CA2070679A1 - Aqueous cleaner/degreaser emulsion compositions - Google Patents
Aqueous cleaner/degreaser emulsion compositionsInfo
- Publication number
- CA2070679A1 CA2070679A1 CA 2070679 CA2070679A CA2070679A1 CA 2070679 A1 CA2070679 A1 CA 2070679A1 CA 2070679 CA2070679 CA 2070679 CA 2070679 A CA2070679 A CA 2070679A CA 2070679 A1 CA2070679 A1 CA 2070679A1
- Authority
- CA
- Canada
- 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.)
- Abandoned
Links
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
Abstract
Stable, aqueous cleaner/degreaser emulsion compositions are formulated with at least one sparingly soluble organic solvent having specified compositional characteristics, a solubilizing additive and water. The solubilizing additive may consist 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 and is 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 so formulated provide enhanced degreasing efficacies.
Description
WO91/09104 PCT/US90/0~215 AQUEOUS CLEANER/DEGREASER
EMULSION COMPOSITIONS
Backaround o the Invention This invention relat2s to cleaner/degreaser compositions and, more particularly, to stable, aqueous cleaner~d2g easer compositions in the form of emulsions which e~hibit improved degreasing efficacies.
~ eretofor~, the conventional and available cleaner/de~LeaseL emulsion compositions have been water in oil or oil in water emulsions ln which the organic solvent component is an inher2ntly ~later insoluble organic solvent. Such available emulsion compositions include, for e~ample, 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 watér 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-Soi", and "DuBois Actusol". In the preparation of such emulsions, an inherently water insoluble organic solvent, typically a hydrocarbon solvent, is emulsified with one or more surfactants soluble in the solvent component. When this nonaqueous emulsion or solution is combined with water, a true milky emulsion is formed in which essentially none of the solvent component and only a relatively small ~` 30 amount of the surfactant component is dissolved in the .~ , .
; aqueous phase. Thus, the cleaning/degreasing efficacy of such emulsion compositions is almost entirely derived from the nonaqueous or discontinuous phase of the emulsion `' containing the solvent component necessary to remove oleophilic (hydrophobic) soilants.
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.~ ., -WO9l/09104 PCT/US90/07215 While conventional cleaner/degreaser emuIsion compositions possess some degree of efficacy, there is a need for cleaner/degreaser 0mulsion compositions which exhibit improved efficacy, particularly with respect to grease and oil removing efficacy.
Summarv of the Invention Among the several objects of the invention may be - noted ~he provision of stable, aqueous cleaner/degreaser emulsion composi~ions having improved cleaning/degreasing -10 efficacyi the provision of such emulsion compositions which ; are 0rm~ll2ted o proYlde a portion of the organic solvent content in ~otn the aqueous and nonaqueous phases of the emulsions; the provision of emulsion compositions of this type which may be formulated in various forms including lot-ions, 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; and the provision of such improved emulsion compositions which incorporate organic solvents with inherently limited aqueous solubility and which may be readily formulated from available components. Other objects and features will be in part apparent and in part pointed out hereinafter.
;~~ Briefly, the present invention is directed to stable, aqueous cleaner/degreaser emulsion compositions ~which comprise:
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EMULSION COMPOSITIONS
Backaround o the Invention This invention relat2s to cleaner/degreaser compositions and, more particularly, to stable, aqueous cleaner~d2g easer compositions in the form of emulsions which e~hibit improved degreasing efficacies.
~ eretofor~, the conventional and available cleaner/de~LeaseL emulsion compositions have been water in oil or oil in water emulsions ln which the organic solvent component is an inher2ntly ~later insoluble organic solvent. Such available emulsion compositions include, for e~ample, 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 watér 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-Soi", and "DuBois Actusol". In the preparation of such emulsions, an inherently water insoluble organic solvent, typically a hydrocarbon solvent, is emulsified with one or more surfactants soluble in the solvent component. When this nonaqueous emulsion or solution is combined with water, a true milky emulsion is formed in which essentially none of the solvent component and only a relatively small ~` 30 amount of the surfactant component is dissolved in the .~ , .
; aqueous phase. Thus, the cleaning/degreasing efficacy of such emulsion compositions is almost entirely derived from the nonaqueous or discontinuous phase of the emulsion `' containing the solvent component necessary to remove oleophilic (hydrophobic) soilants.
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.~ ., -WO9l/09104 PCT/US90/07215 While conventional cleaner/degreaser emuIsion compositions possess some degree of efficacy, there is a need for cleaner/degreaser 0mulsion compositions which exhibit improved efficacy, particularly with respect to grease and oil removing efficacy.
Summarv of the Invention Among the several objects of the invention may be - noted ~he provision of stable, aqueous cleaner/degreaser emulsion composi~ions having improved cleaning/degreasing -10 efficacyi the provision of such emulsion compositions which ; are 0rm~ll2ted o proYlde a portion of the organic solvent content in ~otn the aqueous and nonaqueous phases of the emulsions; the provision of emulsion compositions of this type which may be formulated in various forms including lot-ions, 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; and the provision of such improved emulsion compositions which incorporate organic solvents with inherently limited aqueous solubility and which may be readily formulated from available components. Other objects and features will be in part apparent and in part pointed out hereinafter.
;~~ Briefly, the present invention is directed to stable, aqueous cleaner/degreaser emulsion compositions ~which comprise:
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2~706~9 (a) at least one sparingly soluble organic solvent characterized by:
(i) having a water solubility in the range of approximately 0.05 to approximately -5 ~ weight percent;
(ii) not being a hydrocarbon or halocaroon;
naving one or more similar or disslmilar oxygen, nitrogen, sulfur, or phosphorous containing functional groups;
~ beir.g a sol-tent for hydrophobic soilants; and (v) being present in an amount e~ceeding its aqueous solubility;
(b) a solubilizing additive consisting of from appro~imately 0.1 to appro~imately 100 weight percent of a surfactant and from 0 to approximately 99.9 weight percent of a coupler, said solubilizins additive being present in an amount insufficient to solubilize all of the total organic SO1V2nL content but sufEicient to emulsify the unsolu~ilized portibn of the total organic solvent content;
~, and .. (c) water.
The emulsion compositions of the-invention thus : 25 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.
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Description of the Preferred Embodiments In accordance with the present invention, it has now been found that stable, 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 characteris~ics and being present in an amount e~ceeding its aquaous solubility with a solubilizing additive and water, the solubilizing additive being present in an amount insufEicient to solubilize all of the total organic solvent content but sufficient to emulsify the unsolllbil~ ~o~ portion of the total organic solvent content. ln ~he present invention, 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 2Q 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 derivad 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 wator insoluble organic solvent in u~3T~ 1 ~3-s ~
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the nonaqueous or discontinuous phase of the emulsions.
The emulsions of the present invention also provide greater degreasiny efficacies at equal or equivalent organic solvent levels over those provided by the aqueous cleaner/degr2aser compositions disclosed in my copending, coassigned application Serial No. 373,813, filed June 29, 1989, which are formulated in the orm o~ totally water soluble compositions.
The emulsion compositlons or the invention are therefore characteri~ed by having the sparingly water soluble organic solvent present in both the aqueous phase and nonaqueous or o~l ~hase o~ 'he 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 accivicy e~hlbi'ced by the emulsions of the invention.
For use in the present invention, the sparingly water soluble organic solvent must have the following characteristics: --(a) it must have limited water solubility in therange of approximately 0.05 to 6 weight percent;
~b) it must not be a hydrocarbon or halocarbon, (c) it must have one or more similar or dissimilar o~ygen, nitrogen, sulfur or phosphorous containing functional groups;
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W09l/~9l04 PCT/US9~/07215 (d) it must be a solvent for hydrophobic : soilants; and (e) it must be present in an amount exceeding its limited aqueous solubility.
Preferably, the organ~c sol~ent has a water solubility in the r2ngQ O r ~ppro~imately 0.05 to approximately 2.5 weight percent, morQ 3rersraDly between 1 and 2.5 waight percent.
:;: Organic solYents meeting these criteria provide superior ~` clcaning~dDg easing action when formulated in accordance with the invention.
The principal sla.sses o~ organic sol~ents from ~,7hich useful o-ganic sol-~ents may be selècted include esters, ~ . alchohols, ketones, aldehydes, ethers and nitriles. These : ~ . will generally contain one or more of the desired similar .
;` 15 or dissimilar functional groups listed above. Examples of ~: organic solvents containing similar functional groups from among those listed above include diethyl gluterate (2 ester ~ groups), phenacyl aoetone (2 keto groups), diethylèthylene ;~ diphosphonate (2 phosphonate ester groups), ethylene-dipropionate (2 ester groups), decylene glycol (2 hydroxyl groups), m-dimetho~ybenzen2 (2 ethe:r groups), adiponitrile (~2 nitrile groups), ethylene glycol dibutyl ether (2 ether groups), and diethyl-o-phthalate (2 ester groups). Among ; organic solvents containing dissimilar functional groups `
;~ 25 from among those listed above may be mentioned ; 2-phenoxyethanol (hydroxy, ether groups), l-phenoxy-2-propanol (hydro~y, ether groups), N-phenylmorpholine (amino, ether groups), isopro-: pylacetoacetate (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), ~:~
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~ WO9l/09104 PCT/~S90/07215 2~7~67~
~-anisaldehyde ~ether, aldehyde groups), polypropylene glycol 1200, 2000, and 4000 (ether, hydroxyl groups), n-buto~y acetate (ether, ester groups), and 2-phenylthioethanol (thioether, hydro~yl groups).
In addition to the criteria listsd above, it is also desirable but not essenti31 that the organic sol~ent have a relatively lo~ volatility or hlsh ~lash point, e~hibit a low level of odor, be chemically stable, nonto~.ic, non hazardous, liquid or eas~ly liqui-ied at ambient temperatures, and commercially availa~le.
The sparingly water soluble organic solvents which may be employed in t'ne ?rac" c~ O~ Lhe p.rasen.t ~n'tent ' on ~znd comprising some of tne solvents listad above) cogeclner with their aqueous ambient temperature solubility in wt.%
include 2-pheno~yethanol (2.3) (marketed under the trade designation HDowanol EPh"), ~-pheno~y-2-propanol (1.1) (marketed under the trade designation "Dowanol PPh"), ~l phenylethanol (1.6), acetophenone (0.5), -benzyl alcohol `l (4.4), benzonitrile (1.0), n-butyl acetate (0.7), n-amyl acetate (0.25), benzaldehyde (0.3~, ~,N-diethylaniline l (1.4), diethyl adipate (0.43), dimethyl-o-phthalate (0.43~, ! n-amyl alcohol (2.7), M-phenylmorpholine (1-0), `! n-buto~yethyl acetate (EB acetate) (l.l), cyclohe~anol ` (4.2), polypropylene glycol 1200 (2), dipropylene glycol mono-n-butyl ether (Dowanol DPnB) (5.0) cyclohe~anone (2.3), isophorone (1.2), methylisobutyl ketone- ~-2.0), methylisoamyl ketone (0.5), tri-n-butylphosphate (0.6), l-nitropropane (1.4), nitroethane ~4.5), dimethyl esters of mixed succinic, glutaric and adipic acids (5.7) (marketed under the trade designation "DBE ester" by DuPont), diethyl glutarate (0.88), diethyl malonate (2.08), poly-;~ oxyalkylene polyols (e.g., polyoxypropylene diols and : triols) such as the polypropylene glycols P1200, P2000 and P4000 (Dow Chemical), polypropylene glycol monobutyl ether . .
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(Dow Polyglycol L-1150) and polyglycol copolymers containing ethenoæy and propenoxy units (Dow 112-2). As will be apparent to those skilled in the art, the above-listed sparingly ~ater soluble organic solvents are merely lllustr3tivQ and various oth~or solvents meeting the criteria se-t OUL above may ~lso 'oe utilized in the practice of the invantlon~ ~ecau~e of their performance characteri~t1cs, lac~ of odor, low volatility/high flash point, chemical stability and availa'oility, 2-phenoæ-y-ethanol and l-pheno~-1-2-propanol are the pre~erred organic solvents of choice. N-butoæyethyl acetate (EB
acot~te~ -n~ tho dimQthiTl ~stors o' mi~oa succinic, glutaric and adlplc 2C1dS aro also amor.g the prefer~ed organic solvents. For emulsions of the invention in the form of lotions and creams, the use of oligomeric, hydrophobic solvents having limited aqueous solubility and molecular weights of up to 5000, preferably b~low 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(1,2-buLylene glycol), poly(2,3-'outylene glycol), ' poly(norbornane o~ide glycol), poly(styrene oxide glycol), poly(phenylglycidyl ether glycol), polytisobutylglycidyl ether glycol), poly~methylglycidyl ether glycol), phenoæypolypropylene glycol, butoæypolypropylene glycol (PPG-1~ butyl ether), poiypropylene glycol butyl ether ~PPG-18 butyl ether), polyo~ypropylene n-butyl ether, polytetramethylene ether glycol, poly(tetrahydrofuran), poly(ethyl vinyl ether), poly(isobutyl vinyl ether), poly(diallyl ether), polyoæypropylene (30) trimethylpropanetriol, poly[propylene oæide (lO)/phenylglycidyl ether (lO) glycol], and similar solvents ~nown to the art.
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WO91/0~104 PCT/US90/07215 2~7~79 9. - .
As indicated, a number of otherwise potent 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. l4.3 wt.-5), propylene carbonate (a~. sol. l9.6 wt.%j and N-methyl pyrrolidone (ininite aq. sol.) are not useful in the practice of the invention.
In formulating the stable, aqueous cleaner/desreaser emulsion compositions of the invention, an organic solvent meeting the required cr~ terl a s combin~d wlth a solubilizing additive and water. The solu~ilizing additi~e consists of from approximately O.l to appro~imately lO0 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 ~j 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. The amount of solubilizing additive (surfactant or surfactan~ plus coupl2r) required to accomplish this objective will vary depending upon its solubilizing efficacy and upon the particular organic solvent employed; it can readily be determined by simple e~perimentation in each instance. In s2neral, it is desirable to formulate the emulsion compositions of the invention with as little of the solubilizing additivè as possible while achieving the desired solubilization and emulsification of the organic solvent stated above since emulsions so formed will tend to remain in emulsion form - even upon being diluted many times with water.
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WO9l/~9104 PCT/US90/07215 S
Further, it has been found that the best results are achieved when the emulsion compositions are formulated with organic solvents whose aqueous solubility is between approzimately 0.05 and appro~imately 2.5 weight percent.
Also, it has be~n ~ound that ~lhen an organic solvent is employed having a water so:!ubility in the upper portion of the ov~rall r2nge 0.05 to ~ 7~i~ight percent, it is preferabls co uti7i~e a solubili~1ng addiciYe which is a . relatiYely b~ttQr emulsirving agent than a solubilizing agent ror the organic sol;enL. On th2 other hand, ~7hen employing an organic solvent whose solubility is in the Iower portlon^ of th~ oY~r~ll -?.~ 0.05 to 2.5 weight parc2nL) ~ i L is pr~fe~able to use 3 solubilizing agent (such as dodecylbenzenesulfonic acid) which is a relatively better solubilzing agent than an emulsifying agent for the organic solvent of limited aqueous solubility.
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. As used herein, the term "coupler" is intended to mean a hydrotrope or a substance that increases t~e solubility in water of another matQrial ~,lhich is onl~ partially water soluble, such as organic solvents or surfactants. In some instances, 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 compa-tible surfactant blend in combination with a coupler may be utilized to achieve the desired dual function of the solubilizing additive component. Whether or not a surfactant alone or the combination of a surfactant and coupler is to be used is dèpendent upon the particular organic solvent and surfactant employed and can readily be determined in each partlcular case by simple e~perimentation.
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WO91/09104 PCT/'JS90/07215 :, 11 2~0~79 The surfactants employed in the practice of thisinvention 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 alkylphenozypoly(etheno~y) alkanols, alkoxypolytetheno~y~alkanols and fa~ty acid alkanolamides. Specific illustrative nonionic surfact3ncs ; useful in the practic0 of the invention include octylphe-no~ypoly(ethyleneoxy)(4)ethanol, nonylpheno~ypoly(ecnylene-oxy)(5~ethanol, dodecylphenoxypoly(ethyleneo~y)(8)ethanol, polyo~yethylene (7) lauryl alcohol, polyo~yethylene (4) i tridecyl alcohol, laurylo~ypoly(ethyleneo~y)(8)ethyl m2thyl ether, undecylthiopoly(ethyleneoxy)(6)ethanol, metho~ypoly(o~yethylene(10)/(o~ypropylene(20))-2-propanol block copolymer, nonylosypoly(propyleneosy)(4)/(ethyl-eneosy)(lO)ethanol, dodecyl polyglycoside, polyoxyethylene (9) monolaurate, polyoxyethylene (8) monoundecanoate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (18) sorbitol monotallate, sucrose monolaurate, lauryldimethylamine o~ide, myristyldimethylamine oxide, lauramidopropyl-N,N-dimethylamine o~ide, ~:1 lauric diethanolamide, 1:1 coconut diethanolamide, polyo~yethylene(6)1auramide, 1:1 soya diethanolamidopoly-(ethyleneo~y)(8) ethanol, 1:1 coconut diethanolamide,"modified", and 1:1 coconut diethanolamide, "long chain ; modified". 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. For use in the present invention, the fatty acid alkanolamides resulting from a 1:1 catalyzed reaction bFtween an alkanolamine and a fatty acld (known to those .
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W~91/09104 PCT/US90/07215 ~ ` 12 skilled in the art as "superamides") are preferred since these predominantly consist of the desired nonionic dialkanolamide without apPreciable amounts of ionic amine soaps. Among the illustrative fatty acid alkanolamides (with their respective molar ratios) which may be used may be mentioned soyamidz diet;qanolamide (l:l) (MacXamide S, McIntyre Group Ltd., ~hica~o, Tl1inols), linoleamide diethanolamide ~ ilonainid 1~-70-,1, L~1Ona ~ndustries, Inc., Paterson, ~;lew Je{say3, oleamide diathanolamide (l:l) (Clindrol lO0-0, and ~roduc- ~S l-~, Clint-,~ood Chemical Company, Chicago, IIlinois)~ ricinoleamide diethanolamide (l:l) (Mac3~amide ~! ~c~nt~Tre Grou? T-cd.) isostearamide diethanolamide (l:l)(~onamid l,0-IS, ~qcna Industries, Inc.
and Mackamide ISA, McIn~yre Group Ltd.), oleamide diethanolamide (2:l) (Mackamide O, McIntyre Group Ltd.), soyamide diethanolamide (2:l) (Mackamide SD, McIntyre Group Ltd.), and tail oil diethanolamide (l:l). In addition to those specifically listed above, other ~nown nonionic surfactants may likewise be used.
