EP0479888B1 - Improved builder-containing aqueous cleaner/degreaser microemulsion compositions - Google Patents

Improved builder-containing aqueous cleaner/degreaser microemulsion compositions Download PDF

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Publication number
EP0479888B1
EP0479888B1 EP90910985A EP90910985A EP0479888B1 EP 0479888 B1 EP0479888 B1 EP 0479888B1 EP 90910985 A EP90910985 A EP 90910985A EP 90910985 A EP90910985 A EP 90910985A EP 0479888 B1 EP0479888 B1 EP 0479888B1
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EP
European Patent Office
Prior art keywords
sodium
removal
sulfonate
grease
composition
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EP90910985A
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German (de)
English (en)
French (fr)
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EP0479888A4 (en
EP0479888A1 (en
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Donald N. Vaneenam
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Buckeye International Inc
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Buckeye International Inc
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    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents

Definitions

  • This invention relates to cleaner/degreaser compositions and, more particularly, to stable, aqueous, builder-containing cleaner/degreaser compositions in the form of true microemulsions which exhibit enhanced cleaning and degreasing capability.
  • Such conventional compositions are generally deficient in cleaning action and especially in heavy duty grease, oil, wax, etc. cutting action, often smell objectionably strongly of volative solvent and can sometimes present conbustability problems in concentrated form. They also tend to be harsh on the hands and to defat the skin. Further, heavy scrubbing, mopping or other mechanical action is generally required to attain the desired cleaning/degreasing action, especially where excessive soilant buildup has occurred. Most, even in their concentrated form, are ineffective in their capability to remove graffiti or the like.
  • compositions which are formulated in the form of totally water soluble solutions.
  • Such compositions comprise (a) at least one sparingly water soluble organic solvent having certain defined characteristics; (b) a solubilizing additive consisting of from 0.1 to approximately 100 weight percent of a surfactant and from 0 to approximately 99.9 weight percent of a coupler, the solubilizing additive being present in an amount not exceeding approximately tenfold that required to completely solubilize the organic solvent; and (c) water.
  • compositions containing infinitely water soluble organic solvents exhibit markedly superior cleaning/degreasing efficacy over that achievable with compositions containing infinitely water soluble organic solvents, problems are encountered in incorporating builders therein to further enhance their cleaning/degreasing capability due to the "salting out" characteristics of conventional builders.
  • GB-A-2144763 teaches heavy-duty liquid detergents and cleaners formulated as oil-in-water microemulsions which contain at least 5% of a mixture of hydrocarbon or halogenated hydrocarbon grease-removal solvent and a magnesium salt, builders, surfactants and enzymes.
  • the preferred solvents are n-paraffins and the mono- and bicylic mono-terpenes.
  • US-A-4606840 discloses aqueous compositions for the dispersion of hydrophobic substances.
  • the compositions contain a complex mixture of one or more hydrocarbons, ketones, alcohols and glycol ethers or esters.
  • US-A-4472291 describes oil-in-water microemulsions having increased viscosity. These microemulsions comprise kerosene, a hydrocarbon, as an essential component. This document also teaches the use of solvents such as light mineral oils, toluene and mixtures thereof with fluorocarbons.
  • EP-A-0316726 discloses microemulsion cleaning compositions comprising synthetic organic detergent, water, co-surfactant and a perfume as solvent. All examples of this application contain terpenes.
  • GB-A-2194547 teaches a laundry pre-spotter composition in the form of a microemulsion, solution, or gel which comprises, inter alia, from 10 to 70% of one or more alkanes.
  • US-A-4414128 is concerned with liquid detergent compositions which are particularly for use as hard surface cleaners. All the Examples show the use of a terpene as an essential component.
  • EP-A-0328174 describes hard surface cleaning compositions containing butyl carbitol in conjunction with butoxy propoxy propanol or hexyl carbitol.
  • US-A-4769172 discloses detergent compositions containing an organic synthetic detergent and N-polyalkyleneglycol-N,N-diacetic acid as a builder.
  • EP-A-0337576 published on 18 October 1989, discloses heavy duty hard surface liquid detergent compositions which show the use of butyl carbitol or Exxate solvent (i.e. hexyl acetate) as essential components.
  • the present invention is directed to stable, aqueous cleaner/degreaser compositions which are formulated in the form of true microemulsions and are free from hydrocarbons or halocarbons.
  • the compositions comprise:
  • compositions of the invention exhibit improved cleaner/ degreaser efficacy over compositions which contain no builder component.
  • improved builder-containing aqueous cleaner/ degreaser compositions can be formulated in the form of stable microemulsions by combining at least one sparingly water soluble organic solvent having certain characteristics and being present in an amount exceeding its aqueous solubility with a builder, a solubilizing additive and water, the solubilizing additive being present in an amount not substantially exceeding the amount required to transform the combination of said organic solvent and said builder from the form of a true macroemulsion to the form of a microemulsion and less than that required to form a true solution.
  • microemulsion compositions in accordance with the present invention that the solubilizing additive be present in an amount not substantially exceeding that required to transform the combination of the organic solvent and builder from the form of a true macroemulsion to the form of a microemulsion and less than that required to form a true solution.
  • microemulsions of the invention are clear and exhibit the Tyndall effect. It is believed that the aqueous phase of the microemulsions contains the dissolved builder. Due to the limited aqueous solubility of the organic solvents employed in the practice of the invention, it is unexpected that true microemulsions are formed.
  • microemulsion compositions of the invention provide additional advantages not conferred by cleaning/degreasing compositions which contain no builder component.
  • a builder component in the microemulsion compositions of the invention provides additional advantages not conferred by cleaning/degreasing compositions which contain no builder component.
  • such microemulsions not only achieve an enhanced cleaning/ degreasing efficacy but, moreover, they avoid soil redeposition and generally inhibit metal corrosion.
