CA2057027C

CA2057027C - Improved builder-containing aqueous cleaner/degreaser microemulsion compositions

Info

Publication number: CA2057027C
Application number: CA002057027A
Authority: CA
Inventors: Donald N. Vaneenam
Original assignee: Buckeye International Inc
Current assignee: Buckeye International Inc
Priority date: 1989-06-29
Filing date: 1990-06-12
Publication date: 1999-04-06
Anticipated expiration: 2010-06-12
Also published as: WO1991000337A1; EP0479888B1; JPH05500675A; DE69029472T2; CA2057027A1; DK0479888T3; DE69029472D1; JP2671234B2; EP0479888A4; ES2100884T3; AU6031790A; ATE146521T1; EP0479888A1

Abstract

Stable, aqueous cleaner/degreaser compositions formulated in the form of true mi croemulsions and containing a builder component comprise: (a) at least one sparingly water soluble organic solvent cha racterized by: (i) having a water solubility in the range of approximately 0.2 to approximately 6 weight percent; (ii) not being a h ydrocarbon or halocarbon; (iii) having one or more similar or dissimilar oxygen, nitrogen, sulfur or phosphorus containing fun ctional groups; (iv) being a solvent for hydrophobic soilants; and (v) being present in an amount exceeding its aqueous solubility; ( b) a builder; (c) a solubilizing additive consisting of from approximately 0.1 to approximately 100 weight percent of a su rfactant and from 0 to approximately 99.9 weight percent of a coupler, the solubilizing additive being present in an amount not s ubstantially exceeding the amount required to transform the combination of the organic solvent and said builder from the form of a true macroemulsion to the form of a microemulsion and less than that required to form a true solution; and (d) water . Such compositions exhibit improved cleaning/degreasing efficacy over compositions containing no builder component.

Description

W O 91/00337 PC~r/US90/03317 IMPROVED BUILDER-CONTAINING A~
CLEANER~DEGREASER MICROEMDLSION COMPOSITIONS
- Backqround of the Invention This invention relates to cleaner/degreaser compositions and, more particularly, to stable, aqueous, builder-containing cleaner/degreaser compositions in the form of true microemulsions which e~hibit enhanced cleaning and degreasing capability Heretofore, all of the conventional and available ready to use and concentrated water soluble, dilutable cleaner~degreaser compositions have e~pediently contained infinitely or highly water soluble organic solvents such as butyl cellosolve (ethylene glycol monobutyl ether), butyl carbitol (diethylene glycol monobutyl ether), ethyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether or isopropanol tog~ther with anionic or nonionic surfactants and conventiohal adjuvants such chelants, builders, perfumes, dyes, pH adjustors, etc., these components falling generally within the following compositional wt.% ranges:

2-10% Water soluble solvent(s) 1-3% Anionic or nonionic surfactant 0.1-3% Adjuvants OS Water 100.0%
Such conventional compositions are generally deficient in cleaning action and especially in heavy duty grease, oil, wa~, etc. cutting action, often smell objectionably strongly of volative solvent and can sometimes present conbustability problems in concentrated form. They also tend to be harsh on the hands and to defat the skin.
Further, heavy scrubbing, mopping or other mechanical action is generally required to attain the desired cleaning/degreasing action, especially where e~cessive SUBSTITUTE SHEET

CA 020~7027 1998-12-30 soilant buildup has occurred. Most, even in their concentrated form, are ineffective in their capability to remove graffiti or the like.
In U.S. Patent No. 5,080,831, I disclose stable, aqueous cleaner/degreaser compositions which are formulated in the form of totally water soluble solutions. Such compositions comprise (a) at least one sparingly water soluble organic solvent having certain defined characteristics; (b) solubilizing additive consisting of from 0.1 to approximately 100 weight percent of a surfactant and from O to approximately 99.9 weight percent of a coupler, the solubilizing additive being present in an amount not exceeding approximately tenfold that required to completely solubilize the organic solvent;
and (c) water. While such compositions exhibit markedly superior cleaning/degreasing efficacy over that achievable with compositions containing infinitely water soluble organic solvents, problems are encountered in incorporating builders therein to further enhance their cleaning/degreasing capability due to the "salting out" characteristics of conventional builders.
There is a need, therefore, for improved builder-containing, aqueous cleaner/degreaser compositions which permit still further improvements in cleaner/degreasing activity.

.