; 20 Illustrative anionic surfactants ~or use in the invention include dodecylbenzene sulfonic acid, monoethanolamine dodecylben2eresulfonate, sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate, morpholinium dodecylbPnzene sulfonate, ammonium dodecylbenzene sulfonate, isopropylamine dodecylbenzene sulfonate, sodium tridecyl- benzene sulfonate, sodium dinonylbenzene sulfonats, potassium didodecylbenzene sulfonate, dodecyl diphenyIo~ide disulfonic acid, sodium dodecyl diphenylo~ide disulfonate, isopropylamine decyl diphenylo~ide disulfonate, sodium he~adecyl-oxypoly(ethyleneo~y)(lO~ethyl sulfonate, potassium octylphenozypoly(ethyleneo~y)(9)ethyl sulfonate, sodium alpha Cl2_l4 olefin sulfonate, sodium hexadecane-l `: ~UBST~TE SHE~
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WO91/09104 PCT/U~90/07~15 sulfonate, sodium ethyl oleate sulfonate, potassium octadecenyl-succinate, sodium oleate, potassium laurate, triethanolamine myristate, morpholinium ~allate, potassium tallate, sodium lauryl sulfate, diethanolamine lauryl sulfate, sodium laureth (3) sulfate, ammonium laureth (2) sulfate, sodium nonylpheno~ypoly(ethyleneoxy)(43 sulfate, sodium diisobutylsulfosuccinate, disodium laurylsulfosuccinate, tetrasodium N-laurylsulfosuccinima'ce, sodium decylo~ypoly~ethyl-eneoxy(5)methyl)caroosylat2, sodium octylphenoxypoly(ethyl- eneoxy(8)methyl)carbo~ylate, sodium mono decyloxypoly(ethyl eneoxy)(~)phosphace, sodium didecyloxypoly(ethyleneoxy)- (6)phosphate, and pocassium mono/di octylpheno~ypoly(ethyl- eneo~y)(9)phosphato. Other anionic surfactants known in the art may also be employed.
Illustrative useful cationic surfactants include a mixture of n-alkyl (Cl2 50%, Cl4 30%, Cl6 17%~ Cl8 3%) dimethyl ethylbenzyl ammonium chlorides, hexadecyltrimethyl-ammonium methosulfate, ,~ didecyldimethylammonium bromide and a mi~ture of n-alkyl (68% Cl2, 32% Cl4) dimethyl benzyl ammonium chlorides.
Similarly useful 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.
As mentioned, 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 3S ethylbenzene sulfonate, sodium cumene sulfonate, sodium ' , ,:
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~,~q~9 octane-l-sulfonate, potassium dimethylnaphthalene sulfonate, ammonium ~ylene sulfonate, sodium n-hexyl diphenyo~ide disulfonate, sodium ~-ethylhe:r~yl sulfate, ammonium n-buto~yethyl sulra~P, sodium 2-echylnexanoate, sodium pelargonate, sodium n-buto~methyl carbo~ylate, pot:assium mono/di pheno~yethyl pnospnate, sodium mono/di n-buto~yethyl phosphate, triethanolamine t imathylolpropane phosphate, sodium capryloa~pho?.o~iona~e, disodi~m capryloimincdipro- pionace, sodium 10 isodecylo.~ypropyliminodip opiona'c3, so,-lium c~pro imidazoline amphoglycinata, and caprylamide D~A/capramide U -DEA. Cartain watar-solubls sol~7ent5 Xnown to the art ~s couplers such ~s Prop~rl~n~ g~vcol ~th.~rs (o.~.
tripropyleneglycol monomethyl ether) can be used in the ;15 practice of the invention. Additional couplers or hydrotropes known to the art may also be utilized.
In regard to the 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 mi~ed solubilizing surfactant system. For example, a combination of com~atiole anionic and/or nonionic surfactants may be employed. Likewise, a combination of compatible couplers may also be used as may a combination of one or more compatible surfactants f rom different classes of surfactants together with~ one or more couplers. -Thus, 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 e~perimentation. Similarly, a mi~ture of the sparingly soluble organic solvents may be employed in formulating the emulsion compositions of the invention.
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WO91/09104 PCT/US~0/07215 2070~79 In addition to the sparingly water soluble organic solvent and solubilizing additive components of 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.
Thus, 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 o 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 `i 20 defoamers (e.g., perfluoroalkyl phosphate esters or ~i silicone) or antifoaming agents may need to be incorporated into the emulsion compositions.
Among the viscosifying thickeners useful in the practice of the invention may be mentioned acrylic acid/alkyl methacrylate copolymers, carboxy acrylic polymers, guar gums, ~anthan gums, hydro~yethyl 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, poly(methylvinyl ~ether/maleic) anhydride and sodium alginate. Other viscosifying thickeners known to the art may also be used.
;~ When the viscosifying thickener is anionic in nature such ... .
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W091/09104 PCT/USgO/07215 ~ 3 as the thickener acrylic acid/al~syl methacrylate copolymer (Acrysol ICS-l by Rohm & Haas), an amine such as triethanolamine or other neutralizing base s'nould also be incorporated to neutralize any free carboxylic acid groups and thereby cause enhanced thicl.iening. ~,`lith tho use of nonionic thickeners such as guar gums, nydro~yQthyl cellulose and hydro~ypropyl cellulosa, the lnclusion o such an amine is unnecessary.
Various optional adjuvants can also be ~ncorporaced into the emulsion composi-tlons OL th2 int/-nt 1 on These include chelants such as tne sodium salts of etnylenedia-minetetraacetic acid (Hampene 100 or ~'7er.5Qne 100~, defoamers and foam controlling ~gonts, fr3s~ances, ~yes, preservatives, lubricants, emollients, pH adjustants, dispersants, abrasives, anti-corrosion additives and anti-rust additives. To prevent flash rusting when the emulsion compositions are used to clean and/or degrease metal surfaces, an anti flash-rusting additive such as an alkanolamine (e.g., monoethanolamine) or sodium nitrite may be incorporated. In general, it is preferred that the compositions be formulated to have a pH within a range of about 6.5-10 so as to be gent~o lo the hands and a~Joid defatting the skin.
The emulsion compositions of the invention may be prepared by combining the various components together under mechanical mi~ing conditions to form the desired emulsions. Thus,- for example, 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. In forming emulsions in the form of S~eS~ TE S~EET
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: , WO~ltO9104 PCT/US90/0~215 2~7~6~9 ; 17 ,i lotions or creams for use as hand cleaners, 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.
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 e~perimental test data prasented hereinafter.
-~ As shown by the working examples set forth hereinafter, the invention may be practiced to pr~are 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 ~e achieved by observing the following principles.
Generally speaking, emulsion concentrate compositions (such as described in E~amples 2-4 hereinafter) are more susceptible to destabilization (or "brea~ing") 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 accompIished 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. (such as solubilizing additives, thickeners, chelants, and anti-flash rust/corrosion additives) without ' ' .
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experiencing serious emulsion destabilization and resultant shelf life shortening. In the latter case thicXeners often ; play an important role in promoting long-term emulsion stability. In any case, in practicing the above guidelines, the restrictions placed upon the ract~.ce of the invention must be strictly adhered co.
The concantration of the aqueous cleanar~dasreasel solution, as indicated by the terms "'cotal soli,is concenc"
and "total actives content" in the working zxam ies provided hereinafter refers, respectiY~ly, to ~he corn~s~d percentages of nonvolatile components and ~o tne surn cotal of nonaqueous volatile and nonvolatila componsnts The following examples illustrato the pract ce of Lhe inventlon.
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Example 1 In the following examples of illustrative cleaner/
degreaser emulsion compositions of the present invention, the compositions were subjected as indicated to the definitive, semiquantitative degreasing test method ~ 20 described below in order to measure their cleaning/
;~ degreasing efficacy.
A magnetic stirrer (Fisher Scientific Co., Catalog No.
14-511-lA) 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. In each instance, pre-cleaned,`borosilicate glass microslides (3"
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. The test cleaner/degreaser emulsions or solutions were employed at the strength indicated and in an amount sufficient to fill a 50 ml Pyrex .
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WO9l/09104 2 o 7 ~ 6 7 9 ~CT/US90/07215 bea~er containing the vaned disc magnetic stirrer bar to a level of 40 ml. Each test material and surrounding air were maintained at 21 + 0.5C 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 microslide, in each test, rested upright on the beaker bottom, was allowed to lean agains-t tha lip of the beaker at an appro~imately 75 angle and was positioned with the Vaseline coated face or area facing upward away from the vaned disc magnetic stirrer ~ar.
~ er each test, 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 ad~usted manually to the "3~ stirring ~0 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 up~ard and ~as positioned away from the stirrer bar. The time "0" was noted immediately on a watch or clock with a sweep second hand.
At appropriate time intervals, the glass microslide was briefly removed from thè cleaner/degreaser material bath and immediately "read" for "% Vaseline removed from the l.0" x l.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.
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WO~1/09104 PCT/~S90/07215 The accuracy of the above-described test method is of the order of ~ 5% as determined by replicate run averaging.
Example 2 An aqueous cleaner/degreaser emulsion was prePar2d having the following composition:
ComPonent l-Pheno~y-2-propanol 20.0 (Dowanol PPh~
Isostearamide diethanolamide (1:1~ 3.0 (Monamide 150 IS) Soft H20 177.0 200.0 The isostearamide diethanolamide and water were stirred until the former was dispersed. The 1-phenoxy-2-propanol solvent was then stirred into the dispersion at room temperature for 45 minutes to achieve `~ complete emulsificationO The resulting composition was an intensely bluish/white emulsion having a pH of 8.85, a Brookfield viscosity (L~-#2 spindle, 60 rpm) of 4.0 centipoise, a total solids content ttheory) of 1.50%, and a total actives content (theory) of 11.50%. The emulsion e~hibited no flash point and was found to be storage stable for greater than ~ive 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.
;- At a 1:5 dilution with water, a bluish/white -~ microemulsion formed. The microemulsion very readily and ~ completely removed the following markings from alkyd ::
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WO91/09104 PC~/US90/07215 2 ~
enameled metal surfaces: black, indelible Magic Marker felt pen, blue and black indelible ballpoint pen, #l hardness pencil, red (waxy) crayon and smeared automotive grease.
Th~ above-formed microemulsion was subjected to the degreasing test method of E~ample 1 with the following results:
ls~ attack on greased slide at 1 sec.
60% re~oval of grease at 10 sec.
100% removal of grease at 17 sec.
~ ExamPle 3 :: .
E~ample 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
Com~onent Wt.%
15 1-Phenoxy-2-propanol 20.0 (Dowanol PPh) Isostearamide diethanolamide (1:1) 5.0 (Monamide 150 IS) Monoethanolamine ~0.2 20 Soft H20 174.8 200.0 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.S centipoise, a total solids content (theory) of 2.S0%, and a total actives ` ~ content (iheory) of 12.60%. The emulsion exhibited no v~ 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.
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WO91/~9104 PCT/US90/07215 ~ ~6~9 22 ~ t a 1:5 dilution with water, a bluish/white microemulsion formed. The 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 (wa~y) crayon and smeared automotive grease.
The abova-formed microemulsion was subjected co the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 1 sec.
70-7S% removal of grease at 10 52C.
100~ removal of grease at 14 sec.
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ExamPle 4 ., , lS Example 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
Component Wt.~
Phenoxy-2-propanol 20.0 ~Dowanol PPh) 20 Isostearamide diethanolamide (1:1) 6.0 (Monamide 150 IS) Monoethanolamine 0.2 . .
Soft H20 173.8 ~; 200.0 The resulting composition was an intensely bluish/white émulsion 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 , ~UBSIIIUTE SHEEI
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207 0~79 flash point and was found to have e~cellent storage stability for at least two months- at room temperature with no separation occurring.
At a 1:5 dilution with water, a bluish/white microemulsion formed. The microemulsion very easily, readily and completely rsmoved the following workings from alkyd enameled me~al surfaces: black, indelible Magic Marke~ ~21t ~en, ~lue and Dlack indelible ballpoint pen, #l hardness pencil, red (~axy) crayon and smeared automotive grease.
The a~ove microemulsion was subjected to the ~; degreasing test method of RxamDle l ~ith the following - results:
~` 1st attack on greased slide at l sec.
;~ 15 60% removal of grease at lO sec.
`~ 100% removal of grease at 18 sec.
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Esample 5 Example 2 was repeated in preparing an aqueous cl~ane-~degreaser emulsion having the following composition:
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Component - Wt.~%
.~
`;~`t l-Pheno~y-2-propanol 20.0 (Dowanol PPh) Isostearamide diethanolamide (l:l) 7.0 (Monamide 150 IS) 25 Monoethanolamine 0.2 ... .
Soft H20 172.8 ` 200.0 ~ .
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WO91/0~104 PCT/US90/07215 9~ QJ
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 e~cellent storage stability for at least two months at room temperature with no separakion occurring.
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 E~amples 2-4 from alkyd enameled metal surfaces.
; ~ The microemulsion was subjected to the degreasing test method of E~ample l with the following r~sults:
1st attack on greased slide at l sec.
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~ 75-80% removal of grease at lO sec.
; ~ 100% removaI o~ grease at 13 sec.
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~ E2amPle 6 ., ~ ~ EYample 2 was repeated in preparing an aqueous ! 20 cleaner/degreaser emulsion having the following composition:
, Component Wt.%
l-Pheno~y-2-propanol 20.0 (Dowanol PPh) Isostea~ramide diethanolamide (l:l) 3.0 (Monamide 150 IS) Lauramide diethanolamide (l:l) 3.0 (Superamide)(Clindrol LL-136) Monoethanolamine - 0.2 Soft H20 173.8 - 200.0 . ~ , . ' .
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WO91/09104 PCTtUS90/07215 2~70~79 ;
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%.
5 The emulsion e~hibited no flash point and was found to have good/e~ceil~nt stor~ge staoili~y lor in excess of two months at room temperature.
~ t a 1:5 dilution wit~ watar, a bluish/white microemuision formed. ~he microemulsion ver~ easily and completely remo~led all or the markings set forth in Examples 2-~ from alkyd enameled metal surfaces.
he microemlllslon was su~jected to the degreasing test method o~ am~le 1 with the following results:
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1st attac~ on greased slide at 1 sec.
60% removal of grease at 10 sec.
85% removal of grease at 15 sec.
100% removal of grease at 17 sec.
:
:~ E~ample 7 E~ample 2 ~as repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
Component Wt.%
l-Pheno2y-2-propanol 20.0 (Dowanol PPh) Ricinoleamide diethanolamide (~:1) 7.0 ~Superamide)(Mac~amide R) Monoethanolamine 0.2 Soft H20 172.8 200.0 T~TUT~ SHET
WO91/09104 PCT/US90/07~15 6rl 9 26 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 (~h20LY) of 13.~%. The emulsion exhibited no flash point, and ~as iound to have good storage stability for in e2cess of -two months at room temperature.
A'c a 1:5 dilution with water, a white to bluish/white emulsion ~as formed. The emulsion completely removed all of the markings set forth in E2amples 2-4 from alkyd enameled metal surfaces.
The emulsion was subjected to the degreas-ing test method of Example l with the following results:
~ 1st attack on greased slide at l sec.
'~ 75% removal of grease at 10 sec.
~i lO0~ removal of grease at 12 sec.
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E~ample 8 E~ample 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
Component Wt.%
l-Phenoxy-2-propanol 20.0 (Dowanol PPh) Oleamide diethanolamide (l:l) 6.0 ~Superamide)(Mackamide MO) Monoe~thanolamine 0.2 Soft H20 173.8 200.0 ''`" ~ ' .
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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 e~hibited no flash point, and was found to have good/excellent scorage staoilicy ror cwo moncns at room temperature.
At a 1:5 dilution Witil ~at2r, a -~hice colored emulsion was formed. The emulsion smudsed bu-c complecely removed all of th2 markings SQt forth in ~xamples 2-4 ~rom alkyd enameled metal surraces.
The emulslon ~7as suojected to ,.hs degx~asing test method of Example 1 ~ith the follow-lng results:
`:
- 1st attack on greased slide at 1 sec.
70-75% removal of grease at 10 sec.
100~ removal of grease at 14 sec.
.
ExamPle 9 E~ample 2 was repeated in preparing an aqueous cleaner~degreaser smulsion having the following composition:
ComPonent Wt.%
l-Pheno~y-2-propanol 20.0 (Dowanol PPh) Isostearamide diethanolamide (1~ 7.0 (Mackamide ISA) 25 Monoethanolamine 0.2 ~ Soft H20 172.8 :~ 200.0 ' ~STITDTrr SHE~T
WO91/09l04 PCT/US90/07215 ~9 ~
; 28 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 contant (theory) of 3.5%, and a total actives content (theory) of 13.6%. The emulsion exhi~ited no flash point, and was found ~o be very sta~le over e~tended periods at room temperature.
At a 1:5 dilutlon with. water, a ~luish-white microemuision ~/as formed. The microemulsion readily and complet^-ly -emov2d âll 0_ tlle marXings set forth in E~amples 2-~ from alkyd enarneled metal suraces.
~I The microemulsicn was subjected to the dsgreasing test method sst for'h in ~__mple 1 with the -Eollowing results:
1st attac~ on greased slide at 1 sec.
70% removal of grease at 10 sec.
100% removal of grease at 15 sec.
,, ExamPle 10 :, .
E~ample 2 was repeated in preparing an àqueous cleaner/degreaser emulsion having the follo~ing composition:
1 20 ComPonent Wt.%
l-Pheno~y-2-propanol 20.0 (Dowanol PPh~
Linoleamide diethanoIamide (1:1) 7.0 (soyamide DEA-Clindrol LT-15-73-1) Monoethanolamine- 0.2 Soft H20 172.8 200.0 ;~ .
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(i) having a water solubility in the range of approximately 0.05 to approximately -5 ~ weight percent;
(ii) not being a hydrocarbon or halocaroon;
naving one or more similar or disslmilar oxygen, nitrogen, sulfur, or phosphorous containing functional groups;
~ beir.g a sol-tent for hydrophobic soilants; and (v) being present in an amount e~ceeding its aqueous solubility;
(b) a solubilizing additive consisting of from appro~imately 0.1 to appro~imately 100 weight percent of a surfactant and from 0 to approximately 99.9 weight percent of a coupler, said solubilizins additive being present in an amount insufficient to solubilize all of the total organic SO1V2nL content but sufEicient to emulsify the unsolu~ilized portibn of the total organic solvent content;
~, and .. (c) water.
The emulsion compositions of the-invention thus : 25 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.
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Description of the Preferred Embodiments In accordance with the present invention, it has now been found that stable, 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 characteris~ics and being present in an amount e~ceeding its aquaous solubility with a solubilizing additive and water, the solubilizing additive being present in an amount insufEicient to solubilize all of the total organic solvent content but sufficient to emulsify the unsolllbil~ ~o~ portion of the total organic solvent content. ln ~he present invention, 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 2Q 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 derivad 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 wator insoluble organic solvent in u~3T~ 1 ~3-s ~
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, , WO9l/09104 PCT/US90/07215 207~579 ~
the nonaqueous or discontinuous phase of the emulsions.
The emulsions of the present invention also provide greater degreasiny efficacies at equal or equivalent organic solvent levels over those provided by the aqueous cleaner/degr2aser compositions disclosed in my copending, coassigned application Serial No. 373,813, filed June 29, 1989, which are formulated in the orm o~ totally water soluble compositions.
The emulsion compositlons or the invention are therefore characteri~ed by having the sparingly water soluble organic solvent present in both the aqueous phase and nonaqueous or o~l ~hase o~ 'he 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 accivicy e~hlbi'ced by the emulsions of the invention.
