EP0506744A1 - Compositions aqueuses d'agent de nettoyage/agent de degraissage sous forme d'emulsions - Google Patents

Compositions aqueuses d'agent de nettoyage/agent de degraissage sous forme d'emulsions

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Publication number
EP0506744A1
EP0506744A1 EP91901175A EP91901175A EP0506744A1 EP 0506744 A1 EP0506744 A1 EP 0506744A1 EP 91901175 A EP91901175 A EP 91901175A EP 91901175 A EP91901175 A EP 91901175A EP 0506744 A1 EP0506744 A1 EP 0506744A1
Authority
EP
European Patent Office
Prior art keywords
sodium
stable
emulsion composition
set forth
aqueous cleaner
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.)
Withdrawn
Application number
EP91901175A
Other languages
German (de)
English (en)
Other versions
EP0506744A4 (en
Inventor
Donald N. Vaneenam
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Buckeye International Inc
Original Assignee
Buckeye International Inc
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Filing date
Publication date
Application filed by Buckeye International Inc filed Critical Buckeye International Inc
Publication of EP0506744A1 publication Critical patent/EP0506744A1/fr
Publication of EP0506744A4 publication Critical patent/EP0506744A4/en
Withdrawn legal-status Critical Current

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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
    • 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 cleaner/degreaser compositions in the form of emulsions which exhibit improved degreasing efficacies.
  • the conventional and available cleaner/degreaser emulsion compositions have been water in oil or oil in water emulsions in which the organic solvent component is an inherently water insoluble organic solvent.
  • Such available emulsion compositions include, for example, those marketed under the trade designations "Off" asphalt remover which contains the water insoluble solvents toluene and o-dichlorobenzene emulsified with a tall oil amide.
  • Other available emulsion compositions contain water insoluble aromatic solvents such as xylene, kerosene, mineral spirits, benzene or naphthalene emulsified with various surfactants to form oil in water emulsions.
  • Illustrative of such available emulsions are those marketed under the trade designations "Brulin 512M”, “Spartan WRD-160”, “Betco Emulsifiable Solvent Degreaser”, “Amrep Jel-Sol”, and “DuBois Actusol”.
  • an inherently water insoluble organic solvent typically a hydrocarbon solvent
  • surfactants soluble in the solvent component.
  • emulsion compositions having improved cleaning/degreasing efficacy
  • emulsion compositions which are formulated to provide a portion of the organic solvent content in both the aqueous and nonaqueous phases of the emulsions
  • emulsion compositions of this type which may be formulated in various forms including lotions, creams, and aerosol forms
  • the provision of such emulsion compositions which have a low level of odor, are nontoxic and nonhazardous in use
  • the provision of such improved emulsion compositions which provide enhanced degreasing capabilities
  • the provision of such emulsion compositions which possess either a low order of combustibility or are non-combustible, which have a high flash point, which are safe to use and which are biodegradable
  • such improved emulsion compositions which incorporate organic solvents with inherently limited aqueous solubility and which
  • the present invention is directed to stable, aqueous cleaner/degreaser emulsion compositions which comprise: (a) at least one sparingly soluble organic solvent characterized by:
  • a solubilizing additive consisting of from approximately 0.1 to approximately 100 weight percent of a surfactant and from 0 to approximately 99.9 weight percent of a coupler, said solubilizing additive being present in an amount insufficient to solubilize all of the total organic solvent content but sufficient to emulsify the unsolubilized portion of the total organic solvent content;
  • the emulsion compositions of the invention thus contain a portion of the organic solvent component in the aqueous or continuous phase of the emulsions and the remainder of the organic solvent component in the emulsion or discontinuous phase thereby providing enhanced degreasing efficacies.
  • aqueous cleaner/degreaser emulsion compositions having improved degreasing capabilities can be formulated by combining at least one sparingly water soluble organic solvent having certain compositional and solvency characteristics and being present in an amount exceeding its aqueous solubility with a solubilizing additive and water, the solubilizing additive being present in an amount insufficient to solubilize all of the total organic solvent content but sufficient to emulsify the unsolubilized portion of the total organic solvent content.
  • the solubilizing additive performs a dual function, i.e., it solubilizes a portion of the total content of the organic solvent component above its inherent aqueous solubility limit and it emulsifies the unsolubilized portion of the total organic solvent content.
  • the resulting emulsion thus contains a portion of the sparingly water soluble organic solvent component in the aqueous or continuous phase of the emulsion and the remainder of the organic solvent component in the emulsified or oil phase of the emulsion.
  • the latter phase effectively constitutes an organic solvent reservoir which provides enhanced degreasing efficacy over that provided by the organic solvent in the aqueous phase alone.
  • the enhanced degreasing efficacy derived from the dual function of the solubilizing additive in the present invention is in contrast with the cleaning/degreasing action of available emulsions in which essentially none of the water insoluble hydrocarbon or halocarbon organic solvent is present in the aqueous phase of the emulsions and the cleaning/degreasing activity is wholly dependent upon the presence of the water insoluble organic solvent in the nonaqueous or discontinuous phase of the emulsions.
  • the emulsions of the present invention also provide greater degreasing efficacies at equal or equivalent organic solvent levels over those provided by the aqueous cleaner/degreaser compositions disclosed in my copending, coassigned application Serial No. 373,813, filed June 29, 1989, which are formulated in the form of totally water soluble compositions.
  • the emulsion compositions of the invention are therefore characterized by having the sparingly water soluble organic solvent present in both the aqueous phase and nonaqueous or oil phase of the emulsions.
  • the aqueous phase constitutes a saturated solution of the organic solvent by reason of the portion of the solvent being soluble in the aqueous phase to the extent of its inherent aqueous solubility therein and the portion of the solvent solubilized by the solubilizing additive into the aqueous phase.