  • the compositions of the invention are particularly useful for cleaning/degreasing metallic surfaces.
  • microemulsions are more cost effective in their formulation since they generally contain lower amounts of the organic solvent component than do non-builder formulations.
  • the present invention permits the practical and effective use of normally hydrophobic(oleophilic) solvents in builder-containing compositions, which solvents have great affinity for and dissolving action against oleophilic soilants.
  • the sparingly water soluble organic solvent must have the following characteristics:
  • organic solvents from which useful organic solvents may be selected include esters, alchohols, ketones, aldehydes, ethers and nitriles. These will generally contain one or more of the desired similar or dissimilar functional groups listed above.
  • organic solvents containing similar functional groups from among those listed above include diethyl glutarate (2 ester groups), phenacyl acetone (2 keto groups), diethylethyl phosphonate (2 phosphonate ester groups), ethylenedipropionate (2 ester groups), decylene glycol (2 hydroxyl groups), m -dimethoxybenzene (2 ether groups), adiponitrile (2 nitrile groups), ethylene glycol dibutyl ether (2 ether groups), and diethyl- o -phthalate (2 ester groups).
  • organic solvents containing dissimilar functional groups from among those listed above may be mentioned 2-phenoxyethanol (hydroxy, ether groups), 1-phenoxy-2-propanol (hydroxy, ether groups), N-phenyl-morpholine (amino, ether groups), isopropylacetoacetate (keto, ester groups), o -methoxybenzyl alcohol (ether, hydroxy groups), 4'-methoxyacetophenone (ether, ketone groups), o -nitrophenetole (nitro, ether groups), 2-hexoxyethanol (hydroxy, ether groups), ethylcyano-acetoacetate (cyano, keto, ester groups), p -anisaldehyde (ether, aldehyde groups), polypropylene glycol 1200 (ether, hydroxyl groups), n-butoxy acetate (ether, ester groups), and 2-phenylthioethanol (thioether, hydroxyl groups).
  • 2-phenoxyethanol hydroxy, ether groups
  • the organic solvent have a relatively low volatility or high flash point, exhibit a low level of odor, be chemically stable, nontoxic, nonhazardous and commercially available.
  • the sparingly water soluble organic solvents which may be employed in the practice of the present invention (and comprising some of the solvents listed above) together with their aqueous ambient temperature solubility in wt.% include 2-phenoxyethanol (2.3) (marketed under the trade designation "Dowanol® EPh”), 1-phenoxy-2-propanol (1.1) (marketed under the trade designation “Dowanol® PPh”), ⁇ -phenylethanol (1.6), acetophenone (0.5), benzyl alcohol (4.4), benzonitrile (1.0), n-butyl acetate (0.7), n-amyl acetate (0.25), benzaldehyde (0.3), N,N-diethylaniline (1.4), diethyl adipate (0.43), dimethyl-o-phthalate (0.43), n-amyl alcohol (2.7), N-phenylmorpholine (1.0), n-butoxyethyl acetate (EB acetate) (1.1), cyclo
  • the above-listed sparingly water soluble organic solvents are merely illustrative and various other solvents meeting the criteria set out above may also be utilized in the practice of the invention. Because of their performance characteristics, lack of odor, low volatility/high flash point, chemical stability and availability, 2-phenoxyethanol and 1-phenoxy-2-propanol are the preferred organic solvents of choice. N-butoxyethyl acetate (EB acetate) and the dimethyl esters of mixed succinic, glutaric and adipic acids are also among the preferred organic solvents.
  • EB acetate N-butoxyethyl acetate
  • dimethyl esters of mixed succinic, glutaric and adipic acids are also among the preferred organic solvents.
  • a number of otherwise potent organic solvents having an aqueous solubility of less than 0.2 weight percent such as 2-(2-ethylhexoxy)ethanol (2-ethylhexyl cellosolve) having an aqueous solubility of only 0.095 wt.%, and 2,6-dimethyl -4-heptanone (diisobutyl ketone) (aq. sol. 0.05 wt. %), and organic solvents having an aqueous solubility in excess of 6 weight percent such as propylene glycol monomethyl ether acetate (aq. sol. 16.5 wt.%), ethylene glycol diacetate (aq. sol. 14.3 wt.%), propylene carbonate (aq. sol. 19.6 wt.%) and N-methyl pyrrolidone (infinite aq. sol.) are not useful in the practice of the invention.
  • aqueous cleaner/ degreaser compositions of the invention in the form of microemulsions, an organic solvent meeting the required criteria is combined with a builder, a solubilizing additive and water.
  • a builder is a material that enhances or maintains the cleaning efficiency of surfactants and functions by inactivating water hardness, supplying alkalinity to assist cleaning, providing buffering to maintain alkalinity, preventing removed soil from redepositing during washing, and emulsifying oily and greasy soils. Any of the conventional builders known to the art may be used in the practice of the invention.
  • silicates such as alkali metal silicates and metasilicates, alkali metal hydroxides, alkali metal carbonates, bicarbonates and sesquicarbonates, phosphates such as alkali metal phosphates, pyrophosphates, tripolyphosphates, hexametaphosphates and tetraphosphates, borax and alkali metal borates.
  • builders which may be used in the practice of the invention may be mentioned sodium hydroxide, sodium metasilicate, sodium silicate (Na 2 O:2SiO 2 or Na 2 O:3SiO 2 ), sodium carbonate, sodium sesquicarbonate, sodium bicarbonate, borax, trisodium phosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, sodium tetraphosphate, and sodium perborate.
  • Other builders known to the art may also be used.
  • the builder component will constitute from 0.25 to 10.0 wt.% of the total composition.
