2723377B1 (en) * | 1994-08-02 | 1997-01-10 | Commerciale Du Rhone Sincora S | CLEANING OR STRIPPING COMPOSITIONS, AND PREPARATIONS CONTAINING SAME |
US5827809A (en) * | 1996-10-15 | 1998-10-27 | Vulcan Materials Company | Low-residue macroemulsion cleaner with perchloroethylene |
US6260264B1 (en) | 1997-12-08 | 2001-07-17 | 3M Innovative Properties Company | Methods for making z-axis electrical connections |
DE19824314A1 (en) * | 1998-06-02 | 2000-01-05 | Reinhold Terschluse | Cold cleaning vehicle parts to remove corrosive and burnt-on oil and grease residues in repair and scrap industry |
DE10022419A1 (en) | 2000-05-09 | 2001-11-22 | Henkel Ecolab Gmbh & Co Ohg | Surfactant composition used for removing residues containing silicone from surfaces contains hydrophilic polyethylene oxide monoalk(en)yl ether, N,N-bis(ethoxylated)-N-alk(en)yl amine and/or alkyl sulfonate and other surfactant |
CN1270375C (en) * | 2000-10-17 | 2006-08-16 | 3M创新有限公司 | Solvent assisted burnishing of pre-underfilled solder-bumped wafers for flipchip bonding |
JP4663891B2 (en) * | 2001-02-19 | 2011-04-06 | 東燃化学株式会社 | Method for cleaning molded thermoplastic resin and method for producing microporous thermoplastic resin film using the same |
US20080287331A1 (en) * | 2007-05-18 | 2008-11-20 | Hai-Hui Lin | Low voc cleaning composition for cleaning printing blankets and ink rollers |
ATE554743T1 (en) * | 2007-09-19 | 2012-05-15 | Bubbles & Beyond Gmbh | CLEANING AGENT FOR REMOVAL OF PAINT LAYERS FROM SURFACES, METHOD FOR PRODUCING THE AGENT AND METHOD FOR CLEANING |
US8257484B1 (en) | 2010-08-27 | 2012-09-04 | W. M. Barr & Company | Microemulsion paint thinner |
US8512481B2 (en) | 2010-10-22 | 2013-08-20 | Presstek, Inc. | Press cleaning with low-VOC solvent compositions |
US20220325209A1 (en) * | 2021-04-01 | 2022-10-13 | W.M. Barr & Company, Inc. | Water-in-silicone emulsion based liquid cleaner |
CN114164434B (en) * | 2021-12-10 | 2024-05-03 | 德旭新材料(佛冈)有限公司 | Wax removing composition and preparation method and application thereof |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3929499A (en) * | 1972-09-08 | 1975-12-30 | Frederick L Thomas | High water-content water in oil emulsion |
EP0005309A1 (en) * | 1978-02-14 | 1979-11-14 | Dawley Brook Papers Limited | Cleaning composition and method of removing printing ink from surfaces |
DE3172845D1 (en) * | 1980-11-19 | 1985-12-12 | Du Pont | Aqueous cleaning emulsion |
US5108643A (en) * | 1987-11-12 | 1992-04-28 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
US4921629A (en) * | 1988-04-13 | 1990-05-01 | Colgate-Palmolive Company | Heavy duty hard surface liquid detergent |
US4919839A (en) * | 1989-02-21 | 1990-04-24 | Colgate Palmolive Co. | Light duty microemulsion liquid detergent composition containing an aniocic/cationic complex |
-
1992
- 1992-04-06 WO PCT/US1992/002760 patent/WO1992018600A1/en active IP Right Grant
- 1992-04-06 JP JP4509098A patent/JPH06506496A/en active Pending
- 1992-04-06 CA CA002107579A patent/CA2107579A1/en not_active Abandoned
- 1992-04-06 DE DE69217486T patent/DE69217486T2/en not_active Expired - Fee Related
- 1992-04-06 EP EP92909867A patent/EP0580721B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0580721A1 (en) | 1994-02-02 |
WO1992018600A1 (en) | 1992-10-29 |
JPH06506496A (en) | 1994-07-21 |
DE69217486T2 (en) | 1997-07-10 |
DE69217486D1 (en) | 1997-03-27 |
CA2107579A1 (en) | 1992-10-11 |
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