For use in the present invention, the sparingly water soluble organic solvent must have the following characteristics: --(a) it must have limited water solubility in therange of approximately 0.05 to 6 weight percent;
~b) it must not be a hydrocarbon or halocarbon, (c) it must have one or more similar or dissimilar o~ygen, nitrogen, sulfur or phosphorous containing functional groups;
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W09l/~9l04 PCT/US9~/07215 (d) it must be a solvent for hydrophobic : soilants; and (e) it must be present in an amount exceeding its limited aqueous solubility.
Preferably, the organ~c sol~ent has a water solubility in the r2ngQ O r ~ppro~imately 0.05 to approximately 2.5 weight percent, morQ 3rersraDly between 1 and 2.5 waight percent.
:;: Organic solYents meeting these criteria provide superior ~` clcaning~dDg easing action when formulated in accordance with the invention.
The principal sla.sses o~ organic sol~ents from ~,7hich useful o-ganic sol-~ents may be selècted include esters, ~ . alchohols, ketones, aldehydes, ethers and nitriles. These : ~ . will generally contain one or more of the desired similar .
;` 15 or dissimilar functional groups listed above. Examples of ~: organic solvents containing similar functional groups from among those listed above include diethyl gluterate (2 ester ~ groups), phenacyl aoetone (2 keto groups), diethylèthylene ;~ diphosphonate (2 phosphonate ester groups), ethylene-dipropionate (2 ester groups), decylene glycol (2 hydroxyl groups), m-dimetho~ybenzen2 (2 ethe:r groups), adiponitrile (~2 nitrile groups), ethylene glycol dibutyl ether (2 ether groups), and diethyl-o-phthalate (2 ester groups). Among ; organic solvents containing dissimilar functional groups `
;~ 25 from among those listed above may be mentioned ; 2-phenoxyethanol (hydroxy, ether groups), l-phenoxy-2-propanol (hydro~y, ether groups), N-phenylmorpholine (amino, ether groups), isopro-: pylacetoacetate (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), ~:~
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~Q~STIT~TE SHEET
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~ WO9l/09104 PCT/~S90/07215 2~7~67~
~-anisaldehyde ~ether, aldehyde groups), polypropylene glycol 1200, 2000, and 4000 (ether, hydroxyl groups), n-buto~y acetate (ether, ester groups), and 2-phenylthioethanol (thioether, hydro~yl groups).
In addition to the criteria listsd above, it is also desirable but not essenti31 that the organic sol~ent have a relatively lo~ volatility or hlsh ~lash point, e~hibit a low level of odor, be chemically stable, nonto~.ic, non hazardous, liquid or eas~ly liqui-ied at ambient temperatures, and commercially availa~le.
The sparingly water soluble organic solvents which may be employed in t'ne ?rac" c~ O~ Lhe p.rasen.t ~n'tent ' on ~znd comprising some of tne solvents listad above) cogeclner with their aqueous ambient temperature solubility in wt.%
include 2-pheno~yethanol (2.3) (marketed under the trade designation HDowanol EPh"), ~-pheno~y-2-propanol (1.1) (marketed under the trade designation "Dowanol PPh"), ~l phenylethanol (1.6), acetophenone (0.5), -benzyl alcohol `l (4.4), benzonitrile (1.0), n-butyl acetate (0.7), n-amyl acetate (0.25), benzaldehyde (0.3~, ~,N-diethylaniline l (1.4), diethyl adipate (0.43), dimethyl-o-phthalate (0.43~, ! n-amyl alcohol (2.7), M-phenylmorpholine (1-0), `! n-buto~yethyl acetate (EB acetate) (l.l), cyclohe~anol ` (4.2), polypropylene glycol 1200 (2), dipropylene glycol mono-n-butyl ether (Dowanol DPnB) (5.0) cyclohe~anone (2.3), isophorone (1.2), methylisobutyl ketone- ~-2.0), methylisoamyl ketone (0.5), tri-n-butylphosphate (0.6), l-nitropropane (1.4), nitroethane ~4.5), dimethyl esters of mixed succinic, glutaric and adipic acids (5.7) (marketed under the trade designation "DBE ester" by DuPont), diethyl glutarate (0.88), diethyl malonate (2.08), poly-;~ oxyalkylene polyols (e.g., polyoxypropylene diols and : triols) such as the polypropylene glycols P1200, P2000 and P4000 (Dow Chemical), polypropylene glycol monobutyl ether . .
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(Dow Polyglycol L-1150) and polyglycol copolymers containing ethenoæy and propenoxy units (Dow 112-2). As will be apparent to those skilled in the art, the above-listed sparingly ~ater soluble organic solvents are merely lllustr3tivQ and various oth~or solvents meeting the criteria se-t OUL above may ~lso 'oe utilized in the practice of the invantlon~ ~ecau~e of their performance characteri~t1cs, lac~ of odor, low volatility/high flash point, chemical stability and availa'oility, 2-phenoæ-y-ethanol and l-pheno~-1-2-propanol are the pre~erred organic solvents of choice. N-butoæyethyl acetate (EB
acot~te~ -n~ tho dimQthiTl ~stors o' mi~oa succinic, glutaric and adlplc 2C1dS aro also amor.g the prefer~ed organic solvents. For emulsions of the invention in the form of lotions and creams, the use of oligomeric, hydrophobic solvents having limited aqueous solubility and molecular weights of up to 5000, preferably b~low 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(1,2-buLylene glycol), poly(2,3-'outylene glycol), ' poly(norbornane o~ide glycol), poly(styrene oxide glycol), poly(phenylglycidyl ether glycol), polytisobutylglycidyl ether glycol), poly~methylglycidyl ether glycol), phenoæypolypropylene glycol, butoæypolypropylene glycol (PPG-1~ butyl ether), poiypropylene glycol butyl ether ~PPG-18 butyl ether), polyo~ypropylene n-butyl ether, polytetramethylene ether glycol, poly(tetrahydrofuran), poly(ethyl vinyl ether), poly(isobutyl vinyl ether), poly(diallyl ether), polyoæypropylene (30) trimethylpropanetriol, poly[propylene oæide (lO)/phenylglycidyl ether (lO) glycol], and similar solvents ~nown to the art.
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WO91/0~104 PCT/US90/07215 2~7~79 9. - .
As indicated, a number of otherwise potent 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. l4.3 wt.-5), propylene carbonate (a~. sol. l9.6 wt.%j and N-methyl pyrrolidone (ininite aq. sol.) are not useful in the practice of the invention.
In formulating the stable, aqueous cleaner/desreaser emulsion compositions of the invention, an organic solvent meeting the required cr~ terl a s combin~d wlth a solubilizing additive and water. The solu~ilizing additi~e consists of from approximately O.l to appro~imately lO0 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 ~j 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. The amount of solubilizing additive (surfactant or surfactan~ plus coupl2r) required to accomplish this objective will vary depending upon its solubilizing efficacy and upon the particular organic solvent employed; it can readily be determined by simple e~perimentation in each instance. In s2neral, it is desirable to formulate the emulsion compositions of the invention with as little of the solubilizing additivè as possible while achieving the desired solubilization and emulsification of the organic solvent stated above since emulsions so formed will tend to remain in emulsion form - even upon being diluted many times with water.
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WO9l/~9104 PCT/US90/07215 S
Further, it has been found that the best results are achieved when the emulsion compositions are formulated with organic solvents whose aqueous solubility is between approzimately 0.05 and appro~imately 2.5 weight percent.
Also, it has be~n ~ound that ~lhen an organic solvent is employed having a water so:!ubility in the upper portion of the ov~rall r2nge 0.05 to ~ 7~i~ight percent, it is preferabls co uti7i~e a solubili~1ng addiciYe which is a . relatiYely b~ttQr emulsirving agent than a solubilizing agent ror the organic sol;enL. On th2 other hand, ~7hen employing an organic solvent whose solubility is in the Iower portlon^ of th~ oY~r~ll -?.~ 0.05 to 2.5 weight parc2nL) ~ i L is pr~fe~able to use 3 solubilizing agent (such as dodecylbenzenesulfonic acid) which is a relatively better solubilzing agent than an emulsifying agent for the organic solvent of limited aqueous solubility.
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. As used herein, the term "coupler" is intended to mean a hydrotrope or a substance that increases t~e solubility in water of another matQrial ~,lhich is onl~ partially water soluble, such as organic solvents or surfactants. In some instances, 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 compa-tible surfactant blend in combination with a coupler may be utilized to achieve the desired dual function of the solubilizing additive component. Whether or not a surfactant alone or the combination of a surfactant and coupler is to be used is dèpendent upon the particular organic solvent and surfactant employed and can readily be determined in each partlcular case by simple e~perimentation.
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WO91/09104 PCT/'JS90/07215 :, 11 2~0~79 The surfactants employed in the practice of thisinvention 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 alkylphenozypoly(etheno~y) alkanols, alkoxypolytetheno~y~alkanols and fa~ty acid alkanolamides. Specific illustrative nonionic surfact3ncs ; useful in the practic0 of the invention include octylphe-no~ypoly(ethyleneoxy)(4)ethanol, nonylpheno~ypoly(ecnylene-oxy)(5~ethanol, dodecylphenoxypoly(ethyleneo~y)(8)ethanol, polyo~yethylene (7) lauryl alcohol, polyo~yethylene (4) i tridecyl alcohol, laurylo~ypoly(ethyleneo~y)(8)ethyl m2thyl ether, undecylthiopoly(ethyleneoxy)(6)ethanol, metho~ypoly(o~yethylene(10)/(o~ypropylene(20))-2-propanol block copolymer, nonylosypoly(propyleneosy)(4)/(ethyl-eneosy)(lO)ethanol, dodecyl polyglycoside, polyoxyethylene (9) monolaurate, polyoxyethylene (8) monoundecanoate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (18) sorbitol monotallate, sucrose monolaurate, lauryldimethylamine o~ide, myristyldimethylamine oxide, lauramidopropyl-N,N-dimethylamine o~ide, ~:1 lauric diethanolamide, 1:1 coconut diethanolamide, polyo~yethylene(6)1auramide, 1:1 soya diethanolamidopoly-(ethyleneo~y)(8) ethanol, 1:1 coconut diethanolamide,"modified", and 1:1 coconut diethanolamide, "long chain ; modified". 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. For use in the present invention, the fatty acid alkanolamides resulting from a 1:1 catalyzed reaction bFtween an alkanolamine and a fatty acld (known to those .
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W~91/09104 PCT/US90/07215 ~ ` 12 skilled in the art as "superamides") are preferred since these predominantly consist of the desired nonionic dialkanolamide without apPreciable amounts of ionic amine soaps. Among the illustrative fatty acid alkanolamides (with their respective molar ratios) which may be used may be mentioned soyamidz diet;qanolamide (l:l) (MacXamide S, McIntyre Group Ltd., ~hica~o, Tl1inols), linoleamide diethanolamide ~ ilonainid 1~-70-,1, L~1Ona ~ndustries, Inc., Paterson, ~;lew Je{say3, oleamide diathanolamide (l:l) (Clindrol lO0-0, and ~roduc- ~S l-~, Clint-,~ood Chemical Company, Chicago, IIlinois)~ ricinoleamide diethanolamide (l:l) (Mac3~amide ~! ~c~nt~Tre Grou? T-cd.) isostearamide diethanolamide (l:l)(~onamid l,0-IS, ~qcna Industries, Inc.
and Mackamide ISA, McIn~yre Group Ltd.), oleamide diethanolamide (2:l) (Mackamide O, McIntyre Group Ltd.), soyamide diethanolamide (2:l) (Mackamide SD, McIntyre Group Ltd.), and tail oil diethanolamide (l:l). In addition to those specifically listed above, other ~nown nonionic surfactants may likewise be used.
; 20 Illustrative anionic surfactants ~or use in the invention include dodecylbenzene sulfonic acid, monoethanolamine dodecylben2eresulfonate, sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate, morpholinium dodecylbPnzene sulfonate, ammonium dodecylbenzene sulfonate, isopropylamine dodecylbenzene sulfonate, sodium tridecyl- benzene sulfonate, sodium dinonylbenzene sulfonats, potassium didodecylbenzene sulfonate, dodecyl diphenyIo~ide disulfonic acid, sodium dodecyl diphenylo~ide disulfonate, isopropylamine decyl diphenylo~ide disulfonate, sodium he~adecyl-oxypoly(ethyleneo~y)(lO~ethyl sulfonate, potassium octylphenozypoly(ethyleneo~y)(9)ethyl sulfonate, sodium alpha Cl2_l4 olefin sulfonate, sodium hexadecane-l `: ~UBST~TE SHE~
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WO91/09104 PCT/U~90/07~15 sulfonate, sodium ethyl oleate sulfonate, potassium octadecenyl-succinate, sodium oleate, potassium laurate, triethanolamine myristate, morpholinium ~allate, potassium tallate, sodium lauryl sulfate, diethanolamine lauryl sulfate, sodium laureth (3) sulfate, ammonium laureth (2) sulfate, sodium nonylpheno~ypoly(ethyleneoxy)(43 sulfate, sodium diisobutylsulfosuccinate, disodium laurylsulfosuccinate, tetrasodium N-laurylsulfosuccinima'ce, sodium decylo~ypoly~ethyl-eneoxy(5)methyl)caroosylat2, sodium octylphenoxypoly(ethyl- eneoxy(8)methyl)carbo~ylate, sodium mono decyloxypoly(ethyl eneoxy)(~)phosphace, sodium didecyloxypoly(ethyleneoxy)- (6)phosphate, and pocassium mono/di octylpheno~ypoly(ethyl- eneo~y)(9)phosphato. Other anionic surfactants known in the art may also be employed.
Illustrative useful cationic surfactants include a mixture of n-alkyl (Cl2 50%, Cl4 30%, Cl6 17%~ Cl8 3%) dimethyl ethylbenzyl ammonium chlorides, hexadecyltrimethyl-ammonium methosulfate, ,~ didecyldimethylammonium bromide and a mi~ture of n-alkyl (68% Cl2, 32% Cl4) dimethyl benzyl ammonium chlorides.
Similarly useful 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.
As mentioned, 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 3S ethylbenzene sulfonate, sodium cumene sulfonate, sodium ' , ,:
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~,~q~9 octane-l-sulfonate, potassium dimethylnaphthalene sulfonate, ammonium ~ylene sulfonate, sodium n-hexyl diphenyo~ide disulfonate, sodium ~-ethylhe:r~yl sulfate, ammonium n-buto~yethyl sulra~P, sodium 2-echylnexanoate, sodium pelargonate, sodium n-buto~methyl carbo~ylate, pot:assium mono/di pheno~yethyl pnospnate, sodium mono/di n-buto~yethyl phosphate, triethanolamine t imathylolpropane phosphate, sodium capryloa~pho?.o~iona~e, disodi~m capryloimincdipro- pionace, sodium 10 isodecylo.~ypropyliminodip opiona'c3, so,-lium c~pro imidazoline amphoglycinata, and caprylamide D~A/capramide U -DEA. Cartain watar-solubls sol~7ent5 Xnown to the art ~s couplers such ~s Prop~rl~n~ g~vcol ~th.~rs (o.~.
tripropyleneglycol monomethyl ether) can be used in the ;15 practice of the invention. Additional couplers or hydrotropes known to the art may also be utilized.
In regard to the 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 mi~ed solubilizing surfactant system. For example, a combination of com~atiole anionic and/or nonionic surfactants may be employed. Likewise, a combination of compatible couplers may also be used as may a combination of one or more compatible surfactants f rom different classes of surfactants together with~ one or more couplers. -Thus, 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 e~perimentation. Similarly, a mi~ture of the sparingly soluble organic solvents may be employed in formulating the emulsion compositions of the invention.
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WO91/09104 PCT/US~0/07215 2070~79 In addition to the sparingly water soluble organic solvent and solubilizing additive components of 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.
Thus, 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 o 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 `i 20 defoamers (e.g., perfluoroalkyl phosphate esters or ~i silicone) or antifoaming agents may need to be incorporated into the emulsion compositions.
Among the viscosifying thickeners useful in the practice of the invention may be mentioned acrylic acid/alkyl methacrylate copolymers, carboxy acrylic polymers, guar gums, ~anthan gums, hydro~yethyl 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, poly(methylvinyl ~ether/maleic) anhydride and sodium alginate. Other viscosifying thickeners known to the art may also be used.
;~ When the viscosifying thickener is anionic in nature such ... .
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W091/09104 PCT/USgO/07215 ~ 3 as the thickener acrylic acid/al~syl methacrylate copolymer (Acrysol ICS-l by Rohm & Haas), an amine such as triethanolamine or other neutralizing base s'nould also be incorporated to neutralize any free carboxylic acid groups and thereby cause enhanced thicl.iening. ~,`lith tho use of nonionic thickeners such as guar gums, nydro~yQthyl cellulose and hydro~ypropyl cellulosa, the lnclusion o such an amine is unnecessary.
Various optional adjuvants can also be ~ncorporaced into the emulsion composi-tlons OL th2 int/-nt 1 on These include chelants such as tne sodium salts of etnylenedia-minetetraacetic acid (Hampene 100 or ~'7er.5Qne 100~, defoamers and foam controlling ~gonts, fr3s~ances, ~yes, preservatives, lubricants, emollients, pH adjustants, dispersants, abrasives, anti-corrosion additives and anti-rust additives. To prevent flash rusting when the emulsion compositions are used to clean and/or degrease metal surfaces, an anti flash-rusting additive such as an alkanolamine (e.g., monoethanolamine) or sodium nitrite may be incorporated. In general, it is preferred that the compositions be formulated to have a pH within a range of about 6.5-10 so as to be gent~o lo the hands and a~Joid defatting the skin.
The emulsion compositions of the invention may be prepared by combining the various components together under mechanical mi~ing conditions to form the desired emulsions. Thus,- for example, 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. In forming emulsions in the form of S~eS~ TE S~EET
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: , WO~ltO9104 PCT/US90/0~215 2~7~6~9 ; 17 ,i lotions or creams for use as hand cleaners, 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.
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 e~perimental test data prasented hereinafter.
-~ As shown by the working examples set forth hereinafter, the invention may be practiced to pr~are 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 ~e achieved by observing the following principles.
Generally speaking, emulsion concentrate compositions (such as described in E~amples 2-4 hereinafter) are more susceptible to destabilization (or "brea~ing") 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 accompIished 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. (such as solubilizing additives, thickeners, chelants, and anti-flash rust/corrosion additives) without ' ' .
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experiencing serious emulsion destabilization and resultant shelf life shortening. In the latter case thicXeners often ; play an important role in promoting long-term emulsion stability. In any case, in practicing the above guidelines, the restrictions placed upon the ract~.ce of the invention must be strictly adhered co.
The concantration of the aqueous cleanar~dasreasel solution, as indicated by the terms "'cotal soli,is concenc"
and "total actives content" in the working zxam ies provided hereinafter refers, respectiY~ly, to ~he corn~s~d percentages of nonvolatile components and ~o tne surn cotal of nonaqueous volatile and nonvolatila componsnts The following examples illustrato the pract ce of Lhe inventlon.
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Example 1 In the following examples of illustrative cleaner/
degreaser emulsion compositions of the present invention, the compositions were subjected as indicated to the definitive, semiquantitative degreasing test method ~ 20 described below in order to measure their cleaning/
;~ degreasing efficacy.
A magnetic stirrer (Fisher Scientific Co., Catalog No.