  • the excess or remaining portion of the total organic solvent content is emulsified into the nonaqueous phase of the emulsions and constitutes the reservoir of organic solvent chiefly responsible for the enhanced degreasing activity exhibited by the emulsions of the invention.
  • the sparingly water soluble organic solvent must have the following characteristics:
  • the organic solvent has a water solubility in the range of approximately 0.05 to approximately 2.5 weight percent, more preferably between 1 and 2.5 weight percent.
  • Organic solvents meeting these criteria provide superior cleaning/degreasing action when formulated in accordance with the invention.
  • 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 gluterate (2 ester groups), phenacyl acetone (2 keto groups), diethylethylene diphosphonate (2 phosphonate ester groups), ethylene- dipropionate (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-p_-phthalate (2 ester groups).
  • organic solvents containing dissimilar functional groups from among those listed above may be mentioned 2-phenoxyethanol (hydroxy, ether groups), l-phenoxy-2-propanol (hydroxy, ether groups), N-phenylmorpholine (amino, ether groups), isopro- pylacetoacetate (keto, ester groups), o-methoxybenzyl alcohol (ether, hydroxy groups), 4'-methoxyacetophenone (ether, ketone groups), p_-nitrophenetole (nitro, ether groups), 2-hexoxyethanol (hydroxy, ether groups), ethylcyano-acetoacetate (cyano, keto, ester groups).
  • E-anisaldehyde (ether, aldehyde groups), polypropylene glycol 1200, 2000, and 4000 (ether, hydroxyl groups), n-butoxy acetate (ether, ester groups), and 2-phenylthioethanol (thioether, hydroxyl groups).
  • the organic solvent it is also desirable but not essential that the organic solvent have a relatively low volatility or high flash point, exhibit a low level of odor, be chemically stable, nontoxic, non- hazardous, liquid or easily liquified at ambient temperatures, 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”), ⁇ -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), cyclohex
  • 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 l-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.
  • oligomeric, hydrophobic solvents having limited aqueous solubility and molecular weights of up to 5000, preferably below 4000, are preferred since they also function as emollients, lubricants, humectants, and skin conditioners and do not defat the skin.
  • Such solvents include polypropylene glycols (e.g., Dow P2000, PPG-20, 26 and 30), poly(l,2-butylene glycol), poly(2,3-butylene glycol), poly(norbornane oxide glycol), poly(styrene oxide glycol), poly(phenylglycidyl ether glycol), poly(isobutylglycidyl ether glycol), poly(methylglycidyl ether glycol), phenoxypolypropylene glycol, butoxypolypropylene glycol (PPG-14 butyl ether), polypropylene glycol butyl ether (PPG-18 butyl ether), polyoxypropylene n-butyl ether, polytetramethylene ether glycol, poly(tetrahydrofuran) , poly(ethyl vinyl ether), poly(isobutyl vinyl ether), poly(diallyl ether), polyoxypropylene (30) trimethylpropanetriol, poly[propylene
  • organic solvents having an aqueous solubility of less than approximately 0.05 weight percent and organic solvents having an aqueous solubility in excess of approximately 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.
  • an organic solvent meeting the required criteria is combined with a solubilizing additive and water.
  • the solubilizing additive consists of from approximately 0.1 to approximately 100 weight percent of a surfactant and from 0 to approx ⁇ imately 99.9 weight percent of a coupler and, as stated, the solubilizing additive is present in the formulated compositions in an amount insufficient to solubilize all of the total organic solvent content but sufficient to emulsify the unsolubilized portion of the total organic solvent content.
  • solubilizing additive surfactant or surfactant plus coupler
  • amount of solubilizing additive will vary depending upon its solubilizing efficacy and upon the particular organic solvent employed; it can readily be determined by simple experimentation in each instance.
  • organic solvents whose aqueous solubility is between approximately 0.05 and approximately 2.5 weight percent.
  • the solubilizing additive used in the practice of the invention may consist of one or more compatible surfactants or surfactant(s) 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.
  • the use of a surfactant alone will suffice to achieve the desired solubilization and emulsification of the organic solvent component while in other instances the use of a surfactant or compatible surfactant blend in combination with a coupler may be utilized to achieve the desired dual function of the solubilizing additive component.
  • 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 surfactants employed in the practice of this invention may be nonionic, anionic, cationic or amphoteric in character.
  • the use of nonionic surfactants is generally preferred to avoid the formation or presence of ionic surfactant salts which tend to break emulsions.
  • Preferred nonionic surfactants include alkylphenoxypoly(ethenoxy) alkanols, alkoxypoly(ethenoxy)alkanols and fatty acid alkanolamides.
  • nonionic surfactants useful in the practice of the invention include octylphe- noxypoly(ethyleneoxy)(4)ethanol, nonylphenoxypoly(ethylene- oxy)(5)ethanol, dodecylphenoxypoly(ethyleneoxy)(8)ethanol, polyoxyethylene (7) lauryl alcohol, polyoxye hylene (4) tridecyl alcohol, lauryloxypoly(ethyleneoxy) (8)ethyl methyl ether, undecylthiopoly(ethyleneoxy) (6)ethanol, methoxypoly(oxyethylene(10)/(oxypropylene(20))-2-propanol block copolymer, nonyloxypoly(propyleneoxy)(4)/(ethyl- eneoxy) (10)ethanol, dodecyl polyglycoside, polyoxyethylene (9) monolaurate, polyoxyethylene (8) monoundecanoate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (18) sorbitol mono
  • the fatty acid alkanolamides are a class of nonionic surfactants derived from a 1:1 or 2:1 molar reaction between alkanolamines such as diethanolamine and varying chain length fatty acids such as stearic or oleic acid.