  • the solubilizing additive component of the compositions of the invention consists of from 0.1 to 100 weight percent of a surfactant and from 0 to 99.9 weight percent of a coupler and the solubilizing additive is present in the formulated composition in an amount necessary to form a microemulsion, i.e. an amount not substantially exceeding the amount required to transform the combination of the organic solvent and builder components from the form of a true macroemulsion to the form of a microemulsion and less than that required to form a true solution.
  • the amount of solubilizing additive employed is just sufficient to form a microemulsion.
  • the amount of solubilizing additive (surfactants or surfactant plus coupler) required to effect the formation of a microemulsion will vary depending upon the particular organic solvent and builder employed and can readily be determined by simple experimentation in each instance.
  • the solubilizing additive used in the practice of the invention may consist of a surfactant or a surfactant in combination with a coupler.
  • the term "coupler” is intended to mean a hydrotrope or a substance that increases the solubility in water of another material which is only partially water soluble, such as organic solvents or surfactants.
  • organic solvents or surfactants such as organic solvents or surfactants.
  • the use of a surfactant alone will suffice to render the organic solvent component of the compositions just completely (microcolloidally) soluble while in other instances the use of a surfactant in combination with a coupler may be utilized to achieve the desired microcolloidal solubilization of the organic solvent, i.e.
  • a surfactant alone or the combination of a surfactant and coupler is to be used is dependent upon the particular organic solvent and surfactant employed and can readily be determined in each particular case by simple experimentation.
  • the surfactant used may be an anionic, non ionic, cationic or amphoteric surfactant.
  • Illustrative anionic surfactants for use in the invention include dodecylbenzene sulfonic acid, sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate,triethanolamine dodecylbenzene sulfonate, morpholinium dodecylbenzene sulfonate, ammonium dodecylbenzene sulfonate, isopropylamine dodecylbenzene sulfonate, sodium tridecylbenzene sulfonate, sodium dinonylbenzene sulfonate, potassium didodecylbenzene sulfonate, dodecyl diphenyloxide disulfonic acid, sodium dodecyl diphenyloxide disulfonate, isopropylamine decyl diphenyloxide disulfonate, sodium hexadecyloxypol
  • nonionic surfactants which may be employed may be mentioned octylphenoxypoly(ethyleneoxy)-(11)ethanol, nonylphenoxypoly(ethyleneoxy)(13)ethanol, dodecylphenoxypoly(ethyleneoxy)(10)ethanol, polyoxyethylene (12) lauryl alcohol, polyoxyethylene (14) tridecyl alcohol, lauryloxypoly(ethyleneoxy)(10)ethyl methyl ether, undecylthiopoly(ethyleneoxy)(12)ethanol, methoxypoly(oxyethylene-(10)/(oxypropylene(20))-2-propanol block copolymer, nonyloxypoly(propyleneoxy)(4)/(ethyleneoxy)(l6)ethanol, dodecyl polyglycoside, polyoxyethylene (9) monolaurate, polyoxyethylene (8) monoundecanoate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (18) sorbitol monotallate, sucrose monolaurate, la
  • Illustrative useful cationic surfactants include a mixture of n-alkyl (C 12 50%, C 14 30%, C 16 17%, C 18 3%) dimethyl ethylbenzyl ammonium chlorides, hexadecyltrimethylammonium methosulfate, didecyldimethylammonium bromide and a mixture of n-alkyl (65% C 12 , 32% C 14 ) dimethyl benzyl ammonium chlorides.
  • amphoteric surfactants include cocamidopropyl betaine, sodium palmityloamphopropionate, N-coco beta-aminopropionic acid, disodium N-lauryliminodipropionate, sodium coco imidazoline amphoglycinate and coco betaine.
  • Other cationic and amphoteric surfactants known to the art may also be utilized.
  • the preferred surfactants for general use in the practice of the invention include dodecylbenzenesulfonic acid and the sodium, potassium, triethanolamine, morpholinium, ammonium and isopropylamine salts thereof, and morpholinium tallate.
  • the couplers which may be utilized in the practice of the invention include sodium benzene sulfonate, sodium toluene sulfonate, sodium xylene sulfonate, potassium ethylbenzene sulfonate, sodium cumene sulfonate, sodium octane-1-sulfonate, potassium dimethylnaphthalene sulfonate, ammonium xylene sulfonate, sodium n-hexyl diphenyloxide disulfonate, sodium 2-ethylhexyl sulfate, ammonium n-butoxyethyl sulfate, sodium 2-ethylhexanoate, sodium pelargonate, sodium n-butoxymethyl carboxylate, potassium mono/di phenoxyethyl phosphate, sodium mono/di n-butoxyethyl phosphate, triethanolamine trimethylolpropane phosphate
  • couplers such as propylene glycol ethers (e.g. tripropyleneglycol monomethyl ether) can be used in the practice of the invention, but cannot be substituted for the sparingly water soluble organic solvent component. Additional couplers or hydrotropes known to the art may also be utilized.
  • solubilizing additive component of the compositions of the invention it will be understood that one or more surfactants from one or more compatible classes of surfactants may be employed or utilized in a mixed solubilizing surfactant system.
  • a combination of compatible anionic and nonionic surfactants may be employed.
  • a combination of compatible couplers may also be used as may a combination of one or more compatible surfactants from different classes of surfactants together with one or more couplers.
  • one may use a combination of blended surfactants and couplers to achieve the desired minimal solvent solubilization.
  • the compatibility of the various surfactants and of the various couplers with each other and in combination can be readily determined by simple experimentation.
  • a mixture of the sparingly soluble organic solvents may be employed in formulating the compositions of the invention.
  • each of the solvents should have nearly the same approximate water solubility so that they will solubilize in water at approximately the same point upon addition of the solubilizing additive.
  • various optional adjuvants can be incorporated.