14-511-lA) 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. In each instance, pre-cleaned,`borosilicate glass microslides (3"
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. The test cleaner/degreaser emulsions or solutions were employed at the strength indicated and in an amount sufficient to fill a 50 ml Pyrex .
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WO9l/09104 2 o 7 ~ 6 7 9 ~CT/US90/07215 bea~er containing the vaned disc magnetic stirrer bar to a level of 40 ml. Each test material and surrounding air were maintained at 21 + 0.5C 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 microslide, in each test, rested upright on the beaker bottom, was allowed to lean agains-t tha lip of the beaker at an appro~imately 75 angle and was positioned with the Vaseline coated face or area facing upward away from the vaned disc magnetic stirrer ~ar.
~ er each test, 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 ad~usted manually to the "3~ stirring ~0 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 up~ard and ~as positioned away from the stirrer bar. The time "0" was noted immediately on a watch or clock with a sweep second hand.
At appropriate time intervals, the glass microslide was briefly removed from thè cleaner/degreaser material bath and immediately "read" for "% Vaseline removed from the l.0" x l.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.
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WO~1/09104 PCT/~S90/07215 The accuracy of the above-described test method is of the order of ~ 5% as determined by replicate run averaging.
Example 2 An aqueous cleaner/degreaser emulsion was prePar2d having the following composition:
ComPonent l-Pheno~y-2-propanol 20.0 (Dowanol PPh~
Isostearamide diethanolamide (1:1~ 3.0 (Monamide 150 IS) Soft H20 177.0 200.0 The isostearamide diethanolamide and water were stirred until the former was dispersed. The 1-phenoxy-2-propanol solvent was then stirred into the dispersion at room temperature for 45 minutes to achieve `~ complete emulsificationO The resulting composition was an intensely bluish/white emulsion having a pH of 8.85, a Brookfield viscosity (L~-#2 spindle, 60 rpm) of 4.0 centipoise, a total solids content ttheory) of 1.50%, and a total actives content (theory) of 11.50%. The emulsion e~hibited no flash point and was found to be storage stable for greater than ~ive 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.
;- At a 1:5 dilution with water, a bluish/white -~ microemulsion formed. The microemulsion very readily and ~ completely removed the following markings from alkyd ::
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enameled metal surfaces: black, indelible Magic Marker felt pen, blue and black indelible ballpoint pen, #l hardness pencil, red (waxy) crayon and smeared automotive grease.
Th~ above-formed microemulsion was subjected to the degreasing test method of E~ample 1 with the following results:
ls~ attack on greased slide at 1 sec.
60% re~oval of grease at 10 sec.
100% removal of grease at 17 sec.
~ ExamPle 3 :: .
E~ample 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
Com~onent Wt.%
15 1-Phenoxy-2-propanol 20.0 (Dowanol PPh) Isostearamide diethanolamide (1:1) 5.0 (Monamide 150 IS) Monoethanolamine ~0.2 20 Soft H20 174.8 200.0 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.S centipoise, a total solids content (theory) of 2.S0%, and a total actives ` ~ content (iheory) of 12.60%. The emulsion exhibited no v~ 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.
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WO91/~9104 PCT/US90/07215 ~ ~6~9 22 ~ t a 1:5 dilution with water, a bluish/white microemulsion formed. The 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 (wa~y) crayon and smeared automotive grease.
The abova-formed microemulsion was subjected co the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 1 sec.
70-7S% removal of grease at 10 52C.
100~ removal of grease at 14 sec.
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ExamPle 4 ., , lS Example 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
Component Wt.~
Phenoxy-2-propanol 20.0 ~Dowanol PPh) 20 Isostearamide diethanolamide (1:1) 6.0 (Monamide 150 IS) Monoethanolamine 0.2 . .
Soft H20 173.8 ~; 200.0 The resulting composition was an intensely bluish/white émulsion 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 , ~UBSIIIUTE SHEEI
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. .
207 0~79 flash point and was found to have e~cellent storage stability for at least two months- at room temperature with no separation occurring.
At a 1:5 dilution with water, a bluish/white microemulsion formed. The microemulsion very easily, readily and completely rsmoved the following workings from alkyd enameled me~al surfaces: black, indelible Magic Marke~ ~21t ~en, ~lue and Dlack indelible ballpoint pen, #l hardness pencil, red (~axy) crayon and smeared automotive grease.
The a~ove microemulsion was subjected to the ~; degreasing test method of RxamDle l ~ith the following - results:
~` 1st attack on greased slide at l sec.
;~ 15 60% removal of grease at lO sec.
`~ 100% removal of grease at 18 sec.
.
Esample 5 Example 2 was repeated in preparing an aqueous cl~ane-~degreaser emulsion having the following composition:
' .
Component - Wt.~%
.~
`;~`t l-Pheno~y-2-propanol 20.0 (Dowanol PPh) Isostearamide diethanolamide (l:l) 7.0 (Monamide 150 IS) 25 Monoethanolamine 0.2 ... .
Soft H20 172.8 ` 200.0 ~ .
.
. ~ :
::
ITllTE S5~T
,. . .
.
.
.... ..
WO91/0~104 PCT/US90/07215 9~ QJ
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 e~cellent storage stability for at least two months at room temperature with no separakion occurring.
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 E~amples 2-4 from alkyd enameled metal surfaces.
; ~ The microemulsion was subjected to the degreasing test method of E~ample l with the following r~sults:
1st attack on greased slide at l sec.
.
~ 75-80% removal of grease at lO sec.
; ~ 100% removaI o~ grease at 13 sec.
.
~ E2amPle 6 ., ~ ~ EYample 2 was repeated in preparing an aqueous ! 20 cleaner/degreaser emulsion having the following composition:
, Component Wt.%
l-Pheno~y-2-propanol 20.0 (Dowanol PPh) Isostea~ramide diethanolamide (l:l) 3.0 (Monamide 150 IS) Lauramide diethanolamide (l:l) 3.0 (Superamide)(Clindrol LL-136) Monoethanolamine - 0.2 Soft H20 173.8 - 200.0 . ~ , . ' .
~STIT~T~ â~d~ET
.
.
.
.
WO91/09104 PCTtUS90/07215 2~70~79 ;
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%.
5 The emulsion e~hibited no flash point and was found to have good/e~ceil~nt stor~ge staoili~y lor in excess of two months at room temperature.
~ t a 1:5 dilution wit~ watar, a bluish/white microemuision formed. ~he microemulsion ver~ easily and completely remo~led all or the markings set forth in Examples 2-~ from alkyd enameled metal surfaces.
he microemlllslon was su~jected to the degreasing test method o~ am~le 1 with the following results:
: .
:
1st attac~ on greased slide at 1 sec.
60% removal of grease at 10 sec.
85% removal of grease at 15 sec.
100% removal of grease at 17 sec.
:
:~ E~ample 7 E~ample 2 ~as repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
Component Wt.%
l-Pheno2y-2-propanol 20.0 (Dowanol PPh) Ricinoleamide diethanolamide (~:1) 7.0 ~Superamide)(Mac~amide R) Monoethanolamine 0.2 Soft H20 172.8 200.0 T~TUT~ SHET
WO91/09104 PCT/US90/07~15 6rl 9 26 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 (~h20LY) of 13.~%. The emulsion exhibited no flash point, and ~as iound to have good storage stability for in e2cess of -two months at room temperature.
A'c a 1:5 dilution with water, a white to bluish/white emulsion ~as formed. The emulsion completely removed all of the markings set forth in E2amples 2-4 from alkyd enameled metal surfaces.
The emulsion was subjected to the degreas-ing test method of Example l with the following results:
~ 1st attack on greased slide at l sec.
'~ 75% removal of grease at 10 sec.
~i lO0~ removal of grease at 12 sec.
.'. : .
E~ample 8 E~ample 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
Component Wt.%
l-Phenoxy-2-propanol 20.0 (Dowanol PPh) Oleamide diethanolamide (l:l) 6.0 ~Superamide)(Mackamide MO) Monoe~thanolamine 0.2 Soft H20 173.8 200.0 ''`" ~ ' .
. .
,, iZT~TE ~IE~T
, . . ~.
~ . :
;,'~ . .
"
,. - .... :
-, .,:
27 ~ 6~
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 e~hibited no flash point, and was found to have good/excellent scorage staoilicy ror cwo moncns at room temperature.
At a 1:5 dilution Witil ~at2r, a -~hice colored emulsion was formed. The emulsion smudsed bu-c complecely removed all of th2 markings SQt forth in ~xamples 2-4 ~rom alkyd enameled metal surraces.
The emulslon ~7as suojected to ,.hs degx~asing test method of Example 1 ~ith the follow-lng results:
`:
- 1st attack on greased slide at 1 sec.
70-75% removal of grease at 10 sec.
100~ removal of grease at 14 sec.
.
ExamPle 9 E~ample 2 was repeated in preparing an aqueous cleaner~degreaser smulsion having the following composition:
ComPonent Wt.%
l-Pheno~y-2-propanol 20.0 (Dowanol PPh) Isostearamide diethanolamide (1~ 7.0 (Mackamide ISA) 25 Monoethanolamine 0.2 ~ Soft H20 172.8 :~ 200.0 ' ~STITDTrr SHE~T
WO91/09l04 PCT/US90/07215 ~9 ~
; 28 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 contant (theory) of 3.5%, and a total actives content (theory) of 13.6%. The emulsion exhi~ited no flash point, and was found ~o be very sta~le over e~tended periods at room temperature.
At a 1:5 dilutlon with. water, a ~luish-white microemuision ~/as formed. The microemulsion readily and complet^-ly -emov2d âll 0_ tlle marXings set forth in E~amples 2-~ from alkyd enarneled metal suraces.
~I The microemulsicn was subjected to the dsgreasing test method sst for'h in ~__mple 1 with the -Eollowing results:
1st attac~ on greased slide at 1 sec.
70% removal of grease at 10 sec.
100% removal of grease at 15 sec.
,, ExamPle 10 :, .
E~ample 2 was repeated in preparing an àqueous cleaner/degreaser emulsion having the follo~ing composition:
1 20 ComPonent Wt.%
l-Pheno~y-2-propanol 20.0 (Dowanol PPh~
Linoleamide diethanoIamide (1:1) 7.0 (soyamide DEA-Clindrol LT-15-73-1) Monoethanolamine- 0.2 Soft H20 172.8 200.0 ;~ .
TITUT~ SHtET
. ~ .
.. . .
, "~
, , . , ` .
~, .
o~79 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) o 13.6~,. The emulsion was quite stable at room temperatur~ for 1-2 months.
At a 1:5 dilution with water, a ~luisn/white microemulsion was formed. The microemulsion readily and completely removed all of the markings s~t Lorth in E~amples 2-4 from alkyd enameled metal surfaces.
The microemulsion was subjected to the degreasing test method of ~xample 1 with the followins ,esults:
1st attack on greased slide at 1 sec.
~;~ 15 100% removal of grease at 13 sec.
~ E~amPle 11 Example 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
ComPonent r~l,.,,;
20 1-Phenoxy-2-propanol 30.0 (Dowanol PPh) Isostearamide diethanolamide (1:1) 10.0 ~Mackamide ISA) Monoethanolamine 0.3 25 Soft H20 159.7 200.0 .
The resulting composition was an intensely bluish/white emulsion having a pH of 9.63, a Brookfield viscosity (~V-#2 spindle, 60 rpm) of 7.0 centipoise, a ~ .
S~T~TUTE SHE!ET
:
.
,.
~9 30 total solids content ~theory) o 5.0%~ and a total actives content (theory) or 20~15~o~ The emulsion exhibited excellent stability over an extended period at room temperature.
At a 1:8 dilution ~ith water, a bluish/white microemulsion ~as lormed wnich had a 1.67% conceniration of l-phenoxy-2-~ropanol. The microemulsion vary easily and completely remov2d aLl O:L ~'ne ~nar';inys 3eJC for~h in Examples 2-~ rrom aixyd enam21ed metal surraces.
- 10 The microeml~lsio7.l was su3~-ctedi to -the degreasing test method of E~ample 1 with tne following results:
:~ .
1st attack on r,reased ~lide ar 1 sec.
70~75~ removal of grease at 10 sec.
100% removal of grease at 15 sec.
Esample 12 E~ample 2 was repeated in preparing an aqueous ; cleaner/degreaser emulsion having the following composition:
Componen~ Wt,%
l-Phenoxy-2-propanol 20.0 (Dowanol PPh) I~;ostearamide diethanolamide (1:1) 8.0 (Monamid 150-IS) Monoethanolamine 0.2 Soft H20 171.8 200.0 The resulting composition ~as 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 :
: . .
.~, .
~ . .
. .
~ ~U~IU iir S~I~LE~
~ ~ .
.. . , ~, , .
, .
~, 207067~
total solids content (theory) of 4.0%, and a total actives ` content (theory) of 14.1%. The emulsion e~hibited e~cellent stability over at least a four month period.
At a 1:5 dilution with water, 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 sat -; forth in E~amples 2-4 from alkyd enameled rnetal surfaces.
The microemulsion was subjected to the degraasing ~ 10 test method of E~ample 1 with the following results:
`~ 1st attac~s on greased slide at 1 sec.
40% removal of grease at 10 sec.
65-70% removal of grease at 15 sec.
100% removal of grease at 22 sec.
~xam~le 13 .~ ~
A hand cleaner in the form of a semipaste emulsion was prepared having the following composition:
:
ComPonent ~t.%
Polypropylene glycol 30.0 (Dow P-2000) Linoleamide diethanolamide (1:1)4.5 (Soyamide DEA-Clindrol LT-15-73-1) Acrylic acid/alkyl 0.2 methacrylate copoIymer 30% aqueous ;;~ (Acrysol ICS-l) ~ Triethanolamine 0.5 .
Soft H20 261.0 ;30 , S~ T~TE SH~E~
. ` . . .. ..
. . . . ` i~ .`
., . ` ..
.
.
:
WO9l/09104 PCT/US90/07215 The polypropylene glycol and linoleamide diethanolamide were pre-emulsified in water with stirring and the Acrysol ICS-l thickening agent was then added with stirring. The triethanolamine was then added dropwise with stirring to form a s~mioaste, intens21~7 whit? amulsion.
The emulsion had a pH or 8.22, a Brookfield viscosity (LV-#4 spindle, 6 rpm) of 13,259 c~n-~ipoiss, and 3 -total solids content (theory? of ïl, i~;, The emulsion had a very smootn eel and e.~hibited fair/good r~moval of oily, g-aasy _oils Irom hands.
Fc~a~o 1 ~ 1",1 A hand cleaner in the form or a semipaste emulsion was prepared having the following composition:
Com~onent 'W~
15 1-Phenoxy~2-propanol 15.0 tDowanol PPh) Polypropylene glycol 15.0 (Dow P-2000) Nonylphenoxypoly(ethyleneoxy) . 0.3 (8.5) ethanol (nonionic surfactant-T-Det N-9.5) Polyacrylic acid crosslinked 265.5 : with polyalkenyl polyether (0.12% aq. Carbopol 940) 25 Linoleamide diethanolamide (1:1) 4.2 (Soyamide DEA- Clindrol LT-15-73-1) 300.0 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 : ` ~
., ~ .
. .
TITUT~ SHEEI
.
, 2~70679 .
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 e~hibited e2cellent, fast removal of oily, greasy soils from hands although somewhak irritating to tne skin.
E~am le 15 ~':
A hand cleaner in the form of a thic~, paste/lo~ion emulsion was prepared having the following composition:
ComPonent ~,~
l-Phenoxy-2-propanol 1.0 (Dowanol PPh) 15 Polypropylene glycol g.o (Dow P-2000) Mineral Oil 9.0 (Viscosity, 165 centipoise) 20 Linoleamide diethanolamide (1:1) 2.0 (Soyamide D~A- Clindrol LT-15-73-1) Soft H20 78.0 Acrylic acid/alkyl 1.0 methacrylate copolymer, 30% aqueous (Acrysol ICS-l) -100.0 All of the components except the Acrysol ICS-l thickening agent were pre-emulsified with stirring, and the thickening agent was then added slowly with vigorous ' ' ' ' : .
~ ~iJ~Sli~,~TE SHEEl , .
.~ `
~ ~ 34 stirring. The resulting composition ~as an intensely ; bluish/white emulsion in the form of a thick, paste/lotion. The emulsion had a pH of 7.~2, a Brookfield viscosity (LV-#4 spindle, 6 rpm) o~ 5~,000 centipoise, a total solids content (theory) of ~0.3;, ~nd a otal acti~es content (theory) of 21.3%.
The emulsion had a smooth f9el, good rins~ ng characteristics, and exhibit~d ~ood/~er~f good rer,o~al OL
oily and greasy soils from hands.
ExamPle 16 Example 15 was repeat2d in prepa-~-ng a sem-pas~e :; emulsion having the following composition:
Component Phenoxy-2-propanol l.0 }5 (Dowanol PPh) 2-Phenoxyethanol l.0 (Dowanol EPh) Tripropyleneglycol l.0 monomethyl ether (Dowanol TPM) Polypropylene glycol 9.o ~Dow P-2000) Mineral oil 9.0 (Viscosity, 165 centipoise) 25 Linoleamide diethanolamide (l:l) 2.0 (Soyamide DEA-Clindrol LT-15-73-l) . . ~ .
Soft H20 75.6 Acrylic acid/alkyl l.4 methacrylate copolymer, 30% aqueous (Acrysol ` ICS-l) : ,. .
~: 100.0 -,, . ~
S1~B~TIIUTE SHET
:: ,-,.: . .
:. - .
WO91/09104 PCT/US~0/07215 2070~9 The resulting composition was an intensely ~luish/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, e~cellent rinsability characteristics, and e~hibited very good removal of oily and greasy soils from hands with a low level of irritation to the skin.
E~ample 17 Example 15 was repeated in preparing a thick lotion emulsion having the following composition:
Com~onent Wt.%
15 Polypropylene glycol 9.0 (Dow P-2000) Mineral oil 9.0 (Viscosity, 165 centipoise) Linoleamide diethanolamide (1:1) 5.0 (Soyamide DEA-Clindrol LT-15-73-1) Soft H20 76.1 Acrylic acid/alkyl 0.9 methacrylate copolymer, 30% aqueous (Acrysol ICS-l) 100.. 0 The resulting composition was an intensely white emulsion in the form of a thick lotion. The e~ulsion 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%.
:,~
~BS I ITUTE SHET
.. . . . ;
.
.::
... .- . . .
. .
WO 91tO9104 PCT/US90/07215 ~C ~ 3 6 : The emulsion had a very smooth feel, e~cellent rinsability characteristics, and e~hibited e~cellent removal of oily and greasy soilants from hands.
Example 18 E~ample 15 was repeated in prepari:~g 2 5-~eam/loclon emulsion having the following composit~on:
: Component ,. .~
l-Pheno~y-2-propanol l.0 (Dowanol PPh) - lO Polypropylene glycol 15.0 ~ (Dow P-2000) :, .
Nonylphenoxypoly(ethyleneo~y)3 . O
(7) ethanol (nonionic surfactant-T-Det N-8) :~ 15 Linoleamide diethanolamide (l:l) 2.0 (Soyamide DEA-Clindrol LT-15-73-l) Soft H20 78.0 Acrylic acid/alkyl 1.0 methacrylate copolymer, 30~ aqueous (Acrysol ICS-l) :
10 0 . 0 .