  • alkanolamines such as diethanolamine
  • chain length fatty acids such as stearic or oleic acid.
  • the fatty acid alkanolamides resulting from a 1:1 catalyzed reaction between an alkanolamine and a fatty acid are preferred since these predominantly consist of the desired nonionic dialkanolamide without appreciable amounts of ionic amine soaps.
  • soyamide diethanolamide (1:1) (Mackamide S, Mclntyre Group Ltd., Chicago, Illinois), linoleamide diethanolamide (1:1) (Monamid 15-70W, Mona Industries, Inc., Paterson, New Jersey), oleamide diethanolamide (1:1) (Clindrol 100-0, and Product WRS 1-66, Clintwood Chemical Company, Chicago, Illinois), ricinoleamide diethanolamide (1:1) (Mackamide R, Mclntyre Group Ltd.) isostearamide diethanolamide (1:1) (Monamid 150-IS, Mona Industries, Inc.
  • Illustrative anionic surfactants for use in the invention include dodecylbenzene sulfonic acid, monoethanolamine dodecylbenzenesulfonate, sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate, morpholinium dodecylbenzene sulfonate, ammonium dodecylbenzene sulfonate, isopropylamine dodecylbenzene sulfonate, sodium tridecyl- benzene sulfonate, sodium dinonylbenzene sulfonate, potassium didodecylbenzene sulfonate, dodecyl diphenyloxide disulfonic acid, sodium dodecyl diphenyloxide disulfonate, isopropylamine decyl diphenyl
  • Illustrative useful cationic surfactants include a mixture of n-alkyl (C ⁇ .2 50%, Cl4 30%, C ⁇ 6 17%, Ci ⁇ 3%) dimethyl ethylbenzyl ammonium chlorides, hexadecyltrimethyl-ammonium methosulfate, didecyldimethylammonium bromide and a mixture of n-alkyl (68% C ⁇ 2' 32% C14) dimethyl benzyl ammonium chlorides.
  • amphoteric surfactants include cocamidopropyl betaine, sodium palmityloamphopro- pionate, 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 use in the practice of the invention are the alkylphenoxy poly(ethenoxy) alkanol and fatty acid alkanolamide nonionic surfactants.
  • 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 diphenyoxide 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. Additional couplers or hydrotropes known to the art may also be utilized.
  • solubilizing additive component of the emulsion 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/or 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 solvent solubilization and emulsification.
  • 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 emulsion compositions of the invention.
  • a viscosifying thickener or thickening agent may be incorporated to improve the long term stability of the emulsion compositions.
  • thickened emulsion compositions often retard or totally prevent droplet coalescence, overcome phase separation caused by settling or rising droplet mobility tendencies, and often ameliorate the emulsion destabilizing effects of certain ionic components present in an emulsion composition.
  • the judicious employment of one or more thickening agents may, in fact, allow the propitious use of ionic, but otherwise emulsion destabilizing, solubilizing additives in the practice of this invention.
  • Excessive foaming may occur when certain compositions, viscosified with thickeners, are agitated to the extent that accumulating air bubbles are trapped in the emulsion. Should this occur, or likely occur, the use of suitable defoamers (e.g., perfluoroalkyl phosphate esters or silicone) or antifoaming agents may need to be incorporated into the emulsion compositions.
  • suitable defoamers e.g., perfluoroalkyl phosphate esters or silicone
  • antifoaming agents may need to be incorporated into the emulsion compositions.
  • viscosifying thickeners useful in the practice of the invention may be mentioned acrylic acid/alkyl methacrylate copolymers, carboxy acrylic polymers, guar gums, xanthan gums, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, bentonite clays, organicallly modified magnesium aluminum silicates, polyethylene glycols, polyethylene oxide, fumed silica, polyacrylic acid crosslinked with polyalkenyl polyethers, polyacrylamide, polyvinyl alcohol, ⁇ oly(methylvinyl ether/maleic) anhydride and sodium alginate.
  • Other viscosifying thickeners known to the art may also be used.
  • the viscosifying thickener is anionic in nature such as the thickener acrylic acid/alkyl methacrylate copolymer (Acrysol ICS-1 by Rohm & Haas)
  • an amine such as triethanolamine or other neutralizing base should also be incorporated to neutralize any free carboxylic acid groups and thereby cause enhanced thickening.
  • nonionic thickeners such as guar gums, hydroxyethyl cellulose and hydroxypropyl cellulose, the inclusion of such an amine is unnecessary.
  • chelants such as the sodium salts of ethylenedia- minetetraacetic acid (Hampene 100 or Versene 100), defoamers and foam controlling agents, fragrances, dyes, preservatives, lubricants, emollients, pH adjustants, dispersants, abrasives, anti-corrosion additives and anti-rust additives.
  • an anti flash-rusting additive such as an alkanolamine (e.g., monoethanolamine) or sodium nitrite may be incorporated.
  • the compositions be formulated to have a pH within a range of about 6.5-10 so as to be gentle to the hands and avoid defatting the skin.
  • the emulsion compositions of the invention may be prepared by combining the various components together under mechanical mixing conditions to form the desired emulsions.
  • the solubilizing additive may first be dispersed in water with stirring followed by the addition of the sparingly soluble organic solvent with stirring over a period of time to achieve complete emulsification.
  • Other viable, proven techniques involving formation of either O/W or W/O emulsions or emulsion concentrates, optionally followed by phase inversions, may also be employed.
  • the organic solvent and solubilizing additive components may be pre-emulsified in water with stirring and a thickening agent added to form the final emulsion in semipaste or thickened form.
  • the emulsions of the invention Upon sufficient dilution with water, the emulsions of the invention will first be transformed into microemulsion form and then into solution form with an accompanying decrease in the degreasing efficacy of the composition as shown by the experimental test data presented hereinafter.