  • chelants such as the sodium salts of ethylenediaminetetraacetic acid (Hampene® 100 or Versene® 100), thickeners such as carboxy acrylic polymers (Carbopol® 940) or acrylic acid/alkyl methacrylate copolymers (Acrysol® ICS-1), fragrances, dyes, pH adjustants, defoaming agents, anti-corrosion additives and anti-rust additives.
  • an anti flash-rusting additive such as an alkanolamine (e.g., mono-, di- or triethanolamine) may be incorporated.
  • the various components as brought together may first form an oily suspension which becomes an emulsion upon the addition of a surfactant/coupler, and is then finally transformed into a microemulsion through the addition of the final portion of the solubilizing coupler.
  • a surfactant/coupler For example, 2.0 wt. % sodium metasilicate, 7.5 wt. % 1-phenoxy-2-propanol, 2.5 wt. % tripropyleneglycol monomethyl ether and 76.4 wt. % soft water are stirred to form an oily suspension having a pH of 13.3.
  • 2.4 wt. % dodecylbenzenesulfonic acid is added with stirring to form a creamy white emulsion having a pH of 13.1.
  • microemulsions of the invention can also be formulated by combining the various components together in different sequence to transform any emulsion formed into a microemulsion. The addition of an excess of the solubilizing additive to the formulation will cause the microemulsion to be converted into a solution and is to be avoided if optimum cleaning/ degreasing efficacy of the builder-containing formulations is to be achieved.
  • total solids content refers, respectively, to the combined percentages of nonvolatile components and to the sum total of nonaqueous volatile and nonvolatile components.
  • cloud point indicates the temperature below which the composition exists as a clear, single phase microemulsion and above which phase separation (heterogeneity) occurs.
  • a composition should preferably have a cloud point in excess of, for example 50°C, to have a viably safe, storage-stable shelf life under hot, summertime warehouse conditions.
  • compositions of the invention provide enhanced cleaning/degreasing efficacy over that achievable with compositions containing no builder or with available builder-containing compositions formulated in the form of total solutions.
  • compositions of the present invention were subjected as indicated to the definitive, semiquantitative degreasing test method described below in order to measure their cleaning/degreasing efficacy.
  • a magnetic stirrer (Fisher Scientific Co., Catalog No. 14-511-1A) provided with a vaned disc magnetic stir bar (7/8" (diameter) x 5/8" (height), 22 mm x 15 mm, Fisher Scientific Co., Catalog No. 14-511-98C) was used.
  • borosilicate glass microslides (3" x 1", 1.0 mm thickness) (7.62 cm x 2.54 cm x 1 mm thickness) were thinly smeared/rub-on coated with Vaseline brand white petroleum jelly on one side only to a distance of 1.0" (2.54 cm) from the bottom edge to provide a 1.0" (2.5cm) x 1.0" (2.54 cm) coated area.
  • test cleaner/degreaser solutions were employed at full strength unless otherwise indicated and in an amount sufficient to fill a 50 ml Pyrex beaker containing the vaned disc magnetic stirrer bar to a level of 40 ml.
  • Each test solution and surrounding air were maintained at 21 ⁇ 0.5°C and the test solution stirring rate was determined by a setting of "3" on the stirrer dial of the magnetic stirrer.
  • the stirring disc was positioned off-center to accomodate each microslide, touching neither the beaker walls nor the microslide and rotating freely when in use.
  • the beaker containing the stirrer bar was filled to 40 ml. with the test cleaning/degreasing solution at the indicated concentration, placed atop the magnetic stirrer plate, and positioned off-center to accomodate the glass microslide, and yet allow the vaned disc stirrer bar to rotate or spin freely.
  • the stirrer was turned on, the dial adjusted manually to the "3" stirring rate setting and the Vaseline thin film coated glass microslide was introduced into the test solution bath in such a manner that the coated side faced upward and was positioned away from the stirrer bar.
  • the time "0" was noted immediately on a watch or clock with a sweep second hand.
  • the glass microslide was briefly removed from the cleaner/degreaser solution bath and immediately “read” for "% Vaseline removed from the 1.0" x 1.0" (2.54cm x 2.54cm) treated area", an objective determination, after which the microslide was immediately returned to the stirred aqueous cleaner/degreaser bath.
  • the duration of the degreasing test is determined by the time needed for complete, 100% removal of the Vaseline film from the glass microslide surface.
  • the accuracy of the above-described test method is of the order of ⁇ 5% as determined by replicate run averaging.
  • aqueous, cleaner/degreaser formulation in the form of a microemulsion was prepared having the following composition: Component Wt. % 1-Phenoxy-2-propanol (Dowanol® PPh) 3.0 Monoethanolamine 1.8 Sodium metasilicate 1.5 Dodecylbenzenesulfonic acid 1.0 Soft H 2 O 92.7 100.0 ⁇ The sodium metasilicate was dissolved in water with stirring. The monoethanolamine, 1-phenoxy-2-propanol and dodecylbenzenesulfonic acid were added and stirring of the resultant emulsion/suspension was continued until the emulsion gradually cleared to produce an iridescent (blue) microemulsion.
  • the microemulsion had a pH of 12.65, a total solids content of 2.5% and a total actives content of 7.3%. Upon heating, the microemulsion remained iridescent to 50°C, then developed more turbidity up to 75°C and became a clear, colorless aqueous solution above about 75°C. It exhibited no cloud point to 100°C.
  • the composition readily removed the following soilant markings from alkyd enameled metal surfaces: black Magic Marker, black and blue indelible ballpoint pen, #1 hardness pencil, red (waxy) crayon, and automotive grease smearings. Some trace smudge was left on the surface.
  • the composition readily removed four coats of floor finish (trade designation "Buckeye Citation®” by The Davies-Young Company) from vinyl tile upon 5 minutes contact time at room temperature, followed by swabbing action, a water rinse and air drying.