The resulting composition was an intensely white emulsion in the orm 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%.
. - .
,.
.
:'~
~ .
`.
'', BS~lTUTE SHEET
: . ~ .. .
~ ~ .
.. -.. . ..
.,. :: ~
WO9l/09104 PCT/US90/~72~5 37 .20~Ø~79 The emulsion had a very smooth feel, excellent rinsability characteristics, and exhibited excellent removal of oily and greasy soilants from hands. In addition, the emulsion is fully biodegradable.
ExamPle 19 An emulsion was prepared having the following composition:
ComPonent Wt.%
::
I-Pheno~y-2-propanol 20.0 ;~ 10(Dowanol P~h) ; Nonylphenosypoly(ethyleneo2y) 4.0 (8) ethanol (nonionic surfactant-T-Det N-8) Acrylic acid/alkyl 1.60 methacrylate copolymer, 30~ aqueous (Acrysol ICS-l) Triethanolamine 0.7 ~ Soft H20 173.7 :;. .
200.0 The water was added with stirring to the l-pheno2y-2-propanol and nonionic surfactant components.
The Acrysol ICS-l thickening agent was then added with continued stirring, followed by the dropwise addition of 25 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~o.
, ~ .
- ~:
S~EEI
.. .
. . . ..
- , - . . . .
. . . ~ . , .
, . .
.. ..
~ 38 At both a 1:~ and a 1:5 dilution with water, diluted emulsions were formed which easily removed black Magic Marker markings from alkyd enameled metal surfaces.
At a 1:4 dilution with water, the resulting emulsion was subjected to the degreasing test method of - Example 1 with the following results:
1st attack on greased slide at 3 sec.
55-60~o removal of grease at 10 sec.
100% removal of grease at 15 sec.
.
At a 1:5 dilution ~ith ~ater, the resulting emulsi~n was subjected to the deqreasing test method of E~.amplz 1 with the following results:
.
1st attack on greased slide at 3 sec.
55-60% removal of grea~e at 10 sec.
lS 100% removal of grease at 20 sec.
:,~ .
E~ample 20 :` :
E~xample 19 was repeated in preparing an emulsion having the following composition:
Component Wt,%
20 1-Pheno~y-2-propanol 20.0 ` (Dowanol PPh) Nonylpheno~ypoly(ethyleneoxy) 3.0 (8.5) ethanol (nonionic surfactant-T-Det N-9.5) .
~; 25 Triethanolamlne 0.7 Soft H20 containing 0.06% 176.3 ^ polyacrylic acid crosslinked with polyalkenyl polyether (Carbopol 940 thickener) 200.0 ~'.
S~BST~TlilTE SHET
:
. .. .. . . . j . ,~ ..
.
. . . . -.
..... ..... .
39 207~679 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%.
At a 1:5 dilution with water, an emulsion resulted which e3silY remoYed black Magic Marker markings ~rom an alkyd ~nameled metal surface. The emulsion was subjected to the degreasing test method of Example 1 with the followi~g ~sults:
: , 1st attas~ on greased slide at 1 sec.
(almost instantaneous) 100% removal of grease at 9 sec.
At a 1:10 dilution with water, a slightly hazy ~; .
emulsion-solution was formed which was rather ineffective in removing black Magic Marker markings from an alkyd enameled metal surface. The emulsion-solution was subjected to the degreasing test method of Example 1 with the following results:
: ' ~ .
1st attack on greased slide at 3 sec.
60% removal of grease at 15 sec.
100% removal of grease at 25 sec.
,' :
: ! At a 1:20 dilution with water, a clear solution was .. ,: .
formed which was totally ineffecti~e in removing black Magic Marker markings from an alkyd enameled metal surface. The solution was subjected to the degreasing test ; method of E~ample 1 with the following results:
~ ~ 1st attack on greased slide at 15 sec.
;~ ~ 10-15% removal of grease at 1.0 min.
~; 30 25% removal af grease at 2.0 min.
SUBSTITU~E SRFET
:
.. ~......................... . .
.. . . . ..
. . .
.
WOgl~O9104 PCT/US90/07215 ~,~19~- 40 45% removal of grease at 30 min.
60~ removal of grease at 4.0 min.
70% removal of grease at S.0 min.
75-80% removal of grease at 6.0 min.
85% removal of grease at 7.0 min.
90-95~ removal of grease at 9.0 min.
100% removal of grease at 10.0 min.
The marked change in degreasing erficac~ (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 21 j Example 19 was repeated in preparing an emulsion having the following composition:
Com~Qnent Wt.
l-Phenoxy-2-propanol 20.0 (Dowanol PPh) I Octylphenol ethoxylate (5E.O.) 3.0 ~Triton X-45) ` 20 Triethanolamine 0.5 Soft H20 containing 0.06% 176.5 polyacrylic acid crosslinked with polyalkenyl polyether (Carbopol 940 thickener) 200.0 - 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%.
.
., .
~UBSTITi3T~ SHEET
41 ' ' , ~t a 1:5 dilution with water, an emulsion resulted which was sub~ected to the degreasing test method of Example l with the following results:
' 1st attack on greased slide at 5 sec.
35-40% removal of grease at 10 sec.
80~ removal o graas2 at 20 sec.
lO0~ ~2moval of grease at 25 sec.
.t ~ l:10 ~lluti~n with water, an emulsion resulted which was subjected to t'ne degreasing test method of E~ample 1 with the following results:
~. , 1st attack on greased slide at lO sec.
` 40% removal of grease at 20 sec.
75% removal of grease at 30 sec.
lO0~ removal of grease at 45 sec.
At a 1:20 dilution with water, a hazy emulsion-solution resulted which was subjected to the degreasing test method of E~ample 1 with the following results-~`~' ' 1st attack on greased slide at 20 sec.
106 removal of grease at l min.
20-25% removal of grease at 2 min.
i 40% removal of grease at 3 min.
~ 65% removal of grease at 4.25 min.
, 85-90% removal of grease at 6 min.
~ 100% removal of grease at 7.5 min.
~ ~ , ~ .
. ~
-:: :
.
:~ S'JB~TITUTE S'~EEI
,~
. . ~ ; . . .
. . .
. ~ ~,; . .
, ~ .
;:
~9 Exam~le 22 E2ample 19 was repeated in preparing an emulsion having the following composition:
ComPonent Wt.%
5 1-Pheno~y-2-propanol 30.0 (Dowanol PPh) Dodecylbenzenesulfonic acid 0.6 Acrylic acld/alkyl 2.2 methacrylate copolymer, 30% aqueous (Acrysol ICS-l) Triethanolamine 1.4 ., .
Soft H20 165.8 200.0 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~.
At a 1:5 dilution with water, an emulsion resulted which very easily removed black Magic Marker markings from an alkyd enameled metal surface. The emulsion was subjected to the degreasing test method of E~ample 1 with the following results:
' ' ` 1st attack on greased slide at 1 sec.
(almost instantaneous) 100% removal of grease at 7 sec.
At a dilution of 1:10 with water, a very slight , 30 emulsion or almost hazy solution resulted which was only i moderately effective in removing black Magic Marker .
~ , . .
~æSl'l~U~E S~EEI
- -.
~: :
WO91/09104 , PCT/US90/~7215 2~7067~ ~
markings from an alkyd enameled metal surface. The emulsion or solution was subjected to the degreasing test method of'E~ample 1 with the following results:
1st attack on greased slide at 1+ sec.
100'~ relnoral os grease at 12 sec.
~, At a dilu~ion OL 1:20 -~ith water, a clear solution was formed which was wholly ineffective in removing black Magic ~arl{er mark~ngs ~-rom an alkyd enameled metal surface. The solution was subjected to the degreasing test method of ~ 10 E.sample 1 ~7ith the following results:
'~ 1st attack on greased slide at 5 sec.
40% remo,val of grease at 15 sec.
75% removal of grease at 30 sec.
100% removal of grease at 45 sec.
.- . . . .
' 15 , Example 23 ;!
E~ample 19 was repeated in preparing an emulsion having ths following composition:
Component Wt.%
l-Phenoxy-~-propanol 20.0 (Dowanol PPh) Octylphenol etho~ylate - - 4.0 (7-8 E.O.) tTriton X-114) Triethanolamine' ~ 1.0 Soft H20 172.0 25 Acrylic acid/alkyl 3.0 methacrylate copolymer, 30% aqueous (Acrysol ~ ICS-l) '~ 200.0 ,; .
~ .
SUBSTITUTE SHEET
.. . ... '. i ,. . ~ -- , . .
~ ~ , ~ `.. . .
. ..
. . . .
.~ . . . .
. , .
, . . .
` ~. . ..
All of the components except the Acrysol ICS-l thickening agent were pre-emulsified with a high-speed, motor driven, 3-bladed propeller for 3 minutes, and the Acrysol ICS-1 was then added very slowly with vigorous stirring to provide immediate thickening. The resulting composition was an intensely bluish/white emulsion in the form of a thick lotion or semipaste having a pH of 7.88, a Brookfield viscosity (~V-~4 spindle, 12 rpm) of 8600 centipoise, a total solids content (theory) of 2.8%, and a ; 10 total actives content (theory) of 12.8%.
At a I:5 dilution with water, a bluish/white microemulsion formed which very easily and fully removed the following markings from alkyd enameled metal surfaces:
black ~agic Marker felt pen, blue and black indelible ballpoint pen, #1 hardness pencil and red (waxy) crayon.
`~ The microemulsion was subjected to the degreasing test method of Example 1 with the following results:
;~ 1st attack on greased slide at 1 sec.
60~ removal of grease at 10 sec.
~ 20 100% removal of grease at 20 sec.
`::
ExampIe 24 Example 23 was repeated in preparing an emulsion having the following composition:
wt.%
; 25 1-Pheno~y-2-propanol 20.0 tDowanol PPh) Cg-Cll alkanol/2.5 E.O. 4.0 condensate (Neodol 91-2.5) Triethanolamine 1.0 .
SUBSTITUTE SH~ET
, .~. ... .
-. - .
. . .
.. . .
WO91/09104 P~T/US90/07215 ` 2~7D~79 Soft H20 172.0 :
Acrylic acid/alkyl 3.0 - methacrylate copolymer, 30% aqueous (Acrysol ICS-l) 200 . 0 The rosulting composition was an intensely ~luish-T~7hit~ omulsion ha~ing a pH of 8.27, a Brookfield iscosi!cv ~LV-~3 spindle, 12 rpm) of 3650 centipoise, a ~: 10 total solids ~ontant (thaory) of 2.8~, and a total actives content ~theory) of 12 . 8%.
~ a ':5 dilutlon wl~h .water, a bluish/white - microemul~ion Eormed which very quickly, easily and totally . removed the following markings from alkyd enameled metal ~ 15 surfaces: black Magic Marker felt pen, blue and black ; indelible ballpoint pen, #l hardness pencil, red (waxy) crayon, and automotive grease smearings.
~`` The microemulsion was subjected to the degreasing test method of Example 1 with the following results: ~
,' , 1st attack on greased slide at less than 1 sec.
. 10~0o rcmGYal Of gLaase at 15 sec.
.
Example 25 ; An aquesus cleaner/desreaser emulsion in the form of `~ an aerosol formulation was prepared having the following composition:
~` Component Wt.%
Phenoxy-2-propanol 3.0 . (Dowanol PPh) : Octylphenol etho~ylate 0.2 (Triton X-45) ~ , , ~U8SlIIU~E SH~EI
"~ . . ~ - .
. ~ .
,.. , , ~ ~. .
~ , . . .
.
., ` , ~.. .
~ . . ..
WO91/09l04 PCT/US90/072~5 ,:
.
~ 46 Deionized H20 95.2 Acrylic acid/alkyl 1.2 methacrylate copolymer, 30% aqueous (Acrysol ICS-l) Ammonium hydroxide (23%) 0.2 Sodium Nitrite 0.2 .
~' 100 . O
The fiLsL ~our compon2nts listed above were pre-emulsified undsr hi~h speed stirring for three minutes with a ~7ater d iven 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%, a~d 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 sropellant (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.
It was found that the resulting aerosol formulation very easily, quickly and totally removed the following markings from alkyd enameled metal surfaces (spray on/wipe off): black, indelible Magic Marker felt pen, blue and black indelible ballpoint pen, #1 hardness pencil, red (waxy) crayon and automotive grease smearings. The aerosol formulation also readily removed fingerprints, smudges, and similar markings from walls and woodwork.
.
` S~TITUTE SUEET
~:
..
WO9l/09104 PCT/US9~/0721 :
47 ~ ~ 7 ~ 6 ~ 9 E~ample 26 An aqueous cleaner/degreaser emulsion was prepared ; having the following com~osition:
. Component 1~1t.%
5 Phosphate ester coupler/ 0.30 emulsifier (MonaI3~ 1293~
`Isostearamide diethanolamide 0.40 :. (l:l) (~onamid 150-IS~
Monoethanolamine 0.40 lO Deionized H20 192.9 2-Ethylhe~o~yQthanol 2.0 ~:~ (Ektasolv E~H~Eastman) , l-Pheno~y-2-propanol - 4.0 (Dowanol PPh) 200.0 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 b:luish/white emulsion having a pH of 10.20, a Brookfield viscos:ity (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 ::~ e~cellent stability characteristics.
l'he emulsion possessed excellent, rapid, and efficient cleaning/degreasing action against the following soilants:
;~ : black Magic Marker markings, ballpoint pen markings, #l : hardness pencil markings, red (wa~y) crayon markings, . automotive greases, Vaseline, lard, shortening, and : 30 lipophilic oils.
.
.
~ SUBSTITUT~ Sl!~ET
., . ~
.; . .. . . .
,.,; . ,. . , . , .. .-.. . , . ~ ~, , . ,. . . , . . ;.. ~ . ~ . . . ... . .. ... .
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.. .. , ~ .~ . . ~ . . . ...
. . , -WO9t/09104 PCT/US90/07215 .~9 7~9 ~8 Example 27 Example 26 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
ComPoner.~ Wt.%
5 Diethanolamino lauryl sulrata 0.20 (S-te~arol DEA, 35%) Isostearamide diethanolamide0.40 xlonamid 150-1-S) : Monoethanolamine 0.60 So~t ~2 192.3 l-Phenoxy-2-~ropanol 5.0 : (Dowanol ~Ph) . Acrylic acid/alkyl methacrylate1.5 copolymer, 30% aqueous : 15 ~Acrysol ICS-l) ; 200.0 The resulting composition was a bluish emulsion (iridescent cast) having a pH of 10.21, a Brookfield viscosity (L~-~2 spindle, 60 rpm) of 72 centipoise, a total ; 20 solids content (theory) of 0.46% and a total actives content ttheory) of 3.26%. The emulsion exhibited eæcellent stability characteristics.
The emulsion possessed excellent, rapid, and efficient cleaning/degreasing action against all the soilants listed in Example 26.
.
.
'^ .
~IBS~IIU~E SHEEI
: ~. . . . .
.: - ,. , . .
... . .
, .
WO91/09104 PC~/US~0/07215 :
2 ~ 7 9 ExamPle 28.
Example 26 was repeated in preparing an aqueous :. cleaner/degreaser emulsion having the Eollowing composition:
:
Com~onent ~7t.%
~: . 5 Isostearamide diethanolamide 0.5 onamid 150-IS) Sodium dodecyldiphenyletner O.l disul:Eonate-coupler ~Dowfa~ 2Al, 45%) . lO Monoethanolamine O.S
:; Soft H20 190.3 2-Pheno~yethanol 7.0 - (Dowanol EPh) Acrylic acid/alkyl methacrylate l.5 copolymer, 30% aqueous (Acrysol ICS-l) ,~ .
200.0 ~ The resulting composition was a light, slightly :~. bluish/white emulsion having a p~ of lO:08, a ~rookfield ~ 20 viscosity ~LV-#2 spindle, 60 rpm) of 57 centipoise, a total :~ st~lids content (theory) of 0.50% and a total actives content (theory~ of 4.30~. The emulsion e~hibited e~cellent stability characteristics.
The emulsion possessed excellent, rapid, and complete cleaning/degreasing action against all the soila~ts listed in E~ample 26.
E~ample 29 ..
Example 26 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
:`.' .:
.
. ~
~ SIIIUI~ SHEEI
., .
~`, - .. ~ . . . ;.
., ~ .-. , " :
. .. .
~ .. ` ~. . ; . .
, -,. . ~ , , .
.
~; , ` ` ~ . .
~ 50 Com~onent Wt.%
Isostearamide diethanolamide 0.3 (1:1) (Monamid 150-IS) Mi~ed caprylamide DEA/ 0.2 capramide DEA coupler (Clintwood CP-Z-61-2) Monoethanolamlne 0.3 ~;
; Soft ~2 19~.2 l-Pheno.. ~y-.-p-o~anol . 5.0 ~Dowanol PPhj ~:~ 200.0 The resulting sompos~tion was an intensely .
.~, bluish/white emulsion having a pH of 10.43, a Brookfield : viscosity (L~-#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 e~hibited : . e~cellent stability characteristics.
The emulsion possessed excellent, rapid, and complete cleaning/degreasing action against all the soilants listed in E~ample 26.
, E3ample 30 .
An aqueous cleaner/degreaser emulsion was prepared ~ havlng the following composition:
`~ Component Wt.%
- 25 Isostearamide diethanolamide 0.30 (1:1) (Monamid 150-IS) :~ ~ Soft H20 194.2 : Butoxyethyl acetate 3.0 (EB acetate) ~-,'' ~ ~ . .
.
,'~ .
. .~ -`~ S~'IPl~ITU~E SI~E~
..; ..
~. . .
... . . .. .
~ , ..... ~, . - ..... . . . .
,. .
.
.- ,~. ` . .
. . . . . . .
. . . .
WO91/09104 PCT/US90/~7215 Sl 2i~ 7~
Acrylic acid/alkyl methacrylate 1.0 copolymer, 30% aqueous (Acrysol ICS-l) Aqueous ammonium hydro~ide 0.0 (28% NH3) 100.0 The first two components were stir.ed at room temperature for 15 minutes to complately di~perse 'che ; isostearamide diethanolamide in water. The buto~yetnyl acetate was then added with vigorous stirring at room temperature for 30 minutes. The Acrysol ICS-l was ne~t ` added with stirring followed by dro2wise addition of ~he ; ammonium hydro~ide with ~igorous stirri~.g at room temperature for 15 minutes.
The resulting composition was a slightly ~luish/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 e~hibited excellent stability characteristics.
The emulsion possessed e~cellent, rapid, and complete cleaning/degreasing action against all the soilants listed in Example 26.
Egample 31 A hand cleaner emulsion was prepared having the following composition:
ComPOnent Wt.~
Polypropylene glycol monobutyl 10.0 ether (Dow PolyglycoI
L-1150) ~'' .
: , ~
` S~BSTl~UT~ SHEET
i . . ..
,.~. .
., , " . . .
Mineral oil (Penreco, 30.0 Drakeol 5 L~O) Octylphenol/7-8 E.O. 10.0 ~Triton ~
5 Isostearamide diethanolamide 6.0 ( 1 : 1 ) Soft H20 1~1.0 Acrylic acid/alXyl methacrylata 3.0 copolymer, 30?~ acu~ous (Acrysol IC~
100 . O
- The firs'~ e ,o:;n~onsn~ sre emul~ d and tne Acrysol ICS-l was c~en added ~ith ~tigorous stirring. The resulting composition was an intensely bluish/white emulsion which had a creamy, smoo~h 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. When reformulated to contain no Polyglycol L-1150, the cleaning/degreasing action was ~; drastically reduced.