  • the invention may be practiced to prepare emulsion compositions having varying concentrations of components, especially solvent level, depending upon the end use for the emulsions and, thus, emulsion concentrate compositions and ready-to-use strength emulsion compositions can be prepared. In either case, the desired stabilities for the various emulsions of the invention can be achieved by observing the following principles.
  • emulsion concentrate compositions are more susceptible to destabilization (or "breaking") with increasing ionic strength than their less concentrated, more dilute counterparts. For this reason the use of, e.g. ionic surfactants and couplers, ionic builders, and ionic anti-flash rust/anti-corrosion additives, etc. in formulating concentrates must be kept at a minimum or, if possible, wholly avoided or eliminated. This can often be accomplished simply by substituting equivalent nonionic replacements for ionic ones. On the other hand, ready-to-use strength emulsion compositions (such as described in Example 27 hereinafter) can often safely accommodate modest levels of ionic components, additives, etc.
  • total solids content refers, respectively, to the combined percentages of nonvolatile components and to the sum total of nonaqueous volatile and nonvolatile components.
  • 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) were thinly smeared/rub-on coated with Vaseline brand white petroleum jelly on one side only to a distance of 1.0" from the bottom edge to provide a 1.0" x 1.0" coated area.
  • test cleaner/degreaser emulsions or solutions were employed at the strength indicated and in an amount sufficient to fill a 50 ml Pyrex beaker containing the vaned disc magnetic stixrer bar to a level of 40 ml.
  • Each test material and surrounding air were maintained at 21 ⁇ 0.5°C and the test material 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 emulsion or 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 material 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 material bath and immediately “read” for "% Vaseline removed from the 1.0" x 1.0" 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.
  • An aqueous cleaner/degreaser emulsion was prepared having the following composition:
  • the isostearamide diethanolamide were stirred until the former was dispersed. l-phenoxy-2-propanol solvent was then stirred into the dispersion at room temperature for 45 minutes to achieve complete emulsification.
  • the resulting composition was an intensely bluish/white emulsion having a pH of 8.86, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 4.0 centipoise, a total solids content (theory) of 1.50%, and a total actives content (theory) of 11.50%.
  • the emulsion exhibited no flash point and was found to be storage stable for greater than five months at room temperature. If forced to slowly separate or oil out, e.g., in freeze/thaw cycling, the composition is easily redispersed into emulsion form by agitation.
  • microemulsion At a 1:5 dilution with water, a bluish/white microemulsion formed.
  • the microemulsion very readily and completely removed the following markings from alkyd enameled metal surfaces: black, indelible Magic Marker felt pen, blue and black indelible ballpoint pen, #1 hardness pencil, red (waxy) crayon and smeared automotive grease.
  • the above-formed microemulsion was subjected to the degreasing test method of Example 1 with the following results:
  • Example 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
  • the resulting composition was an intensely bluish/white emulsion having a pH of 10.07, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 5.5 centipoise, a total solids content (theory) of 2.50%, and a total actives content (theory) of 12.60%.
  • the emulsion exhibited no flash point and was found to be storage stable for in excess of five months at room temperature. Upon very slight, slow oiling out, the composition was readily redispersed on shaking. At a 1:5 dilution with water, a bluish/white microemulsion formed.
  • microemulsion very easily, readily and completely removed the following markings from alkyd enameled metal surfaces: black, indelible Magic Marker felt pen, blue and black indelible ballpoint pen, #1 hardness pencil, red (waxy) crayon and smeared automotive grease.
  • Example 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition: Component Wt.% l-Phenoxy-2-propanol 20.0
  • the resulting composition was an intensely bluish/white emulsion having a pH of 9.76, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 6.5 centipoise, a total solids content (theory) of 3.00%, and a total actives content (theory) of 13.10%.
  • the emulsion exhibited no flash point and was found to have excellent storage stability for at least two months at room temperature with no separation occurring.
  • microemulsion At a 1:5 dilution with water, a bluish/white microemulsion formed.
  • the microemulsion very easily, readily and completely removed the following workings from alkyd enameled metal surfaces: black, indelible Magic Marker felt pen, blue and black indelible ballpoint pen, #1 hardness pencil, red (waxy) crayon and smeared automotive grease.
  • Example 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
  • the resulting composition was an intensely bluish/white emulsion having a pH of 9.72, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 4.8 centipoise, a total solids content (theory) of 3.5%, and a total actives content (theory) of 13.6%.
  • the emulsion exhibited no flash point and was found to have excellent storage stability for at least two months at room temperature with no separation occurring.
  • microemulsion At a 1:5 dilution with water, a bluish/white microemulsion formed. The microemulsion very quickly and completely removed all of the markings set forth in Examples 2-4 from alkyd enameled metal surfaces.
  • microemulsion was subjected to the degreasing test method of Example 1 with the following results:
  • Example 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
  • the resulting composition was a bluish/white emulsion having a pH of 9.92, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 4.0 centipoise, a total solids content (theory) of 3.0%, and a total actives content (theory) of 13.1%.
  • the emulsion exhibited no flash point and was found to have good/excellent storage stability for in excess of two months at room temperature.
  • microemulsion At a 1:5 dilution with water, a bluish/white microemulsion formed. The microemulsion very easily and completely removed all of the markings set forth in Examples 2-4 from alkyd enameled metal surfaces.
  • microemulsion was subjected to the degreasing test method of Example 1 with the following results:
  • Example 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
  • the latter three components were stirred until fully dispersed and the l-phenoxy-2-propanol was then stirred into the dispersion for one hour to form an emulsion.