  • Example 2 was repeated in formulating an aqueous cleaner/degreaser microemulsion having the following composition: Component Wt. % 1-Phenoxy-2-propanol (Dowanol® PPh) 3.5 Monoethanolamine 0.5 Sodium Metasilicate 1.2 Dodecylbenzenesulfonic acid 1.2 Sodium xylene sulfonate (40%) 5.0 Soft H 2 O 88.6 100.00 ⁇
  • the composition was a bluish, iridescent microemulsion having a pH of 12.5, a total solids content of 4.4% and a total actives content of 8.4%. Upon heating, the composition remained an iridescent microemulsion to 48°C, became a turbid emulsion between 48-59°C and a clear, colorless solution above about 60°C.
  • composition effected 100% removal of the markings set forth in Example 2 and also effected 100% removal of four coats of "Buckeye Citation®" floor finish as in Example 2.
  • Example 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following composition: Component Wt. % 1-Phenoxy-2-propanol (Dowanol® PPh) 3.5 Monoethanolamine 0.5 Sodium metasilicate 1.2 Dodecylbenzenesulfonic acid 1.2 Sodium cumene sulfonate (45%) 3.5 Soft H 2 O 90.1 100.0 ⁇
  • the composition was a bluish, iridescent microemulsion having a pH of 12.6, a total solids content of 3.98% and a total actives content of 7.98%. Upon heating, the composition remained an iridescent microemulsion to 39°C and became a clear, colorless solution above about 39°C. It exhibited no cloud point to 100°C.
  • composition effected 100% removal of the markings set forth in Example 2 with no smudging, and also effected 100% removal of four coats of "Buckwye Citation”® floor finish as in Example 2.
  • Example 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following composition: Component Wt. % 1-Phenoxy-2-propanol (Dowanol® PPh) 3.5 Monoethanolamine 0.5 Sodium metasilicate 1.2 Dodecylbenzenesulfonic acid 1.2 Sodium Capryloamphopropionate, 50% Monateric® CY-Na-50 2.0 Soft H 2 O 91.6 100.00 ⁇
  • the composition was a pale yellow, iridescent microemulsion having a pH of 12.5, a total solids content of 3.4% and a total actives content of 7.4%. Upon heating, the composition remained an iridescent microemulsion to 50°C and became a clear solution at temperatures above 50°C. It exhibited no cloud point.
  • composition effected 100% removal of the markings set forth in Example 2 with no to very slight smudging, and also effected 95-100% removal of four coats of "Buckeye Citation®" floor finish as in Example 2.
  • Example 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following composition: Component Wt. % 1-Phenoxy-2-propanol (Dowanol® PPh) 4.0 Sodium metasilicate 1.0 Sodium hydroxide (50%) 0.2 Dodecylbenzenesulfonic acid 1.5 Sodium xylene sulfonate (40%) 5.0 Monoethanolamine 0.5 Soft H 2 O 87.8 100.00 ⁇
  • the composition was a bluish, iridescent microemulsion having a pH of 12.65, a total solids content of 4.6% and a total actives content of 9.1%. Upon heating, the composition remained an iridescent microemulsion to 51.5°C, was turbid in the range 50-60°C, and was a clear, colorless solution above about 60°C.
  • composition effected 100% removal of the markings set forth in Example 2 with slight smudging and also effected 100% removal of four coats of "Buckeye Citation®" floor finish as in Example 2.
  • a control composition was prepared by combining the following components in the amounts indicated: Component Wt. % 1-Phenoxy-1-propanol (Dowanol® PPh) 4.0 Dodecylbenzenesulfonic acid 1.7 Sodium hydroxide (50%) 0.5 Monoethanolamine 1.5 Soft H 2 O 92.3 100.0 ⁇
  • the composition was a clear, essentially colorless solution containing no builder component. It had a pH of 11.7, a total solids content of 1.844% and a total actives content of 7.344%. It exhibited no cloud point to 100°C.
  • aqueous, cleaner/degreaser formulation in the form of a microemulsion was prepared having the following composition: Component Wt. % 1-Phenoxy-2-propanol (Dowanol® PPh) 4.0 Dodecylbenzenesulfonic acid 1.7 Sodium hydroxide (50%) 0.4 Monoethanolamine 0.9 Soft H 2 O 92.6 Sodium metasilicate 0.4 100.0 ⁇ All of the above components except the sodium metasilicate were stirred together to form an aqueous solution. The sodium metasilicate was then added as granules and upon dissolving in the solution, a microemulsion was formed having a bluish, iridescent appearance.
  • the microemulsion had a pH of 12.1, a total solids content of 2.22% and a total actives content of 7.12%. Upon heating, the microemulsion remained iridescent to 37°C. and became a clear, colorless solution above about 37°C. It exhibited no cloud point.
  • composition effected 100% removal of the markings set forth in Example 2 with no smudging and also effected 100% removal of four coats of "Buckeye Citation®" floor finish as in Example 2.
  • aqueous, cleaner/degreaser formulation in the form of a microemulsion was prepared having the following composition: Component Wt. % 1-Phenoxy-2-propanol (Dowanol® PPh) 4.0 Dodecylbenzenesulfonic acid 1.7 Sodium Hydroxide (50%) 0.5 Monoethanolamine 1.5 Soft H 2 O 91.9 Sodium metasilicate 0.4 100.0 ⁇ All of the above components except the sodium metasilicate were stirred together to form a clear, aqueous solution. The sodium metasilicate was then added as granules and upon dissolving in the solution, a microemulsion was formed having a bluish, iridescent appearance.
  • the microemulsion had a pH of 12.3, a total solids content of 2.24% and a total actives content of 7.74%. Upon heating, the microemulsion remained iridescent to 41°C. Above about 41°C it became a clear, colorless solution. It exhibited no cloud point.