E~ample 32 An aqueous cleaner/degreaser emulsion in the form of an aerosol formulation was prepared having the following composition:
, ! ~ Component ~t %
Liquid lauramide 0.30 diethanolamide (1:1 Superamide) ~ 30 (Mackamide LLM) :,.
~; Monethanolamine 0.60 .~.
.:
.
~BSTITUTE SI~EET
. ~
WO91/09104 PCT/US90/~7215 2070~79 `
Sodium nitrite 0.30 Perfluoroalkylphosphate 0.40 ester antifoaming agent (Atsurf F-12, 15%) Deionized H20 191.80 l-Phenoxy-2-propanol 5.00 (Dowanol PPh) Acrylic acid/alkyl 1.~0 methacrylate copolymer, 30% aqueous (Acrysol ICS-1) ~' 200.00 The first fiYe components lis~ed aDov2 wer2 s~i red at high speed for 15 minutes to fully disperse the lauramide diethanolamide and to form a microemulsion. The 1-pheno~y-2-propanol was then added with vigorous stirring for 30 minutes at room temperature after which the Acrysol ICS-l was added dropwise with good stirring. The resulting composition was a bluishiwhite emulsion with a pH of 9.86, a Brookfield viscosity (LV-#2 spindle, ~0 rpm) of 28 centipoise, a total solids content (theory) of 0.57~, and a total actives content (theory) of 3.37~. Ths emulsion ,:
exhibited excellent stability.
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-br~aking foam-with ~` e~cellent vertical cling. The formulation exhibited excellent cleaner/degreaser action against the markings listed in Example 25 and had good/excellent wet-out properties.
., .
.' `
::, `~:
., SUBSTlTUTr SHEET
... ~. ... . . -.~ ~ , , .
.
.
WO~I/09104 PCT/US90/07215 Ex2mple 33 An aqueous cleaner/degreaser emulsion was prepared having the rollowing composition: -Component r~7t.~
5 Isostearamida diet'nanolamide8.0 ; (l:l)(Monamid 150-IS) Monethanolamine 0.95 Tap Water ~pH 9.55, '55p~170.05 hardness) 10 1-Phenoxy-2-propanol 20.0 (Dowanol P h) Perfluoroalkylphosphate~ 1.0 ester antifoaming agant ; (Atsurf F-12, 15%) 200.00 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 microamulsion with stirring continued for one hour at room temperature after which the antifoaming agent was added with stirring. The rasulting composition was a very intense bluish whita emulsion having a pH of 10.53, a ~rookfield viscosity ~LV-~2 spindlP, S0 'pm) of 7.5 centipoise, a total solids content (theory)-of 9.08%, and a total actives content (theory) ~of 14.55%. The emulsion e~hibited excellen~ stability.
At a 1:5 dilution with water, a bluish to bluish/white microemulsion formed which very ~asily, quickly, and completely removed all of the markings set forth in Examples 2-4 from alkyd enameled metal surfaces.
, . .
S~IB~,TITU~ SH~LET
.,.
., j , .
WO91/~9104 PCT/US90/07215 2070~79 The microemulsion was subjected to the degreasing test method of E~ample 1 with the following results:
1st attack on greased slide at l sec.
45% removal of grease at 10 sec.
75% removal of grease at 15 sec.
100% removal of grease at 20 sec.
- .
This emulsion composition is especially suitable rsr use in mechanized high pressure/spray equipment T,qhere Soam ~' generation cannot be tolerated.
~: , E~amPle 34 An aqueous cleaner/degreaser emulsion was prepared ~-~, having the following composition:
~ Component Wt.
.,.j .
Phosphate ester coupler/ 0.10 emulsifier (Monafa~ 1293) ., .
Isostearamide diethanolamide 0.40 (l:l)(Monamid 150-IS) Monethanolamine 0.60 :.~
Soft H20 192.40 20 1-Pheno~y-2-propanol 5.00 ~` (Dowano1 PPh) Acrylic acid/alkyl 1.50 ;~ Methacrylate copolymer 30% aqueous (Acrysol ICS-l) 200.00 ~ .
The first four components listed above were stirred at room temperature until fully dispersed (ca 15 minutes).
The l-phenoxy-2-propanol was added with vigorous stirring ' .~ .
~ , ~ .
~U~STI~UTE SHEET
,: . - . , .
. .
. .
~ , . . . ..
.~ , . .
: . .
.
WO91/091~4 PCr/US90/07215 6q9 56 for 0.5 hour at room temperature and ths Acrysol ICS-1 was added dropwise with vigorous stirring to viscosify 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 csnkipo1se, a total solids content (theory~ OL 0 . ~a~, and a cocal accives content (theory) of 3.28~. The emlilsion e~r.hi-3ited excellent stability.
The emulsion e~hi`oited exceïl2nt cleaneridegreaser action agai.nst all OL the ma, lSings a't Eor'c'1 tn Examples 2-4 and against Vaseline, iard, short~ning and iipophilic oils.
; This emulsion is suitabls rfor US~ as a r~ady-to-l~2 formulation applied by pump spray or trigger spray action.
Exam~le 35 An aqueous cleaner/degreaser emulsion was prepared having the following composition:
` ComPonent Wt.
Polyglycol copolymer ~ 3.0 containing ethylene oxide and propylene oxide (Dow Polyglycol 112-2) Octylphenol ethoxylate 0.3 (5 E.O.)~Triton X-45) Soft H20 96.7 100.00 The water was added very slowly to the stirred mixture of the other two components llsted 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.
~ .
S'~B~TlTll~ SH~ET
.
..
.. . .
57 2~067g 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.
Example 36 An aqueous cleaner/degreaser emulsion was prepared having the following composition:
Gom~onent Wt.
Polypropylene glycol 6.0 (Dow P-2000) Soft H20 190.8 . Octylphenol ethoxylate (5 E.O.)0.6 (Triton X-45) Triethanolamine 0.6 : .
;~ 20 Acrylic acid/alkyl 2.0 ~, Methacrylate copolymer 30% aqueous (Acrysol ICS-l) :~ .
200.00 The first four components listed above were pre-emulsified with high speed stirring and the Acrysol ICS-l was added dropwise under vigorous high speed/hiah shear stirring conditions. The resulting composition was a white, creamy :; :
~: .
~ .
'leSll~U~E SHEET
- : -~ ` 58 emuls~ion having a pH of 7.81, a Brookfield viscosi~y (LV-~3 spindle, 12 rpm) of 870 centipoise and a to~al solids/total actives content (theory) of 3.9%.
This emulsion readily removed tar, grease, asphalt, black (rubber) heel and red (wa7y) crayon mar~s from vinyl tile coated with polymeric floor finish usin~ a w2ttea paper towel or cloth. The tile ouf rS to 3 cl~ar, colorless, high shine on ai r dryiny Wi tn no damaging solvent action occurring on the floor finis'n.
I0 In view of the above, it will be s22n t.1a~ ~'n._ several objects of the invention are achieved and othsr advantageous results attained.
As various changes could b2 mad2 in t'n_ abov2 :
~` compositions without departing from the scope of the ;~ 15 invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not ln a limiting sense.
~ `
:~
:: ' `'~'i .,~
:-:: , , .
.
: .
- SU~SIITUTE SHET
~. . .
-.
At a 1:5 dilution with water, a ~luisn/white microemulsion was formed. The microemulsion readily and completely removed all of the markings s~t Lorth in E~amples 2-4 from alkyd enameled metal surfaces.
The microemulsion was subjected to the degreasing test method of ~xample 1 with the followins ,esults:
1st attack on greased slide at 1 sec.
~;~ 15 100% removal of grease at 13 sec.
~ E~amPle 11 Example 2 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
ComPonent r~l,.,,;
20 1-Phenoxy-2-propanol 30.0 (Dowanol PPh) Isostearamide diethanolamide (1:1) 10.0 ~Mackamide ISA) Monoethanolamine 0.3 25 Soft H20 159.7 200.0 .
The resulting composition was an intensely bluish/white emulsion having a pH of 9.63, a Brookfield viscosity (~V-#2 spindle, 60 rpm) of 7.0 centipoise, a ~ .
S~T~TUTE SHE!ET
:
.
,.
~9 30 total solids content ~theory) o 5.0%~ and a total actives content (theory) or 20~15~o~ The emulsion exhibited excellent stability over an extended period at room temperature.
At a 1:8 dilution ~ith water, a bluish/white microemulsion ~as lormed wnich had a 1.67% conceniration of l-phenoxy-2-~ropanol. The microemulsion vary easily and completely remov2d aLl O:L ~'ne ~nar';inys 3eJC for~h in Examples 2-~ rrom aixyd enam21ed metal surraces.
- 10 The microeml~lsio7.l was su3~-ctedi to -the degreasing test method of E~ample 1 with tne following results:
:~ .
1st attack on r,reased ~lide ar 1 sec.
70~75~ removal of grease at 10 sec.
100% removal of grease at 15 sec.
Esample 12 E~ample 2 was repeated in preparing an aqueous ; cleaner/degreaser emulsion having the following composition:
Componen~ Wt,%
l-Phenoxy-2-propanol 20.0 (Dowanol PPh) I~;ostearamide diethanolamide (1:1) 8.0 (Monamid 150-IS) Monoethanolamine 0.2 Soft H20 171.8 200.0 The resulting composition ~as 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 :
: . .
.~, .
~ . .
. .
~ ~U~IU iir S~I~LE~
~ ~ .
.. . , ~, , .
, .
~, 207067~
total solids content (theory) of 4.0%, and a total actives ` content (theory) of 14.1%. The emulsion e~hibited e~cellent stability over at least a four month period.
At a 1:5 dilution with water, 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 sat -; forth in E~amples 2-4 from alkyd enameled rnetal surfaces.
The microemulsion was subjected to the degraasing ~ 10 test method of E~ample 1 with the following results:
`~ 1st attac~s on greased slide at 1 sec.
40% removal of grease at 10 sec.
65-70% removal of grease at 15 sec.
100% removal of grease at 22 sec.
~xam~le 13 .~ ~
A hand cleaner in the form of a semipaste emulsion was prepared having the following composition:
:
ComPonent ~t.%
Polypropylene glycol 30.0 (Dow P-2000) Linoleamide diethanolamide (1:1)4.5 (Soyamide DEA-Clindrol LT-15-73-1) Acrylic acid/alkyl 0.2 methacrylate copoIymer 30% aqueous ;;~ (Acrysol ICS-l) ~ Triethanolamine 0.5 .
Soft H20 261.0 ;30 , S~ T~TE SH~E~
. ` . . .. ..
. . . . ` i~ .`
., . ` ..
.
.
:
WO9l/09104 PCT/US90/07215 The polypropylene glycol and linoleamide diethanolamide were pre-emulsified in water with stirring and the Acrysol ICS-l thickening agent was then added with stirring. The triethanolamine was then added dropwise with stirring to form a s~mioaste, intens21~7 whit? amulsion.
The emulsion had a pH or 8.22, a Brookfield viscosity (LV-#4 spindle, 6 rpm) of 13,259 c~n-~ipoiss, and 3 -total solids content (theory? of ïl, i~;, The emulsion had a very smootn eel and e.~hibited fair/good r~moval of oily, g-aasy _oils Irom hands.
Fc~a~o 1 ~ 1",1 A hand cleaner in the form or a semipaste emulsion was prepared having the following composition:
Com~onent 'W~
15 1-Phenoxy~2-propanol 15.0 tDowanol PPh) Polypropylene glycol 15.0 (Dow P-2000) Nonylphenoxypoly(ethyleneoxy) . 0.3 (8.5) ethanol (nonionic surfactant-T-Det N-9.5) Polyacrylic acid crosslinked 265.5 : with polyalkenyl polyether (0.12% aq. Carbopol 940) 25 Linoleamide diethanolamide (1:1) 4.2 (Soyamide DEA- Clindrol LT-15-73-1) 300.0 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 : ` ~
., ~ .
. .
TITUT~ SHEEI
.
, 2~70679 .
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 e~hibited e2cellent, fast removal of oily, greasy soils from hands although somewhak irritating to tne skin.
E~am le 15 ~':
A hand cleaner in the form of a thic~, paste/lo~ion emulsion was prepared having the following composition:
ComPonent ~,~
l-Phenoxy-2-propanol 1.0 (Dowanol PPh) 15 Polypropylene glycol g.o (Dow P-2000) Mineral Oil 9.0 (Viscosity, 165 centipoise) 20 Linoleamide diethanolamide (1:1) 2.0 (Soyamide D~A- Clindrol LT-15-73-1) Soft H20 78.0 Acrylic acid/alkyl 1.0 methacrylate copolymer, 30% aqueous (Acrysol ICS-l) -100.0 All of the components except the Acrysol ICS-l thickening agent were pre-emulsified with stirring, and the thickening agent was then added slowly with vigorous ' ' ' ' : .
~ ~iJ~Sli~,~TE SHEEl , .
.~ `
~ ~ 34 stirring. The resulting composition ~as an intensely ; bluish/white emulsion in the form of a thick, paste/lotion. The emulsion had a pH of 7.~2, a Brookfield viscosity (LV-#4 spindle, 6 rpm) o~ 5~,000 centipoise, a total solids content (theory) of ~0.3;, ~nd a otal acti~es content (theory) of 21.3%.
The emulsion had a smooth f9el, good rins~ ng characteristics, and exhibit~d ~ood/~er~f good rer,o~al OL
oily and greasy soils from hands.
ExamPle 16 Example 15 was repeat2d in prepa-~-ng a sem-pas~e :; emulsion having the following composition:
Component Phenoxy-2-propanol l.0 }5 (Dowanol PPh) 2-Phenoxyethanol l.0 (Dowanol EPh) Tripropyleneglycol l.0 monomethyl ether (Dowanol TPM) Polypropylene glycol 9.o ~Dow P-2000) Mineral oil 9.0 (Viscosity, 165 centipoise) 25 Linoleamide diethanolamide (l:l) 2.0 (Soyamide DEA-Clindrol LT-15-73-l) . . ~ .
Soft H20 75.6 Acrylic acid/alkyl l.4 methacrylate copolymer, 30% aqueous (Acrysol ` ICS-l) : ,. .
~: 100.0 -,, . ~
S1~B~TIIUTE SHET
:: ,-,.: . .
:. - .
WO91/09104 PCT/US~0/07215 2070~9 The resulting composition was an intensely ~luish/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, e~cellent rinsability characteristics, and e~hibited very good removal of oily and greasy soils from hands with a low level of irritation to the skin.
E~ample 17 Example 15 was repeated in preparing a thick lotion emulsion having the following composition:
Com~onent Wt.%
15 Polypropylene glycol 9.0 (Dow P-2000) Mineral oil 9.0 (Viscosity, 165 centipoise) Linoleamide diethanolamide (1:1) 5.0 (Soyamide DEA-Clindrol LT-15-73-1) Soft H20 76.1 Acrylic acid/alkyl 0.9 methacrylate copolymer, 30% aqueous (Acrysol ICS-l) 100.. 0 The resulting composition was an intensely white emulsion in the form of a thick lotion. The e~ulsion 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%.
:,~
~BS I ITUTE SHET
.. . . . ;
.
.::
... .- . . .
. .
WO 91tO9104 PCT/US90/07215 ~C ~ 3 6 : The emulsion had a very smooth feel, e~cellent rinsability characteristics, and e~hibited e~cellent removal of oily and greasy soilants from hands.
Example 18 E~ample 15 was repeated in prepari:~g 2 5-~eam/loclon emulsion having the following composit~on:
: Component ,. .~
l-Pheno~y-2-propanol l.0 (Dowanol PPh) - lO Polypropylene glycol 15.0 ~ (Dow P-2000) :, .
Nonylphenoxypoly(ethyleneo~y)3 . O
(7) ethanol (nonionic surfactant-T-Det N-8) :~ 15 Linoleamide diethanolamide (l:l) 2.0 (Soyamide DEA-Clindrol LT-15-73-l) Soft H20 78.0 Acrylic acid/alkyl 1.0 methacrylate copolymer, 30~ aqueous (Acrysol ICS-l) :
10 0 . 0 .
The resulting composition was an intensely white emulsion in the orm 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%.
. - .
,.
.
:'~
~ .
`.
'', BS~lTUTE SHEET
: . ~ .. .
~ ~ .
.. -.. . ..
.,. :: ~
WO9l/09104 PCT/US90/~72~5 37 .20~Ø~79 The emulsion had a very smooth feel, excellent rinsability characteristics, and exhibited excellent removal of oily and greasy soilants from hands. In addition, the emulsion is fully biodegradable.
ExamPle 19 An emulsion was prepared having the following composition:
ComPonent Wt.%
::
I-Pheno~y-2-propanol 20.0 ;~ 10(Dowanol P~h) ; Nonylphenosypoly(ethyleneo2y) 4.0 (8) ethanol (nonionic surfactant-T-Det N-8) Acrylic acid/alkyl 1.60 methacrylate copolymer, 30~ aqueous (Acrysol ICS-l) Triethanolamine 0.7 ~ Soft H20 173.7 :;. .
200.0 The water was added with stirring to the l-pheno2y-2-propanol and nonionic surfactant components.
The Acrysol ICS-l thickening agent was then added with continued stirring, followed by the dropwise addition of 25 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~o.
, ~ .
- ~:
S~EEI
.. .
. . . ..
- , - . . . .
. . . ~ . , .
, . .
.. ..
~ 38 At both a 1:~ and a 1:5 dilution with water, diluted emulsions were formed which easily removed black Magic Marker markings from alkyd enameled metal surfaces.
At a 1:4 dilution with water, the resulting emulsion was subjected to the degreasing test method of - Example 1 with the following results:
1st attack on greased slide at 3 sec.
55-60~o removal of grease at 10 sec.
100% removal of grease at 15 sec.
.
At a 1:5 dilution ~ith ~ater, the resulting emulsi~n was subjected to the deqreasing test method of E~.amplz 1 with the following results:
.
1st attack on greased slide at 3 sec.
55-60% removal of grea~e at 10 sec.
lS 100% removal of grease at 20 sec.
:,~ .
E~ample 20 :` :
E~xample 19 was repeated in preparing an emulsion having the following composition:
Component Wt,%
20 1-Pheno~y-2-propanol 20.0 ` (Dowanol PPh) Nonylpheno~ypoly(ethyleneoxy) 3.0 (8.5) ethanol (nonionic surfactant-T-Det N-9.5) .
~; 25 Triethanolamlne 0.7 Soft H20 containing 0.06% 176.3 ^ polyacrylic acid crosslinked with polyalkenyl polyether (Carbopol 940 thickener) 200.0 ~'.
S~BST~TlilTE SHET
:
. .. .. . . . j . ,~ ..
.
. . . . -.
..... ..... .
39 207~679 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%.
At a 1:5 dilution with water, an emulsion resulted which e3silY remoYed black Magic Marker markings ~rom an alkyd ~nameled metal surface. The emulsion was subjected to the degreasing test method of Example 1 with the followi~g ~sults:
: , 1st attas~ on greased slide at 1 sec.