  • the resulting composition was a white, colorless emulsion with a slightly bluish cast, having a pH of 9.93, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 4.6 centipoise, a total solids content (theory) of 3.5%, and a total actives content (theory) of 13.6%.
  • the emulsion exhibited no flash point, and was found to have good storage stability for in excess of two months at room temperature.
  • Example 2 At a 1:5 dilution with water, a white to bluish/white emulsion was formed. The emulsion completely removed all of the markings set forth in Examples 2-4 from alkyd enameled metal surfaces. The emulsion was subjected to the degreasing test method of Example 1 with the following results:
  • Example 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
  • the resulting composition was a white emulsion having a pH of 10.21, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 4.5 centipoise, a total solids content (theory) of 3.0%, and a total actives content (theory) of 13.1%.
  • the emulsion exhibited no flash point, and was found to have good/excellent storage stability for two months at room temperature.
  • Example 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition: Component Wt.% l-Phenoxy-2-propanol 20.0
  • the resulting composition was an intensely bluish/white emulsion having a pH of 9.79, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 6.2 centipoise, a total solids content (theory) of 3.5%, and a total actives content (theory) of 13.6%.
  • the emulsion exhibited no flash point, and was found to be very stable over extended periods at room temperature.
  • microemulsion readily and completely removed all of the markings set forth in Examples 2-4 from alkyd enameled metal surfaces.
  • microemulsion was subjected to the degreasing test method set forth in Example 1 with the following results:
  • Example 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition: Component Wt.% l-Phenoxy-2-propanol 20.0
  • the resulting composition was an intensely white emulsion with a slight bluish cast and having a pH of 10.42, a Brookfield viscosity (LV-#2, spindle, 60 rpm) of 5.0 centipoise, a total solids content (theory) of 3.5%, and a total actives content (theory) of 13.6%.
  • the emulsion was quite stable at room temperature for 1-2 months.
  • microemulsion readily and completely removed all of the markings set forth in Examples 2-4 from alkyd enameled metal surfaces.
  • microemulsion was subjected to the degreasing test method of Example 1 with the following results:
  • Example 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition: Component Wt.% l-Phenoxy-2-propanol 30.0
  • the resulting composition was an intensely bluish/white emulsion having a pH of 9.63, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 7.0 centipoise, a total solids content (theory) of 5.0%, and a total actives content (theory) of 20.15%.
  • the emulsion exhibited excellent stability over an extended period at room temperature.
  • a bluish/white microemulsion was formed which had a 1.67% concentration of l-phenoxy-2-propanol.
  • the microemulsion very easily and completely removed all of the markings set forth in Examples 2-4 from alkyd enameled metal surfaces.
  • the microemulsion was subjected to the degreasing test method of Example 1 with the following results:
  • Example 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
  • the resulting composition was a very intense bluish/white emulsion having a pH of 9.85, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 6.5 centipoise, a total solids content (theory) of 4.0%, and a total actives content (theory) of 14.1%.
  • the emulsion exhibited excellent stability over at least a four month period.
  • a bluish to bluish/white microemulsion was formed which had a 1.67% concentration of l-phenoxy-2-propanol.
  • the microemulsion very easily and completely removed all of the markings set forth in Examples 2-4 from alkyd enameled metal surfaces.
  • the microemulsion was subjected to the degreasing test method of Example 1 with the following results:
  • a hand cleaner in the form of a semipaste emulsion was prepared having the following composition:
  • Soft H 2 0 261.0 300.0 The polypropylene glycol and linoleamide diethanolamide were pre-emulsified in water with stirring and the Acrysol ICS-1 thickening agent was then added with stirring. The triethanolamine was then added dropwise with stirring to form a semipaste, intensely white emulsion.
  • the emulsion had a pH of 8.22, a Brookfield viscosity (LV-#4 spindle, 6 rpm) of 19,250 centipoise, and a total solids content (theory) of 11.9%.
  • the emulsion had a very smooth feel and exhibited fair/good removal of oily, greasy soils from hands.
  • a hand cleaner in the form of a semipaste emulsion was prepared having the following composition:
  • the first four components listed were pre-emulsified with stirring, and the linoleamide diethanolamide was added with vigorous stirring to form a semipaste, intensely white emulsion.
  • the emulsion had a pH of 6.72, a Brookfield viscosity (LV-#4 spindle, 6 rpm) of 23,000 centipoise, a total solids content (theory) of 6.61%, and a total actives content (theory) of 11.61%.
  • the emulsion had a smooth feel, excellent rinsing properties, and exhibited excellent, fast removal of oily, greasy soils from hands although somewhat irritating to the skin.
  • a hand cleaner in the form of a thick, paste/lotion emulsion was prepared having the following composition:
  • the emulsion had a pH of 7.62, a Brookfield viscosity (LV-#4 spindle, 6 rpm) of 54,000 centipoise, a total solids content (theory) of 20.3%, and a total actives content (theory) of 21.3%.
  • the emulsion had a smooth feel, good rinsing characteristics, and exhibited good/very good removal of oily and greasy soils from hands.
  • Example 15 was repeated in preparing a semipaste emulsion having the following composition:
  • Tripropyleneglycol 1.0 monomethyl ether Dowanol TPM
  • the resulting composition was an intensely bluish/white emulsion in the form of a semipaste.
  • the emulsion had a pH of 7.02, a Brookfield viscosity (LV-#4 spindle, 6 rpm) of 28,000 centipoise, a total solids content (theory) of 20.4%, and a total actives content (theory) of 23.42%.
  • the emulsion had a very smooth feel, excellent rinsability characteristics, and exhibited very good removal of oily and greasy soils from hands with a low level of irritation to the skin.