  • composition effected 100% removal of the markings set forth in Example 2 with very slight tendency to smudge and also effected 100% removal of four coats of "Buckeye Citation®" floor finish as in Example 2.
  • Examples 8 and 9 were repeated in preparing a microemulsion cleaner/degreaser formulation having the following composition: Component Wt.% 1-Phenoxy-2-propanol (Dowanol® PPh) 4.0 Dodecylbenzenesulfonic acid 1.6 Soduim hydroxide (50%) 0.4 Monoethanolamine 1.5 Soft H 2 O 92.1 Sodium metasilicate 0.4 100.0 ⁇
  • the microemulsion had a bluish, iridescent appearance, a pH of 12.3, a total solids content of 2.12% and a total actives content of 7.62%. Upon heating, the microemulsion remained iridescent to 44°C and above which it formed a clear, colorless solution. It exhibited no cloud point.
  • composition effected 100% removal of all markings including auto grease as set forth in Example 2 and also effected 100% removal of four coats of "Buckeye Citation®" floor finish as in Example 2.
  • Examples 8 and 9 were repeated in preparing a microemulsion cleaner/degreaser formulation having the following composition: Component Wt. % 1-Phenoxy-2-propanol (Dowanol® PPh) 4.0 Dodecylbenzenesulfonic acid 1.6 Sodium hydroxide (50%) 0.4 Monoethanolamine 1.5 Soft H 2 O 92.0 Sodium metasilicate 0.5 100.0 ⁇
  • the microemulsion had a bluish, iridescent appearance, a pH of 12.4, a total solids contents of 2.22% and a total actives content of 7.72% Upon heating, the microemulsion remained iridescent to 52.5°C and became a clear solution above 52.5°C It exhibited no cloud point.
  • composition effected 100% removal of all markings set forth in Example 2 with no smudging and also effected 100% removal of four coats of "Buckeye Citation®" floor finish as in Example 2.
  • aqueous, cleaner/degreaser formulation in the form of a microemulsion was prepared having the following composition: Component Wt. % 1-Phenoxy-2-propanol (Dowanol® PPh) 4.0 Dodecylbenzenesulfonic acid 1.5 Sodium hydroxide (50%) 0.4 Soft H 2 O 93.7 Tetrapotassium pyrophosphate 0.4 100.0 ⁇ All of the above components except tetrapotassium pyrophosphate were stirred together and the pH adjusted to 7.0 with a trace of sodium sesquicarbonate to obtain a clear, colorless aqueous solution.
  • the tetrapotassium pyrophosphate was then added as granules and the solution immediately changed to a bluish, iridescent microemulsion.
  • the microemulsion had a pH of 9.11, a total solids content of 2.11% and a total actives content of 6.115%. Upon heating, the microemulsion remained iridescent to 42°C. It exhibited no cloud point to 100°C and no flash point.
  • composition effected 100%, easy and fast removal of all markings set forth in Example 2.
  • Example 12 was repeated in preparing a microemulsion cleaner/degreaser formulation having following composition: Component Wt. % 1-Phenoxy-2-propanol 4.0 Dodecylbenzenesulfonic acid 1.5 Sodium hydroxide (50%) 0.4 Soft H 2 O 93.7 Borax 0.4 100.0 ⁇
  • the microemulsion formed upon the addition of borax granules to the other components and the slow dissolution of the borax produced a gradual change from a clear, aqueous solution to a bluish, iridescent microemulsion.
  • the microemulsion had a pH of 8.93, a total solids content of 2.115% and a total actives content of 6.115%.
  • the microemulsion Upon heating, the microemulsion remained iridescent to 38°C, clearing at 38.5°C and becoming a clear, colorless solution above about 39°C. It exhibited no cloud point to 100°C and no flash point.
  • composition effected 100% facile removal of all markings set forth in Example 2.
  • Example 12 was repeated in preparing a microemulsion cleaner/degreaser formulation having the following composition: Component Wt. % 1-Phenoxy-2-propanol (Dowanol® PPh) 4.0 Dodecylbenzenesulfonic acid 1.5 Sodium hydroxide (50%) 0.4 Soft H 2 O 93.6 Sodium carbonate 0.5 100.0 ⁇
  • the addition of the sodium carbonate in powder form to a clear, colorless aqueous solution of the other components produced the instantaneous development of a bluish, iridescent microemulsion.
  • the microemulsion had a pH of 10.75, a total solids content of 2.215% and a total actives content of 6.215%.
  • microemulsion unlike those of Examples 12 and 13, was slightly viscous and had a Brookfield viscosity of 37 cps. at 21°C. Upon heating, the microemulsion remained iridescent to 60.5°C and became a clear, colorless aqueous solution above about 61°C. It exhibited no cloud point to 100°C.
  • composition effected 100%, fast removal of all markings set forth in Example 2.
  • Example 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following composition: Component Wt. % 2-Phenoxyethanol (Dowanol® EPh) 6.4 Dodecylbenzenesulfonic acid 2.5 Anhydrous sodium metasilicate 3.5 Chelating agent (Hampene® 100, 40%) 2.0 Sodium xylene sulfonate (40%) 7.5 Soft H 2 O 78.1 100.0 ⁇ The composition was a faint bluish, microemulsion having a pH of 12.86, a total solids content of 9.8% and a total actives content of 16.2%. It exhibited no cloud content of point to 100°C and no flash point.
  • the composition effected 75% removal of black Magic Marker markings from an alkyd enameled steel panel.