(almost instantaneous) 100% removal of grease at 9 sec.
At a 1:10 dilution with water, a slightly hazy ~; .
emulsion-solution was formed which was rather ineffective in removing black Magic Marker markings from an alkyd enameled metal surface. The emulsion-solution was subjected to the degreasing test method of Example 1 with the following results:
: ' ~ .
1st attack on greased slide at 3 sec.
60% removal of grease at 15 sec.
100% removal of grease at 25 sec.
,' :
: ! At a 1:20 dilution with water, a clear solution was .. ,: .
formed which was totally ineffecti~e in removing black Magic Marker markings from an alkyd enameled metal surface. The solution was subjected to the degreasing test ; method of E~ample 1 with the following results:
~ ~ 1st attack on greased slide at 15 sec.
;~ ~ 10-15% removal of grease at 1.0 min.
~; 30 25% removal af grease at 2.0 min.
SUBSTITU~E SRFET
:
.. ~......................... . .
.. . . . ..
. . .
.
WOgl~O9104 PCT/US90/07215 ~,~19~- 40 45% removal of grease at 30 min.
60~ removal of grease at 4.0 min.
70% removal of grease at S.0 min.
75-80% removal of grease at 6.0 min.
85% removal of grease at 7.0 min.
90-95~ removal of grease at 9.0 min.
100% removal of grease at 10.0 min.
The marked change in degreasing erficac~ (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 21 j Example 19 was repeated in preparing an emulsion having the following composition:
Com~Qnent Wt.
l-Phenoxy-2-propanol 20.0 (Dowanol PPh) I Octylphenol ethoxylate (5E.O.) 3.0 ~Triton X-45) ` 20 Triethanolamine 0.5 Soft H20 containing 0.06% 176.5 polyacrylic acid crosslinked with polyalkenyl polyether (Carbopol 940 thickener) 200.0 - 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%.
.
., .
~UBSTITi3T~ SHEET
41 ' ' , ~t a 1:5 dilution with water, an emulsion resulted which was sub~ected to the degreasing test method of Example l with the following results:
' 1st attack on greased slide at 5 sec.
35-40% removal of grease at 10 sec.
80~ removal o graas2 at 20 sec.
lO0~ ~2moval of grease at 25 sec.
.t ~ l:10 ~lluti~n with water, an emulsion resulted which was subjected to t'ne degreasing test method of E~ample 1 with the following results:
~. , 1st attack on greased slide at lO sec.
` 40% removal of grease at 20 sec.
75% removal of grease at 30 sec.
lO0~ removal of grease at 45 sec.
At a 1:20 dilution with water, a hazy emulsion-solution resulted which was subjected to the degreasing test method of E~ample 1 with the following results-~`~' ' 1st attack on greased slide at 20 sec.
106 removal of grease at l min.
20-25% removal of grease at 2 min.
i 40% removal of grease at 3 min.
~ 65% removal of grease at 4.25 min.
, 85-90% removal of grease at 6 min.
~ 100% removal of grease at 7.5 min.
~ ~ , ~ .
. ~
-:: :
.
:~ S'JB~TITUTE S'~EEI
,~
. . ~ ; . . .
. . .
. ~ ~,; . .
, ~ .
;:
~9 Exam~le 22 E2ample 19 was repeated in preparing an emulsion having the following composition:
ComPonent Wt.%
5 1-Pheno~y-2-propanol 30.0 (Dowanol PPh) Dodecylbenzenesulfonic acid 0.6 Acrylic acld/alkyl 2.2 methacrylate copolymer, 30% aqueous (Acrysol ICS-l) Triethanolamine 1.4 ., .
Soft H20 165.8 200.0 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~.
At a 1:5 dilution with water, an emulsion resulted which very easily removed black Magic Marker markings from an alkyd enameled metal surface. The emulsion was subjected to the degreasing test method of E~ample 1 with the following results:
' ' ` 1st attack on greased slide at 1 sec.
(almost instantaneous) 100% removal of grease at 7 sec.
At a dilution of 1:10 with water, a very slight , 30 emulsion or almost hazy solution resulted which was only i moderately effective in removing black Magic Marker .
~ , . .
~æSl'l~U~E S~EEI
- -.
~: :
WO91/09104 , PCT/US90/~7215 2~7067~ ~
markings from an alkyd enameled metal surface. The emulsion or solution was subjected to the degreasing test method of'E~ample 1 with the following results:
1st attack on greased slide at 1+ sec.
100'~ relnoral os grease at 12 sec.
~, At a dilu~ion OL 1:20 -~ith water, a clear solution was formed which was wholly ineffective in removing black Magic ~arl{er mark~ngs ~-rom an alkyd enameled metal surface. The solution was subjected to the degreasing test method of ~ 10 E.sample 1 ~7ith the following results:
'~ 1st attack on greased slide at 5 sec.
40% remo,val of grease at 15 sec.
75% removal of grease at 30 sec.
100% removal of grease at 45 sec.
.- . . . .
' 15 , Example 23 ;!
E~ample 19 was repeated in preparing an emulsion having ths following composition:
Component Wt.%
l-Phenoxy-~-propanol 20.0 (Dowanol PPh) Octylphenol etho~ylate - - 4.0 (7-8 E.O.) tTriton X-114) Triethanolamine' ~ 1.0 Soft H20 172.0 25 Acrylic acid/alkyl 3.0 methacrylate copolymer, 30% aqueous (Acrysol ~ ICS-l) '~ 200.0 ,; .
~ .
SUBSTITUTE SHEET
.. . ... '. i ,. . ~ -- , . .
~ ~ , ~ `.. . .
. ..
. . . .
.~ . . . .
. , .
, . . .
` ~. . ..
All of the components except the Acrysol ICS-l thickening agent were pre-emulsified with a high-speed, motor driven, 3-bladed propeller for 3 minutes, and the Acrysol ICS-1 was then added very slowly with vigorous stirring to provide immediate thickening. The resulting composition was an intensely bluish/white emulsion in the form of a thick lotion or semipaste having a pH of 7.88, a Brookfield viscosity (~V-~4 spindle, 12 rpm) of 8600 centipoise, a total solids content (theory) of 2.8%, and a ; 10 total actives content (theory) of 12.8%.
At a I:5 dilution with water, a bluish/white microemulsion formed which very easily and fully removed the following markings from alkyd enameled metal surfaces:
black ~agic Marker felt pen, blue and black indelible ballpoint pen, #1 hardness pencil and red (waxy) crayon.
`~ The microemulsion was subjected to the degreasing test method of Example 1 with the following results:
;~ 1st attack on greased slide at 1 sec.
60~ removal of grease at 10 sec.
~ 20 100% removal of grease at 20 sec.
`::
ExampIe 24 Example 23 was repeated in preparing an emulsion having the following composition:
wt.%
; 25 1-Pheno~y-2-propanol 20.0 tDowanol PPh) Cg-Cll alkanol/2.5 E.O. 4.0 condensate (Neodol 91-2.5) Triethanolamine 1.0 .
SUBSTITUTE SH~ET
, .~. ... .
-. - .
. . .
.. . .
WO91/09104 P~T/US90/07215 ` 2~7D~79 Soft H20 172.0 :
Acrylic acid/alkyl 3.0 - methacrylate copolymer, 30% aqueous (Acrysol ICS-l) 200 . 0 The rosulting composition was an intensely ~luish-T~7hit~ omulsion ha~ing a pH of 8.27, a Brookfield iscosi!cv ~LV-~3 spindle, 12 rpm) of 3650 centipoise, a ~: 10 total solids ~ontant (thaory) of 2.8~, and a total actives content ~theory) of 12 . 8%.
~ a ':5 dilutlon wl~h .water, a bluish/white - microemul~ion Eormed which very quickly, easily and totally . removed the following markings from alkyd enameled metal ~ 15 surfaces: black Magic Marker felt pen, blue and black ; indelible ballpoint pen, #l hardness pencil, red (waxy) crayon, and automotive grease smearings.
~`` The microemulsion was subjected to the degreasing test method of Example 1 with the following results: ~
,' , 1st attack on greased slide at less than 1 sec.
. 10~0o rcmGYal Of gLaase at 15 sec.
.
Example 25 ; An aquesus cleaner/desreaser emulsion in the form of `~ an aerosol formulation was prepared having the following composition:
~` Component Wt.%
Phenoxy-2-propanol 3.0 . (Dowanol PPh) : Octylphenol etho~ylate 0.2 (Triton X-45) ~ , , ~U8SlIIU~E SH~EI
"~ . . ~ - .
. ~ .
,.. , , ~ ~. .
~ , . . .
.
., ` , ~.. .
~ . . ..
WO91/09l04 PCT/US90/072~5 ,:
.
~ 46 Deionized H20 95.2 Acrylic acid/alkyl 1.2 methacrylate copolymer, 30% aqueous (Acrysol ICS-l) Ammonium hydroxide (23%) 0.2 Sodium Nitrite 0.2 .
~' 100 . O
The fiLsL ~our compon2nts listed above were pre-emulsified undsr hi~h speed stirring for three minutes with a ~7ater d iven 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%, a~d 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 sropellant (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.
It was found that the resulting aerosol formulation very easily, quickly and totally removed the following markings from alkyd enameled metal surfaces (spray on/wipe off): black, indelible Magic Marker felt pen, blue and black indelible ballpoint pen, #1 hardness pencil, red (waxy) crayon and automotive grease smearings. The aerosol formulation also readily removed fingerprints, smudges, and similar markings from walls and woodwork.
.
` S~TITUTE SUEET
~:
..
WO9l/09104 PCT/US9~/0721 :
47 ~ ~ 7 ~ 6 ~ 9 E~ample 26 An aqueous cleaner/degreaser emulsion was prepared ; having the following com~osition:
. Component 1~1t.%
5 Phosphate ester coupler/ 0.30 emulsifier (MonaI3~ 1293~
`Isostearamide diethanolamide 0.40 :. (l:l) (~onamid 150-IS~
Monoethanolamine 0.40 lO Deionized H20 192.9 2-Ethylhe~o~yQthanol 2.0 ~:~ (Ektasolv E~H~Eastman) , l-Pheno~y-2-propanol - 4.0 (Dowanol PPh) 200.0 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 b:luish/white emulsion having a pH of 10.20, a Brookfield viscos:ity (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 ::~ e~cellent stability characteristics.
l'he emulsion possessed excellent, rapid, and efficient cleaning/degreasing action against the following soilants:
;~ : black Magic Marker markings, ballpoint pen markings, #l : hardness pencil markings, red (wa~y) crayon markings, . automotive greases, Vaseline, lard, shortening, and : 30 lipophilic oils.
.
.
~ SUBSTITUT~ Sl!~ET
., . ~
.; . .. . . .
,.,; . ,. . , . , .. .-.. . , . ~ ~, , . ,. . . , . . ;.. ~ . ~ . . . ... . .. ... .
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, . . . `
. . . . .~ ~. , ;.
, . , ` .
.. .. , ~ .~ . . ~ . . . ...
. . , -WO9t/09104 PCT/US90/07215 .~9 7~9 ~8 Example 27 Example 26 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
ComPoner.~ Wt.%
5 Diethanolamino lauryl sulrata 0.20 (S-te~arol DEA, 35%) Isostearamide diethanolamide0.40 xlonamid 150-1-S) : Monoethanolamine 0.60 So~t ~2 192.3 l-Phenoxy-2-~ropanol 5.0 : (Dowanol ~Ph) . Acrylic acid/alkyl methacrylate1.5 copolymer, 30% aqueous : 15 ~Acrysol ICS-l) ; 200.0 The resulting composition was a bluish emulsion (iridescent cast) having a pH of 10.21, a Brookfield viscosity (L~-~2 spindle, 60 rpm) of 72 centipoise, a total ; 20 solids content (theory) of 0.46% and a total actives content ttheory) of 3.26%. The emulsion exhibited eæcellent stability characteristics.
The emulsion possessed excellent, rapid, and efficient cleaning/degreasing action against all the soilants listed in Example 26.
.
.
'^ .
~IBS~IIU~E SHEEI
: ~. . . . .
.: - ,. , . .
... . .
, .
WO91/09104 PC~/US~0/07215 :
2 ~ 7 9 ExamPle 28.
Example 26 was repeated in preparing an aqueous :. cleaner/degreaser emulsion having the Eollowing composition:
:
Com~onent ~7t.%
~: . 5 Isostearamide diethanolamide 0.5 onamid 150-IS) Sodium dodecyldiphenyletner O.l disul:Eonate-coupler ~Dowfa~ 2Al, 45%) . lO Monoethanolamine O.S
:; Soft H20 190.3 2-Pheno~yethanol 7.0 - (Dowanol EPh) Acrylic acid/alkyl methacrylate l.5 copolymer, 30% aqueous (Acrysol ICS-l) ,~ .
200.0 ~ The resulting composition was a light, slightly :~. bluish/white emulsion having a p~ of lO:08, a ~rookfield ~ 20 viscosity ~LV-#2 spindle, 60 rpm) of 57 centipoise, a total :~ st~lids content (theory) of 0.50% and a total actives content (theory~ of 4.30~. The emulsion e~hibited e~cellent stability characteristics.
The emulsion possessed excellent, rapid, and complete cleaning/degreasing action against all the soila~ts listed in E~ample 26.
E~ample 29 ..
Example 26 was repeated in preparing an aqueous cleaner/degreaser emulsion having the following composition:
:`.' .:
.
. ~
~ SIIIUI~ SHEEI
., .
~`, - .. ~ . . . ;.
., ~ .-. , " :
. .. .
~ .. ` ~. . ; . .
, -,. . ~ , , .
.
~; , ` ` ~ . .
~ 50 Com~onent Wt.%
Isostearamide diethanolamide 0.3 (1:1) (Monamid 150-IS) Mi~ed caprylamide DEA/ 0.2 capramide DEA coupler (Clintwood CP-Z-61-2) Monoethanolamlne 0.3 ~;
; Soft ~2 19~.2 l-Pheno.. ~y-.-p-o~anol . 5.0 ~Dowanol PPhj ~:~ 200.0 The resulting sompos~tion was an intensely .
.~, bluish/white emulsion having a pH of 10.43, a Brookfield : viscosity (L~-#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 e~hibited : . e~cellent stability characteristics.
The emulsion possessed excellent, rapid, and complete cleaning/degreasing action against all the soilants listed in E~ample 26.
, E3ample 30 .
An aqueous cleaner/degreaser emulsion was prepared ~ havlng the following composition:
`~ Component Wt.%
- 25 Isostearamide diethanolamide 0.30 (1:1) (Monamid 150-IS) :~ ~ Soft H20 194.2 : Butoxyethyl acetate 3.0 (EB acetate) ~-,'' ~ ~ . .
.
,'~ .
. .~ -`~ S~'IPl~ITU~E SI~E~
..; ..
~. . .
... . . .. .
~ , ..... ~, . - ..... . . . .
,. .
.
.- ,~. ` . .
. . . . . . .
. . . .
WO91/09104 PCT/US90/~7215 Sl 2i~ 7~
Acrylic acid/alkyl methacrylate 1.0 copolymer, 30% aqueous (Acrysol ICS-l) Aqueous ammonium hydro~ide 0.0 (28% NH3) 100.0 The first two components were stir.ed at room temperature for 15 minutes to complately di~perse 'che ; isostearamide diethanolamide in water. The buto~yetnyl acetate was then added with vigorous stirring at room temperature for 30 minutes. The Acrysol ICS-l was ne~t ` added with stirring followed by dro2wise addition of ~he ; ammonium hydro~ide with ~igorous stirri~.g at room temperature for 15 minutes.
The resulting composition was a slightly ~luish/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 e~hibited excellent stability characteristics.
The emulsion possessed e~cellent, rapid, and complete cleaning/degreasing action against all the soilants listed in Example 26.
Egample 31 A hand cleaner emulsion was prepared having the following composition:
ComPOnent Wt.~
Polypropylene glycol monobutyl 10.0 ether (Dow PolyglycoI
L-1150) ~'' .
: , ~
` S~BSTl~UT~ SHEET
i . . ..
,.~. .
., , " . . .
Mineral oil (Penreco, 30.0 Drakeol 5 L~O) Octylphenol/7-8 E.O. 10.0 ~Triton ~
5 Isostearamide diethanolamide 6.0 ( 1 : 1 ) Soft H20 1~1.0 Acrylic acid/alXyl methacrylata 3.0 copolymer, 30?~ acu~ous (Acrysol IC~
100 . O
- The firs'~ e ,o:;n~onsn~ sre emul~ d and tne Acrysol ICS-l was c~en added ~ith ~tigorous stirring. The resulting composition was an intensely bluish/white emulsion which had a creamy, smoo~h 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. When reformulated to contain no Polyglycol L-1150, the cleaning/degreasing action was ~; drastically reduced.
E~ample 32 An aqueous cleaner/degreaser emulsion in the form of an aerosol formulation was prepared having the following composition:
, ! ~ Component ~t %
Liquid lauramide 0.30 diethanolamide (1:1 Superamide) ~ 30 (Mackamide LLM) :,.
~; Monethanolamine 0.60 .~.
.:
.
~BSTITUTE SI~EET
. ~
WO91/09104 PCT/US90/~7215 2070~79 `
Sodium nitrite 0.30 Perfluoroalkylphosphate 0.40 ester antifoaming agent (Atsurf F-12, 15%) Deionized H20 191.80 l-Phenoxy-2-propanol 5.00 (Dowanol PPh) Acrylic acid/alkyl 1.~0 methacrylate copolymer, 30% aqueous (Acrysol ICS-1) ~' 200.00 The first fiYe components lis~ed aDov2 wer2 s~i red at high speed for 15 minutes to fully disperse the lauramide diethanolamide and to form a microemulsion. The 1-pheno~y-2-propanol was then added with vigorous stirring for 30 minutes at room temperature after which the Acrysol ICS-l was added dropwise with good stirring. The resulting composition was a bluishiwhite emulsion with a pH of 9.86, a Brookfield viscosity (LV-#2 spindle, ~0 rpm) of 28 centipoise, a total solids content (theory) of 0.57~, and a total actives content (theory) of 3.37~. Ths emulsion ,:
exhibited excellent stability.
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-br~aking foam-with ~` e~cellent vertical cling. The formulation exhibited excellent cleaner/degreaser action against the markings listed in Example 25 and had good/excellent wet-out properties.
., .
.' `
::, `~:
., SUBSTlTUTr SHEET
... ~. ... . . -.~ ~ , , .
.
.
WO~I/09104 PCT/US90/07215 Ex2mple 33 An aqueous cleaner/degreaser emulsion was prepared having the rollowing composition: -Component r~7t.~
5 Isostearamida diet'nanolamide8.0 ; (l:l)(Monamid 150-IS) Monethanolamine 0.95 Tap Water ~pH 9.55, '55p~170.05 hardness) 10 1-Phenoxy-2-propanol 20.0 (Dowanol P h) Perfluoroalkylphosphate~ 1.0 ester antifoaming agant ; (Atsurf F-12, 15%) 200.00 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 microamulsion with stirring continued for one hour at room temperature after which the antifoaming agent was added with stirring. The rasulting composition was a very intense bluish whita emulsion having a pH of 10.53, a ~rookfield viscosity ~LV-~2 spindlP, S0 'pm) of 7.5 centipoise, a total solids content (theory)-of 9.08%, and a total actives content (theory) ~of 14.55%. The emulsion e~hibited excellen~ stability.