  • Example 15 was repeated in preparing a thick lotion emulsion having the following composition: Component Wt.% Polypropylene glycol 9.0 (Dow P-2000)
  • Linoleamide diethanolamide (1:1) 5.0 (Soyamide DEA-Clindrol LT-15-73-1)
  • the resulting composition was an intensely white emulsion in the form of a thick lotion.
  • the emulsion had a pH of 9.33, a Brookfield viscosity (LV-#4 spindle, 6 rpm) of 24,400 centipoise, and a total solids content (theory) of 23.27 %.
  • the emulsion had a very smooth feel, excellent rinsability characteristics, and exhibited excellent removal of oily and greasy soilants from hands.
  • Example 15 was repeated in preparing a cream/lotion emulsion having the following composition:
  • the resulting composition was an intensely white emulsion in the form of a cream/lotion.
  • the emulsion had a pH of 8.07, a Brookfield viscosity (LV-#3 spindle, 12 rpm) of 4300 centipoise, a total solids content (theory) of 20.3%, and a total actives content (theory) of 21.3%.
  • the emulsion had a very smooth feel, excellent rinsability characteristics, and exhibited excellent removal of oily and greasy soilants from hands.
  • the emulsion is fully biodegradable.
  • An emulsion was prepared having the following composition:
  • the water was added with stirring to the l-phenoxy-2-propanol and nonionic surfactant components.
  • the Acrysol ICS-1 thickening agent was then added with continued stirring, followed by the dropwise addition of the triethanolamine with stirring.
  • the resulting composition was a white, creamy emulsion having a pH of 7.82, a Brookfield viscosity (LV-#2 spindle, 30 rpm) of 120 centipoise, a total solids content (theory) of 2.59%, and a total actives content (theory) of 12.59%.
  • diluted emulsions were formed which easily removed black Magic Marker markings from alkyd enameled metal surfaces.
  • Example 19 was repeated in preparing an emulsion having the following composition:
  • the resulting composition was a white, creamy emulsion having a pH of 8.42, a Brookfield viscosity (LV-#2 spindle, 30 rpm) of 217 centipoise, a total solids content (theory) of 1.75%, and a total actives content (theory) of 11.75%.
  • the marked change in degreasing efficacy (rates) between the 1:10 and 1:20 composition dilution ratios can, in part, be attributable to the change from emulsion to solution form of the cleaner/degreaser.
  • Example 19 was repeated in preparing an emulsion having the following composition: Component Wt.% l-Phenoxy-2-propanol 20.0
  • the resulting composition was a white, creamy emulsion having a pH of 8.39, a Brookfield viscosity (LV-#2 spindle, 30 rpm) of 162 centipoise, a total solids content (theory) of 1.75%, and a total actives content (theory) of 11.75%.
  • LV-#2 spindle 30 rpm
  • Example 19 was repeated in preparing an emulsion having the following composition:
  • the resulting composition was an intense white, creamy emulsion having a pH of 7.67, a Brookfield viscosity (LV-#2 spindle, 30 rpm) of 230 centipoise, a total solids content (theory) of 1.33% and a total actives content (theory) of 16.33%.
  • Example 19 was repeated in preparing an emulsion having the following composition:
  • a bluish/white microemulsion formed which very easily and fully removed the following markings from alkyd enameled metal surfaces: black Magic Marker felt pen, blue and black indelible ballpoint pen, #1 hardness pencil and red (waxy) crayon.
  • microemulsion was subjected to the degreasing test method of Example 1 with the following results:
  • Example 23 was repeated in preparing an emulsion having the following composition:
  • the resulting composition was an intensely bluish-white emulsion having a pH of 8.27, a Brookfield viscosity (LV-#3 spindle, 12 rpm) of 3650 centipoise, a total solids content (theory) of 2.8%, and a total actives content (theory) of 12.8%.
  • microemulsion was subjected to the degreasing test method of Example 1 with the following results:
  • aqueous cleaner/degreaser emulsion in the form of an aerosol formulation was prepared having the following composition:
  • the first four components listed above were pre-emulsified under high speed stirring for three minutes with a water driven impeller, the ammonium hydroxide was then very slowly added with vigorous stirring to give immediate thickening, and the sodium nitrite was added last with vigorous stirring until it was dissolved.
  • the resulting composition was a white emulsion/fluid with a pH of 8.78, a Brookfield viscosity (LV-#2 spindle, 30 rpm) of 68 centipoise, a total solids content (theory) of 0.79%, and a total actives content (theory) of 3.79%.
  • the above composition was aerosolized in a 6 oz. aerosol can using 8.32 g (15.0 ml) of a propane-isobutane blend propellant (sold under the trade designation A-55) .
  • the can was equipped with an AR-75 valve and Mark-18-1525 actuator.
  • the fill ratio was 87/13.
  • An aqueous cleaner/degreaser emulsion was prepared having the following composition:
  • the first four components were stirred at room temperature until fully dispersed.
  • the two organic solvents were then added with vigorous stirring for 0.5 hr.
  • the resulting composition was an intensely bluish/white emulsion having a pH of 10.20, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 4.5 centipoise, a total solids content (theory) of 0.35% and a total actives content (theory) of 3.55%.
  • the emulsion exhibited excellent stability characteristics.
  • the emulsion possessed excellent, rapid, and efficient cleaning/degreasing action against the following soilants: black Magic Marker markings, ballpoint pen markings, #1 hardness pencil markings, red (waxy) crayon markings, automotive greases, Vaseline, lard, shortening, and lipophilic oils.
  • soilants black Magic Marker markings, ballpoint pen markings, #1 hardness pencil markings, red (waxy) crayon markings, automotive greases, Vaseline, lard, shortening, and lipophilic oils.