  • Example 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following composition: Component Wt. % Anhydrous sodium metasilicate 3.6 Dodecylbenzenesulfonic acid 2.80 Chelating Agent (Hampene® 100) 2.00 Propyleneglycol monomethyl ether 2.00 Dipropyleneglycol monomethyl ether 0.95 Tripropyleneglycol monomethyl ether 0.70 1-Phenoxy-2-propanol (Dowanol® PPh) 6.35 Sodium xylene sulfonate 8.50 Soft H 2 O 73.10 100.00 ⁇ The composition was a faint, bluish, colloidal microemulsion having a pH of 13.23, a total solids content of 10.6% and a total actives content of 20.6%. It exhibited no cloud point and no flash point.
  • Component Wt. % Anhydrous sodium metasilicate 3.6
  • Dodecylbenzenesulfonic acid 2.80
  • the composition effected 90% removal of black Magic Marker markings from an alkyd enameled steel panel.
  • Example 2 was repeated in formulating an aqueous having the following composition: Component Wt. % Anhydrous sodium metasilicate 5.50 Dodecylbenzenesulfonic acid 5.00 Chelating agent (Hampene® 100) 2.00 Propyleneglycol monomethyl ether 2.00 Dipropyleneglycol monomethyl ether 0.95 Tripropyleneglycol monomethyl ether 0.70 1-Phenoxy-2-propanol (Dowanol® PPh) 6.35 Sodium xylene sulfonate (40%) 8.5 Soft H 2 O 69.0 100.0 ⁇ The components formed a clear, aqueous solution rather than a microemulsion because the composition included an excess of solubilizing additive over that required to form a microemulsion.
  • the solution effected 0% removal of black Magic Marker markings from an alkyd enameled steel panel.
  • Example 2 was repeated in formulating an aqueous microemulsion having the following composition: Component Wt. % Anhydrous sodium metasilicate 4.0 Dodecylbenzenesulfonic acid 2.0 Propylene glycol mono-t-butyl ether (Arcosolve® PTB) 9.5 Chelating agent (Hampene® 100) 3.0 Soft H 2 O 81.5 100.0 ⁇
  • the organic solvent component, propylene glycol mono-t-butyl ether has an aqueous solubility of 13.9 wt. % at 21°C.
  • the composition was a very faint bluish, colloidal microemulsion having a pH of 13.73, a total solids content of 7.2% and a total actives content of 16.7%. It had a cloud point of 28°C.
  • the composition effected 60% removal of black Magic Marker markings from an alkyd enameled steel surface.
  • Example 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following composition:
  • the composition was a slightly bluish, colloidal microemulsion having a pH 13.62, a total solids content of 10.7% and a total actives content of 20.7%. It had a cloud point of 26°C and no flash point.
  • the composition effected 100% removal of black Magic Marker markings from an alkyd enameled steel panel.
  • Example 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following composition:
  • the composition was faint bluish microemulsion having a pH of 13.19, a total solids content of 9.3% and a total actives content of 19.3%. It had a cloud point in excess of 100°C and no flash point.
  • the composition effected 50% removal of black Magic Marker markings from an alkyd enameled steel panel.
  • Example 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following composition:
  • the composition was a faint bluish microemulsion having a pH of 13.05 a total solids content of 8.7% and a total actives content of 18.2%. It had a cloud point of approximately 75°C and no flash point.
  • the composition effected approximately 95% of black Magic Marker markings from an alkyd enameled steel panel.
  • Example 21 was repeated in formulating an aqueous microemulsion containing no builder component and having the following composition:
  • the small amount of sodium hydroxide was included to partially neutralize the dodecylbenzenesulfonic acid and cause salt formation.
  • the composition was a faint opalescent microemulsion having a pH of 7.0, a total solids content of 5.9% and a total actives content of 15.4%. It had a cloud point in excess of 100°C and exhibited no flash point.
  • the composition effected only 0-5% removal of black Magic Marker markings from an alkyd enameled steel panel.
  • Example 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following composition: Component Wt. % Anhydrous sodium metasilicate 2.2 Dodecylbenzenesulfonic acid 2.5 Polyglycol 112-2(Dow)® Block ethylene oxide/ propylene oxide copolyol, terminated by glycerol) 10.0 Soft H 2 O 85.3 100.0 ⁇
  • the composition was a very faint microemulsion having a pH of 12.73, and a total solids and total actives content of 14.7%. It had a cloud point of 40°C and exhibited no flash point.
  • the composition effected 100% removal of black Magic Marker markings from an alkyd enameled steel panel.
  • Example 2 was repeated in preparing the following composition containing a highly water soluble organic solvent instead of a sparingly water soluble organic solvent:
  • the composition was a clear, very pale yellow solution having a pH of 12.53, a total solids content of 4.4% and a total actives content of 14.4%. It had a cloud point in excess of 100°C.
  • the composition effected less than 5% removal of black Magic Marker markings from an alkyd enameled steel panel.
  • Example 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following composition: Component Wt. % Anhydrous sodium metasilicate 2.3 Dodecylbenzenesulfonic acid 2.8 Tripropyleneglycol monomethyl ether 5.0 Acetophenone 5.0 Soft H 2 O 84.9 100.0 ⁇
  • the composition was a bluish, iridescent microemulsion having a pH of 12.61, a total solids content of 5.1% and a total actives content of 15.1%. It had a cloud point in excess of 100°C and exhibited no flash point.
  • the composition effected 100% removal of black Magic Marker markings from an alkyd enameled steel panel.
  • Example 2 was repeated in formulating an aqueous cleaner/degreaser microemulsion having the following composition:
  • the composition was a faint bluish microemulsion having a pH of 12.74, a total solids content of 6.66% and a total actives content of 16.66%. It had a cloud point of 65°C.
  • the composition effected approximately 65% removal of black Magic Marker markings from an alkyd enameled steel panel.
  • Example 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following composition:
  • the composition was a light bluish, iridescent microemulsion having a pH of 13.42, a total solids content of 7.04 and a total actives content of 16.04%. It had a cloud point above 100°C and no flash point.