At a 1:5 dilution with water, a bluish to bluish/white microemulsion formed which very ~asily, quickly, and completely removed all of the markings set forth in Examples 2-4 from alkyd enameled metal surfaces.
, . .
S~IB~,TITU~ SH~LET
.,.
., j , .
WO91/~9104 PCT/US90/07215 2070~79 The microemulsion was subjected to the degreasing test method of E~ample 1 with the following results:
1st attack on greased slide at l sec.
45% removal of grease at 10 sec.
75% removal of grease at 15 sec.
100% removal of grease at 20 sec.
- .
This emulsion composition is especially suitable rsr use in mechanized high pressure/spray equipment T,qhere Soam ~' generation cannot be tolerated.
~: , E~amPle 34 An aqueous cleaner/degreaser emulsion was prepared ~-~, having the following composition:
~ Component Wt.
.,.j .
Phosphate ester coupler/ 0.10 emulsifier (Monafa~ 1293) ., .
Isostearamide diethanolamide 0.40 (l:l)(Monamid 150-IS) Monethanolamine 0.60 :.~
Soft H20 192.40 20 1-Pheno~y-2-propanol 5.00 ~` (Dowano1 PPh) Acrylic acid/alkyl 1.50 ;~ Methacrylate copolymer 30% aqueous (Acrysol ICS-l) 200.00 ~ .
The first four components listed above were stirred at room temperature until fully dispersed (ca 15 minutes).
The l-phenoxy-2-propanol was added with vigorous stirring ' .~ .
~ , ~ .
~U~STI~UTE SHEET
,: . - . , .
. .
. .
~ , . . . ..
.~ , . .
: . .
.
WO91/091~4 PCr/US90/07215 6q9 56 for 0.5 hour at room temperature and ths Acrysol ICS-1 was added dropwise with vigorous stirring to viscosify 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 csnkipo1se, a total solids content (theory~ OL 0 . ~a~, and a cocal accives content (theory) of 3.28~. The emlilsion e~r.hi-3ited excellent stability.
The emulsion e~hi`oited exceïl2nt cleaneridegreaser action agai.nst all OL the ma, lSings a't Eor'c'1 tn Examples 2-4 and against Vaseline, iard, short~ning and iipophilic oils.
; This emulsion is suitabls rfor US~ as a r~ady-to-l~2 formulation applied by pump spray or trigger spray action.
Exam~le 35 An aqueous cleaner/degreaser emulsion was prepared having the following composition:
` ComPonent Wt.
Polyglycol copolymer ~ 3.0 containing ethylene oxide and propylene oxide (Dow Polyglycol 112-2) Octylphenol ethoxylate 0.3 (5 E.O.)~Triton X-45) Soft H20 96.7 100.00 The water was added very slowly to the stirred mixture of the other two components llsted 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.
~ .
S'~B~TlTll~ SH~ET
.
..
.. . .
57 2~067g 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.
Example 36 An aqueous cleaner/degreaser emulsion was prepared having the following composition:
Gom~onent Wt.
Polypropylene glycol 6.0 (Dow P-2000) Soft H20 190.8 . Octylphenol ethoxylate (5 E.O.)0.6 (Triton X-45) Triethanolamine 0.6 : .
;~ 20 Acrylic acid/alkyl 2.0 ~, Methacrylate copolymer 30% aqueous (Acrysol ICS-l) :~ .
200.00 The first four components listed above were pre-emulsified with high speed stirring and the Acrysol ICS-l was added dropwise under vigorous high speed/hiah shear stirring conditions. The resulting composition was a white, creamy :; :
~: .
~ .
'leSll~U~E SHEET
- : -~ ` 58 emuls~ion having a pH of 7.81, a Brookfield viscosi~y (LV-~3 spindle, 12 rpm) of 870 centipoise and a to~al solids/total actives content (theory) of 3.9%.
This emulsion readily removed tar, grease, asphalt, black (rubber) heel and red (wa7y) crayon mar~s from vinyl tile coated with polymeric floor finish usin~ a w2ttea paper towel or cloth. The tile ouf rS to 3 cl~ar, colorless, high shine on ai r dryiny Wi tn no damaging solvent action occurring on the floor finis'n.
I0 In view of the above, it will be s22n t.1a~ ~'n._ several objects of the invention are achieved and othsr advantageous results attained.
As various changes could b2 mad2 in t'n_ abov2 :
~` compositions without departing from the scope of the ;~ 15 invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not ln a limiting sense.
~ `
:~
:: ' `'~'i .,~
:-:: , , .
.
: .
- SU~SIITUTE SHET
~. . .
-.
Claims (33)
1. A stable, aqueous cleaner/degreaser emulsion composition comprising:
(a) at least one sparingly soluble organic solvent characterized by:
(i) having a water solubility in the range of approximately 0.05 to approximately 5 weight percent;
(ii) not being a hydrocarbon or halocarbon;
(iii) having one or more similar or dissimilar oxygen, nitrogen, sulfur, or phosphorous containing functional groups;
(iv) being a solvent for hydrophobic soilants; and (v) being present in an amount exceeding its aqueous solubility;
(b) 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; and (c) water.
(a) at least one sparingly soluble organic solvent characterized by:
(i) having a water solubility in the range of approximately 0.05 to approximately 5 weight percent;
(ii) not being a hydrocarbon or halocarbon;
(iii) having one or more similar or dissimilar oxygen, nitrogen, sulfur, or phosphorous containing functional groups;
(iv) being a solvent for hydrophobic soilants; and (v) being present in an amount exceeding its aqueous solubility;
(b) 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; and (c) water.
2. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 further comprising a viscosifying thickener.
3. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said organic solvent has a water solubility in the range of approximately 0.05 to approximately 2.5 weight percent.
4. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said organic solvent is selected from the group consisting of esters, alcohols, ketones, aldehydes, ethers, and nitriles.
5. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said solvent is selected from the group consisting of 2-phenoxyethanol, 1-phenoxy-2-propanol, dipropylene glycol monobutyl ether, polypropylene glycols, .beta.-phenylethanol, acetophenone, benzyl alcohol, butoxyethyl acetate, isophorone and the dimethyl esters of mixed succinic, glutaric, and adipic acids.
6. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said surfactant is selected from the group consisting of nonionic, anionic, cationic, and amphoteric surfactants.
7. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 6 wherein said surfactant is a nonionic surfactant.
8. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 7 wherein said nonionic surfactant is selected from the group consisting of alkoxy poly(ethenoxy)alkanols, alkylphenoxypoly(ethenoxy) alkanols and fatty acid alkanolamide surfactants.
9. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 7 wherein said nonionic surfactant is selected from the group consisting of octylphenoxypoly(ethyleneoxy)(4)ethanol, nonylphenoxy-poly(ethyleneoxy)(5)ethanol, dodecylphenoxypoly(ethyl-eneoxy)(8)ethanol, polyoxyethylene (7) lauryl alcohol, polyoxyethylene (4) tridecyl alcohol, lauryloxy-polytethyleneoxy)(8)ethyl methyl ether, undecylthiopoly-(ethyleneoxy)(6)ethanol, methoxypoly(oxyethylene(10)/(oxy-propylene(20))-2-propanol block copolymer, nonyloxy-poly(propyleneoxy)(4)/(ethyleneoxy)(10)ethanol, dodecyl polyglycoside, polyoxyethylene (9) monolaurate, poly-oxyethylene (8) monoundecanoate, polyoxyethylene (20) sorbitan monostrearate, polyoxyethylene (18) sorbitol monotallate, sucrose monolaurate, lauramidopro-pyl-N,N-dimethylamine oxide, 1:1 lauric diethanolamide, 1:1 coconut diethanolamide, 1:1 mixed fatty acid diethanolamide, polyoxyethylene(6)lauramide, 1:1 soya diethanolamidopoly(ethyleneoxy)(8)ethanol, 1:1 soyamide diethanolamide, 1:1 linoleamide diethanolamide, 1:1 oleamide diethanolamide, 1:1 ricinoleamide diethanolamide, 1:1 isostearamide diethanolamide, 2:1 oleamide diethanolamide, 2:1 soyamide diethanolamide, and 1:1 tall oil diethanolamide.
10. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said surfactant is an anionic surfactant selected from the group consisting of dodecylbenzene sulfonic acid, monoethanolamine dodecylbenzene sulfonate, sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate, morpholinium dodecylbenzene sulfonate, ammonium dodecylbenzene sulfonate, isopro-pylamine dodecylbenzene sulfonate, sodium tridecylbenzene sulfonate, sodium dinonylbenzene sulfonate, potassium didodecylbenzene sulfonate, dodecyl diphenyloxide disulfonic acid, sodium dodecyl diphenyloxide disulfonate, isopropylamine decyl diphenyloxide disulfonate, sodium hexadecyloxpoly(ethyleneoxy)(10)ethyl sulfonate, potassium octylphenoxypoly(ethyleneoxy)(9)ethyl sulfonate, sodium alpha C12-14 olefin sulfonate, sodium hexadecane-1 sulfonate, sodium ethyl oleate sulfonate, potassium octadecenylsuccinate, sodium oleate, potassium laurate, triethanolamine myristate, morpholinium tallate, potassium tallate, sodium lauryl sulfate, diethanolamine lauryl sulfate, sodium laureth (3) sulfate, ammonium laureth (2) sulfate, sodium nonylphenoxypoly(ethyleneoxy)(4) sulfate, sodium decyloxypoly(ethyleneoxy(5)methyl)carboxylate, sodium octylphenoxypoly(ethyleneoxy(8)methyl)carboxylate, sodium mono decyloxypoly(ethyleneoxy)(4)phosphate, sodium didecyloxypoly(ethyleneoxy)(6)phosphate, and potassium mono/di octylphenoxypoly(ethyleneoxy)(9)phosphate.
11. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said surfactant is a cationic surfactant selected from the group consisting of a mixture of n-alkyl dimethyl ethylbenzyl ammonium chlorides, hexadecyltrimethylammonium methosulfate, didecyldimethylammonium bromide and a mixture of n-alkyl dimethyl benzyl ammonium chlorides.
12. A stable, aqueous cleaner/degreaser emulsion composition as set forth in.claim 1 wherein said surfactant is an amphoteric surfactant selected from the group consisting of cocamidopropyl betaine, sodium palmitylo-amphopropionate, N-coco beta-aminopropionic acid, disodium N-lauryliminodipropionate, sodium coco imidazoline amphoglycinate and coco betaine.
13. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said coupler is selected from the group consisting of 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, sodium capryloamphopropionate, disodium capryloiminodipropionate, sodium isodecyloxypropyliminodipropionate, and sodium capro imidazoline amphoglycinate, and mixed caprylamide DEA/capramide DEA.
14. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 2 wherein said viscosifying thickener is selected from the group consisting of acrylic acid/alkyl methacrylate copolymers, carboxy acrylic polymers, polyacrylic acid crosslinked with polyalkenyl polyethers, polyacrylamide, poly(methylvinyl ether/Maleic) anhydride, guar gums, xanthan gums, bentonite clays, organically modified magnesium aluminum silicates, fumed silica, sodium alginate, polyethylene glycols, polyethylene oxide, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose.
15. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said emulsion additionally comprises one or more optional adjuvants selected from the group consisting of chalants, defoamers, foam control agents, preservatives, fragrances, dyes, lubricants, emollients, pH adjustants, dispersants, abrasives, anti-corrosion additives, and anti-rust additives.
16. A stable, aqueous cleaner/degreaser emulsion compbsition as set forth in claim 1 wherein said organic solvent is 1-phenoxy-2-propanol.
17. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said organic solvent is 2-phenoxyethanol.
18. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said organic solvent is a polypropylene glycol.
19. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said organic solvent is dipropylene glycol monobutyl ether.
20. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said surfactant is 1:1 isostearamide diethanolamide.
21. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said surfactant is 1:1 ricinoleamide diethanolamide.
22. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said surfactant is 1:1 soyamide diethanolamide.
23. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said surfactant is 1:1 linoleamide diethanolamide.
24. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said surfactant is 1:1 oleamide diethanolamide.
25. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said surfactant is dodecylbenzene sulfonic acid.
26. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said surfactant is nonylphenoxypoly(ethyleneoxy)(8.5) ethanol.
27. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 1 wherein said coupler is sodium isodecyloxypropyliminodipropionate.
28. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 2 wherein said viscosifying thickener is an acrylic acid/alkyl methacrylate copolymer.
29. A stable, aqueous cleaner/degreaser emulsion composition as set forth in claim 2 wherein said viscosifying thickener is a neutralized acrylic acid/alkyl methacrylate copolymer.
30. A stable, aqueous cleaner/degreaser emulsion composition comprising:
(a) 1-phenoxy-2-propanol in an amount exceeding its aqueous solubility;
(b) 1:1 isostearamide diethanolamide in an amount insufficient to solubilize all of said 1-phenoxy-2-propanol but sufficient to emulsify the unsolubilized portion of said 1-phenoxy-2-propanol; and (c) water.
(a) 1-phenoxy-2-propanol in an amount exceeding its aqueous solubility;
(b) 1:1 isostearamide diethanolamide in an amount insufficient to solubilize all of said 1-phenoxy-2-propanol but sufficient to emulsify the unsolubilized portion of said 1-phenoxy-2-propanol; and (c) water.
31. A stable, aqueous cleaner/degreaser emulsion composition comprising:
(a) 2-phenoxyethanol in an amount exceeding its aqueous solubility;
(b) 1:1 isostearamide diethanolamide in an amount insufficient to solubilize all of said 2-phenoxyethanol but sufficient to amulsify the unsolubilized portion of said 2-phenoxyethanol; and (c) water.
(a) 2-phenoxyethanol in an amount exceeding its aqueous solubility;
(b) 1:1 isostearamide diethanolamide in an amount insufficient to solubilize all of said 2-phenoxyethanol but sufficient to amulsify the unsolubilized portion of said 2-phenoxyethanol; and (c) water.
32. A stable, aqueous cleaner/degreaser emulsion composition comprising:
(a) a polypropylene glycol having a water solubility in the range of approximately 0.05 to approximately 6 weight percent and being present in an amount exceeding its aqueous solubility;
(b) a fatty acid alkanolamide in an amount insufficient to solubilize all of said polypropylene glycol but sufficient to emulsify the unsolubilized portion of said polypropylene glycol; and (c) water.
(a) a polypropylene glycol having a water solubility in the range of approximately 0.05 to approximately 6 weight percent and being present in an amount exceeding its aqueous solubility;
(b) a fatty acid alkanolamide in an amount insufficient to solubilize all of said polypropylene glycol but sufficient to emulsify the unsolubilized portion of said polypropylene glycol; and (c) water.
33. A stable, aqueous cleaner/degreaser aerosol emulsion composition comprising:
(a) 1-phenoxy-2-propanol in an amount exceeding its aqueous solubility;
(b) 1:1 lauramide diethanolamide in an amount insufficient to solubilize all of said 1-phenoxy-2-propanol but sufficient to emulsify the unsolubilized portion of said 1-phenoxy-2-propanol;
(c) a viscosifying thickener; and (d) water.
(a) 1-phenoxy-2-propanol in an amount exceeding its aqueous solubility;
(b) 1:1 lauramide diethanolamide in an amount insufficient to solubilize all of said 1-phenoxy-2-propanol but sufficient to emulsify the unsolubilized portion of said 1-phenoxy-2-propanol;
(c) a viscosifying thickener; and (d) water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US45262389A | 1989-12-19 | 1989-12-19 | |
| US452,623 | 1989-12-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2070679A1 true CA2070679A1 (en) | 1991-06-20 |
Family
ID=23797225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2070679 Abandoned CA2070679A1 (en) | 1989-12-19 | 1990-12-07 | Aqueous cleaner/degreaser emulsion compositions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0506744A4 (en) |
| JP (1) | JPH05504584A (en) |
| AU (1) | AU6910191A (en) |
| CA (1) | CA2070679A1 (en) |
| WO (1) | WO1991009104A1 (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5342549A (en) * | 1990-01-29 | 1994-08-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbyl-amidoalkylenebetaine |
| JP3452406B2 (en) * | 1993-10-07 | 2003-09-29 | 有限会社ケントス | Composition having performance of removing organic deposits |
| AU8132894A (en) * | 1993-11-12 | 1995-05-29 | Procter & Gamble Company, The | Liquid hard surface detergent compositions containing amphoteric detergent surfactant and perfume |
| 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 |
| US5762648A (en) * | 1997-01-17 | 1998-06-09 | The Procter & Gamble Company | Fabric treatment in venting bag |
| US5849039A (en) * | 1997-01-17 | 1998-12-15 | The Procter & Gamble Company | Spot removal process |
| 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 (en) * | 1999-02-26 | 2000-10-05 | Wack O K Chemie Gmbh | Process and cleaning liquid for liquid cleaning objects |
| 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 |
| WO2014144091A1 (en) | 2013-03-15 | 2014-09-18 | Klear Solutions | Multi-purpose, hard surface cleaner |
| WO2019108990A1 (en) * | 2017-12-01 | 2019-06-06 | Ecolab Usa Inc. | Cleaning compositions and methods for removing baked on grease from fryers and other hot surfaces |
| CN115710538B (en) * | 2022-11-11 | 2024-01-19 | 国网上海市电力公司 | Self-emulsifying cleaning material and preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4040977A (en) * | 1973-10-16 | 1977-08-09 | Sterling Drug Inc. | Preservative and disinfectant |
| EP0106266B1 (en) * | 1980-05-27 | 1988-02-24 | The Procter & Gamble Company | Terpene-solvent mixture useful for making liquid detergent compositions |
| EP0058637A1 (en) * | 1981-02-12 | 1982-08-25 | Ciba-Geigy Ag | Stable preparation of a treatment product for a textile substrate |
| US4769172A (en) * | 1986-09-22 | 1988-09-06 | The Proctor & Gamble Company | Built detergent compositions containing polyalkyleneglycoliminodiacetic acid |
| DE3717600A1 (en) * | 1987-05-25 | 1988-12-08 | Henkel Kgaa | Aqueous hand cleaning composition |
| AU605858B2 (en) * | 1987-06-04 | 1991-01-24 | Minnesota Mining And Manufacturing Company | Aqueous-based composition for removing coatings |
| US4832802A (en) * | 1988-06-10 | 1989-05-23 | Mcgean-Rohco, Inc. | Acid zinc-nickel plating baths and methods for electrodepositing bright and ductile zinc-nickel alloys and additive composition therefor |
-
1990
- 1990-12-07 EP EP19910901175 patent/EP0506744A4/en not_active Withdrawn
- 1990-12-07 AU AU69101/91A patent/AU6910191A/en not_active Abandoned
- 1990-12-07 WO PCT/US1990/007215 patent/WO1991009104A1/en not_active Application Discontinuation
- 1990-12-07 CA CA 2070679 patent/CA2070679A1/en not_active Abandoned
- 1990-12-07 JP JP50161890A patent/JPH05504584A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO1991009104A1 (en) | 1991-06-27 |
| EP0506744A4 (en) | 1993-09-22 |
| JPH05504584A (en) | 1993-07-15 |
| AU6910191A (en) | 1991-07-18 |
| EP0506744A1 (en) | 1992-10-07 |
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