  • Example 26 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
  • the resulting composition was a bluish emulsion (iridescent cast) having a pH of 10.21, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 72 centipoise, a total solids content (theory) of 0.46% and a total actives content (theory) of 3.26%.
  • the emulsion exhibited excellent stability characteristics.
  • Example 28 The emulsion possessed excellent, rapid, and efficient cleaning/degreasing action against all the soilants listed in Example 26.
  • Example 28
  • Example 26 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
  • the resulting composition was a light, slightly bluish/white emulsion having a pH of 10:08, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 57 centipoise, a total solids content (theory) of 0.50% and a total actives content (theory) of 4.30%.
  • the emulsion exhibited excellent stability characteristics.
  • the emulsion possessed excellent, rapid, and complete cleaning/degreasing action against all the soilants listed in Example 26.
  • Example 26 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition: Component Wt.%
  • the resulting composition was an intensely bluish/white emulsion having a pH of 10.43, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 4.3 centipoise, a total solids content (theory) of 0.25% and a total actives content (theory) of 2.90%.
  • the emulsion exhibited excellent stability characteristics.
  • the emulsion possessed excellent, rapid, and complete cleaning/degreasing action against all the soilants listed in Example 26.
  • An aqueous cleaner/degreaser emulsion was prepared having the following composition:
  • EB acetate Butoxyethyl acetate (EB acetate) Acrylic acid/alkyl methacrylate 1.0 copolymer, 30% aqueous (Acrysol ICS-1)
  • the first two components were stirred at room temperature for 15 minutes to completely disperse the isostearamide diethanolamide in water.
  • the butoxyethyl acetate was then added with vigorous stirring at room temperature for 30 minutes.
  • the Acrysol ICS-1 was next added with stirring followed by dropwise addition of the ammonium hydroxide with vigorous stirring at room temperature for 15 minutes.
  • the resulting composition was a slightly bluish/white, milky emulsion having a pH of 7.17, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 134 centipoise, a total solids content (theory) of 0.62% and a total actives content (theory) of 3.62%.
  • the emulsion exhibited excellent stability characteristics.
  • the emulsion possessed excellent, rapid, and complete cleaning/degreasing action against all the soilants listed in Example 26.
  • a hand cleaner emulsion was prepared having the following composition:
  • the first five components were emulsified and the Acrysol ICS-1 was then added with vigorous stirring.
  • the resulting composition was an intensely bluish/white emulsion which had a creamy, smooth feel.
  • the emulsion had a pH of 6.98, a Brookfield viscosity (LV-#4 spindle, 6 rpm) of 9500 centipoise and a total actives content (theory) of 28.45%.
  • the emulsion exhibited superior removal of oily/greasy soilants from hands.
  • the cleaning/degreasing action was drastically reduced.
  • aqueous cleaner/degreaser emulsion in the form of an aerosol formulation was prepared having the following composition:
  • the first five components listed above were stirred at high speed for 15 minutes to fully disperse the lauramide diethanolamide and to form a microemulsion.
  • the l-phenoxy-2-pro ⁇ anol was then added with vigorous stirring for 30 minutes at room temperature after which the Acrysol ICS-1 was added dropwise with good stirring.
  • the resulting composition was a bluish/white emulsion with a pH of 9.86, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 28 centipoise, a total solids content (theory) of 0.57%, and a total actives content (theory) of 3.37%.
  • the emulsion exhibited excellent stability.
  • Example 33 The above composition was aerosolized as described in Example 25 using a fill ratio of 100/15. It was found that the resulting aerosol formulation produced a moderately wet, fast-breaking foam with excellent vertical cling. The formulation exhibited excellent cleaner/degreaser action against the markings listed in Example 25 and had good/excellent wet-out properties.
  • Example 33
  • An aqueous cleaner/degreaser emulsion was prepared having the following composition: Component Isostearamide diethanolamide (1:1) (Monamid 150-IS)
  • the first three components listed above were stirred until the mixture was fully homogeneous and formed a microemulsion.
  • the l-phenoxy-2-propanol was then stirred into the microemulsion with stirring continued for one hour at room temperature after which the antifoaming agent was added with stirring.
  • the resulting composition was a very intense bluish white emulsion having a pH of 10.53, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 7.5 centipoise, a total solids content (theory) of 4.08%, and a total actives content (theory) of 14.55%.
  • the emulsion exhibited excellent stability.
  • Example 2 At a 1:5 dilution with water, a bluish to bluish/white microemulsion formed which very easily, quickly, and completely removed all of the markings set forth in Examples 2-4 from alkyd enameled metal surfaces.
  • the microemulsion was subjected to the degreasing test method of Example 1 with the following results:
  • This emulsion composition is especially suitable for use in mechanized high pressure/spray equipment where foam generation cannot be tolerated.
  • An aqueous cleaner/degreaser emulsion was prepared having the following composition:
  • the first four components listed above were stirred at room temperature until fully dispersed (c_a. 15 minutes) .
  • the l-phenoxy-2-propanol was added with vigorous stirring for 0.5 hour at room temperature and the Acrysol ICS-1 was added dropwise with vigorous stirring to viscosity the composition.
  • the resulting composition was an intensely bluish/white emulsion having a pH of 10.38, a Brookfield viscosity (LV-#2 spindle, 60 rpm) of 49 centipoise, a total solids content (theory) of 0.48%, and a total actives content (theory) of 3.28%.
  • the emulsion exhibited excellent stability.
  • the emulsion exhibited excellent cleaner/degreaser action against all of the markings set forth in Examples 2-4 and against Vaseline, lard, shortening and lipophilic oils.
  • This emulsion is suitable for use as a ready-to-use formulation applied by pump spray or trigger spray action.
  • An aqueous cleaner/degreaser emulsion was prepared having the following composition:
  • the water was added very slowly to the stirred mixture of the other two components listed above.