  • the composition effected 100% removal of black Magic Marker markings from an alkyd enameled steel panel.
  • An aqueous, cleaner/degreaser formulation in the form of a microemulsion was prepared having the following composition: The sodium metasilicate was dissolved in water with stirring. The monoethanolamine was added followed by the addition of the 1-phenoxy-2-propanol, tripropyleneglycol monomethyl ether and dodecylbenzenesulfonic acid with stirring. Stirring was continued until a homogeneous emulsion formed. The Alkali Surfactant was then added and the emulsion was transformed into a microemulsion after which the defoaming agent was added. The resulting microemulsion had a slightly bluish, iridescent appearance, a pH of 12.42, a total solids content of 5.7% and a total actives content of 16.2%. It exhibited a cloud point in excess of 100°C.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
EP90910985A 1989-06-29 1990-06-12 Improved builder-containing aqueous cleaner/degreaser microemulsion compositions Expired - Lifetime EP0479888B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US37391089A 1989-06-29 1989-06-29
US373910 1989-06-29
PCT/US1990/003317 WO1991000337A1 (en) 1989-06-29 1990-06-12 Improved builder-containing aqueous cleaner/degreaser microemulsion compositions

Publications (3)

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EP0479888A1 EP0479888A1 (en) 1992-04-15
EP0479888A4 EP0479888A4 (en) 1992-06-03
EP0479888B1 true EP0479888B1 (en) 1996-12-18

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EP (1) EP0479888B1 (ja)
JP (1) JP2671234B2 (ja)
AT (1) ATE146521T1 (ja)
AU (1) AU6031790A (ja)
CA (1) CA2057027C (ja)
DE (1) DE69029472T2 (ja)
DK (1) DK0479888T3 (ja)
ES (1) ES2100884T3 (ja)
WO (1) WO1991000337A1 (ja)

Cited By (2)

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Publication number Priority date Publication date Assignee Title
US8329630B2 (en) 2008-04-18 2012-12-11 Ecolab Usa Inc. Ready to use thickened degreaser and associated methods
US8420586B2 (en) 2008-04-18 2013-04-16 Ecolab Usa Inc. Thickened oven cleaner comprising a glutamic acid salt or disodium ethanol diglycine chelant

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KR960701189A (ko) * 1993-03-30 1996-02-24 테릴 켄트 퀼리 세정 조성물 및 이의 사용방법(cleaning compositions and method of use)
JPH08508523A (ja) * 1993-03-30 1996-09-10 ミネソタ マイニング アンド マニュファクチャリング カンパニー 改良した床塗膜除去用組成物および方法
BR9406028A (pt) * 1993-03-30 1995-12-26 Minnesota Mining & Mfg Composição e processo de limpeza
BR9609495A (pt) * 1995-07-18 1999-03-02 Unilever Nv Composição e processos de remoção de gordura cozida sobre uma superfície de metal e de limpeza de uma área para estacionamento
US5922665A (en) * 1997-05-28 1999-07-13 Minnesota Mining And Manufacturing Company Aqueous cleaning composition including a nonionic surfactant and a very slightly water-soluble organic solvent suitable for hydrophobic soil removal
FR2795088B1 (fr) * 1999-06-21 2002-05-24 Atofina Compositions de nettoyage a froid du type microemulsions
US6407051B1 (en) * 2000-02-07 2002-06-18 Ecolab Inc. Microemulsion detergent composition and method for removing hydrophobic soil from an article
GB2400375A (en) * 2003-04-09 2004-10-13 Hassan Scott Lisa Non-emulsifying aqueous cleaner-degreaser
DE10353986A1 (de) * 2003-11-19 2005-06-30 Henkel Kgaa Tensidgranulat mit hydrophoben Inhaltsstoffen
EP2045320B1 (de) * 2007-09-19 2012-04-25 Bubbles & Beyond Gmbh Reinigungsmittel zur Entfernung von Farbschichten von Oberflächen, Verfahren zur Herstellung des Mittels und Verfahren zur Reinigung
EP2304011B1 (en) * 2008-07-14 2013-03-27 The Procter & Gamble Company Solvent system for microemulsion or protomicroemulsion and compositions using the solvent system
DE102009014380A1 (de) 2009-03-26 2010-10-07 Bubbles And Beyond Gmbh Verfahren und Zusammensetzung zum Reinigen von Gegenständen
US20120252713A1 (en) * 2010-09-24 2012-10-04 Invista North America S.A.R.L. Composition for surface treatment and process
ES2428799B1 (es) * 2012-05-04 2014-09-29 Javier DÍAZ RODRIGUEZ Producto desengrasante de limpieza para múltiples superficies
WO2015193280A1 (de) * 2014-06-17 2015-12-23 Chemetall Gmbh Reinigungsmittel zur schonenden entfernung von tinten und marker
CN112481621B (zh) * 2020-11-27 2023-07-25 德旭新材料(佛冈)有限公司 一种金属清洗剂及其制备方法

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US8420586B2 (en) 2008-04-18 2013-04-16 Ecolab Usa Inc. Thickened oven cleaner comprising a glutamic acid salt or disodium ethanol diglycine chelant

Also Published As

Publication number Publication date
WO1991000337A1 (en) 1991-01-10
JPH05500675A (ja) 1993-02-12
DE69029472T2 (de) 1997-07-03
CA2057027A1 (en) 1990-12-30
DK0479888T3 (da) 1997-06-09
DE69029472D1 (de) 1997-01-30
JP2671234B2 (ja) 1997-10-29
EP0479888A4 (en) 1992-06-03
ES2100884T3 (es) 1997-07-01
AU6031790A (en) 1991-01-17
CA2057027C (en) 1999-04-06
ATE146521T1 (de) 1997-01-15
EP0479888A1 (en) 1992-04-15

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