  • the formulation goes through a water/oil to oil/water transformation to form a bluish/white emulsion without the addition of a viscosifying thickener.
  • the emulsion had a pH of 7.67, a Brookfield viscosity (LV-#2 spindle, 30 rpm) of 53 centipoise and a total solids/total actives content (theory) of 3.3%.
  • This emulsion readily removed tar, grease, asphalt, black (rubber) heel and red (waxy) crayon marks from floor tile coated with polymeric floor finish using a wetted paper towel or cloth.
  • the tile buffs to a clear, colorless, high shine on air drying with no damage/solvent action on the floor finish.
  • An aqueous cleaner/degreaser emulsion was prepared having the following composition:
  • the first four components listed above were pre-emulsified with high speed stirring and the Acrysol ICS-1 was added dropwise under vigorous high speed/high shear stirring conditions.
  • the resulting composition was a white, creamy emulsion having a pH of 7.81, a Brookfield vrscosity (LV-#3 spindle, 12 rpm) of 870 centipoise and a total solids/total actives content (theory) of 3.9%.

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Abstract

On formule des compositions aqueuses stables d'agents de nettoyage/agent de dégraissage sous forme d'émulsions, à l'aide d'au moins un solvant organique modérément soluble présentant des caractéristiques de compositions spécifiées, d'un additif de solubilisation et d'eau. L'additif de solubilisation peut se composer d'approximativement 0,1 à approximativement 100 % en poids d'un tensio-actif, et de 0 à approximativement 99,9 % en poids d'un coupleur, et il est présent en une quantité insuffisante pour solubiliser tout le contenu du solvant organique total, mais suffisante pour émulsionner la partie non solubilisée du contenu du solvant organique total. Les compositions sous forme d'émulsions ainsi formulées présentent des efficacités de dégraissage améliorées.
EP19910901175 1989-12-19 1990-12-07 Aqueous cleaner/degreaser emulsion compositions Withdrawn EP0506744A4 (en)

Applications Claiming Priority (2)

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US45262389A 1989-12-19 1989-12-19
US452623 1989-12-19

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EP0506744A1 true EP0506744A1 (fr) 1992-10-07
EP0506744A4 EP0506744A4 (en) 1993-09-22

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EP (1) EP0506744A4 (fr)
JP (1) JPH05504584A (fr)
AU (1) AU6910191A (fr)
CA (1) CA2070679A1 (fr)
WO (1) WO1991009104A1 (fr)

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JP3452406B2 (ja) * 1993-10-07 2003-09-29 有限会社ケントス 有機系付着物の除去性能を有する組成物
WO1995013345A1 (fr) * 1993-11-12 1995-05-18 The Procter & Gamble Company Compositions detergentes liquides pour surfaces dures contenant un agent tensioactif detergent amphotere ainsi qu'un parfum
US5534198A (en) * 1994-08-02 1996-07-09 The Procter & Gamble Company Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity
US5942484A (en) * 1995-03-30 1999-08-24 The Procter & Gamble Company Phase-stable liquid fabric refreshment composition
US5681355A (en) * 1995-08-11 1997-10-28 The Procter & Gamble Company Heat resistant dry cleaning bag
US6010995A (en) * 1995-12-28 2000-01-04 Buckeye International, Inc. No/low volatile organic compound cleaner/degreaser composition
US5789368A (en) * 1996-01-26 1998-08-04 The Procter & Gamble Company Fabric care bag
US6233771B1 (en) 1996-01-26 2001-05-22 The Procter & Gamble Company Stain removal device
US5840675A (en) * 1996-02-28 1998-11-24 The Procter And Gamble Company Controlled released fabric care article
US5891197A (en) * 1996-08-02 1999-04-06 The Proctor & Gamble Company Stain receiver for dry cleaning process
US5872090A (en) * 1996-10-25 1999-02-16 The Procter & Gamble Company Stain removal with bleach
US5849039A (en) * 1997-01-17 1998-12-15 The Procter & Gamble Company Spot removal process
US5762648A (en) * 1997-01-17 1998-06-09 The Procter & Gamble Company Fabric treatment in venting bag
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
DE19908434A1 (de) * 1999-02-26 2000-10-05 Wack O K Chemie Gmbh Verfahren und Reinigungsflüssigkeit zum Flüssigreinigen von Gegenständen
US6583101B1 (en) 1999-08-25 2003-06-24 Ecolab Inc. Aqueous organic dispersions suitable for removing organic films and soils
US6916773B2 (en) 2002-07-31 2005-07-12 Ecolab, Inc. Non-surfactant solubilizing agent
US7008911B2 (en) 2002-09-06 2006-03-07 Ecolab, Inc. Non-surfactant solubilizing agent
US6767881B1 (en) 2003-03-19 2004-07-27 Ecolab, Inc. Cleaning concentrate
US8415286B1 (en) * 2012-06-13 2013-04-09 Green On Industries Inc. Solvent-free oil dispersant
JP6571632B2 (ja) * 2013-03-15 2019-09-04 クリアー ソリューションズ 多用途の硬質表面清浄剤
WO2019108990A1 (fr) * 2017-12-01 2019-06-06 Ecolab Usa Inc. Compositions de nettoyage et procédés d'élimination des graisses cuites sur les friteuses et autres surfaces chaudes
CN115710538B (zh) * 2022-11-11 2024-01-19 国网上海市电力公司 一种自乳化清洗材料及其制备方法与应用

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WO1991009104A1 (fr) 1991-06-27
EP0506744A4 (en) 1993-09-22
CA2070679A1 (fr) 1991-06-20
JPH05504584A (ja) 1993-07-15
AU6910191A (en) 1991-07-18

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