CA 020~7027 1998-12-30 - 2a -Summary of the Invention Among the several objects of the invention may be noted the provision of stable, aqueous cleaner/degreaser compositions containing builders which boost the cleaning/degreasing action of such compositions; the provision of such compositions which are formulated in the form of stable microemulsions; the provision of compositions of ~o 570 27 thls type whlch lncorporate organlc solvent of lnherently llmlted aqueous solublllty; the provlslon of such composltlons whlch are nontoxlc, nonhazardous ln use and exhlblt a low level of odor; the provlslon of such composltlons whlch avold soll redeposltlon and lnhlblt metal corroslon; and the provlslon of such lmproved bullder-contalnlng composltlons whlch may be readlly formulated from avallable components. Other ob~ects and features wlll be ln part apparent and ln part polnted out herelnafter.
Brlefly, the present lnventlon ls dlrected to stable, aqueous cleaner/degreaser composltlons whlch are formulated ln the form of true mlcroemulslons. The composltlons comprlse:
(a) at least one sparlngly water soluble organlc solvent characterlzed by (1) havlng a water solublllty ln the range of approxlmately 0.2 to approxlmately 6 welght, percent;
(11) not belng a hydrocarbon or halocarbon;
(lil) havlng one or more slmllar or dlsslmllar oxygen, nltrogen, sulfur or phosphorous contalnlng functlonal groups;

(lv) belng a solvent for hydrophoblc sollants;
and (v) belng present ln an amount exceedlng lts aqueous solublllty.

~0 57~27 ~
3a ~ b) from approxlmately 0.25 to 10.0 wt.%, based on the total composition, of a builder;
(c) a solubillzlng additive consisting of from approximately 0.1 to approxlmately 100 welght percent of a surfactant and from 0 to approxlmately 99.9 weight percent of a coupler, said solubilizing additive being present in an amount not substantially exceeding the amount required W O 91/00337 PC~r/US90/03317 to transform the combination of said organic solvent and said builder from the form of a true macroemulsion to the form of a microemulsion and less than that reguired to form a true solution; and (d) water.
The compositions of the invention e~hibit improved cleaner/
degreaser efficacy over compositions which contain no builder component.

Description of the Preferred Embodiments In accordance with the present invention, it has been found that improved builder-containing agueous cleaner/ degreaser compositions can be formulated in the form of stable microemulsions by combining at least one sparingly water soluble organic solvent having certain characteristics and being present in an amount e~ceeding its aqueous solubility with a builder, a solubilizing additive and water, the solubilizing additive beinq present in an amount not substantially e~ding the amount required to transform the combination of said organic solvent and said builder from the form of a true macroemulsion to the form of a microemulsion and less than that required to form a true solution. Surprisingly, as demonstrated by the e~perimental data presented hereinafter, it has been discovered that the incorporation of builders into such compositions formulated as microemulsions boosts or enhances the cleaning~degreasing efficacy as compared to compositions containing no builder component. As indicated, it is essential to the formation of microemulsion compositions in accordance with the present invention that the solubilizing additive be present in an amount not substantially e~ceeding that required to transform the combination of the organic solvent and builder from the form of a true macroemulsion to the form of a microemulsion and less than that required to form a SUBSTITUTE SHEET

W O 91/00337 PC~r/US90/03317 ~ ~ ~ 7 ~ ~ ~ ' 5 microemulsions of the invention are clear and e~hibit the Tyndall effect. It is believed that the aqueous phase of the microemulsions contains the dissolved builder. Due to the limited aqueous solubility of the organic solvents employed in the practice of the invention, it is ~ln~ cLed that true microemulsions are formed.
The incorporation of a builder component in the microemulsion compositions of the invention provides additional advantages not conferred by cleaning~degreasing compositions which contain no builder component. Thus, such microemulsions not only achieve an ~nhanred cleaning/
degreasing efficacy but, moreover, they avoid soil redeposition and generally inhibit metal corrosion.
Accordingly, the compositions of the invention are particularly useful for cleaning~degreasing metallic surfaces. Further, such microemulsions are more cost effective in their formulation since they generally contain lower amounts of the organic solvent component than do non-builder formulations. Also, the present invention permits the practical and effective use of normally hydrophobic (oliophilic) solvents in builder-containing compositions, which solvents have great affinity for and dissolving action against oleophilic soilants.
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 the range of appro~imately O.Z 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;
(d) it must be a solvent for hydrophobic soilants; and (e) it must be present in an amount e~ceeding SUBSTITUTE SHEET

W O 91/00337 PC~r/US90/03317 c~
~i Organic solvents meeting these criteria provide superior cleaning~degreasing action when formulated in accordance with the invention.
The principal classes of organic solvents from which useful organic solvents may be selected include esters, alchohols, ketones, aldehydes, ethers and nitriles. These will generally contain one or more of the desired similar or dissimilar functional groups listed above. Esamples of organic solvents containing similar functional groups from among those listed above include diethyl gluterate (2 ester groups), phenacyl acetone (2 ~eto groups), diethylethyl phosphonate (2 phosphonate ester groups), ethylenedipropionate (2 ester groups), decylene glycol (2 hydro~yl groups), m-dimetho~ybenzene (2 ether 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 from among those listed above may be mentioned 2-phenosyethanol (h~drosy, ether groups), 1-pheno~y-2-propanol (hydrosy, ether groups), N-phenyl-morpholine (amino, ether groups), isopropylacetoacetate (keto, ester groups), _-metho~ybenzyl alcohol (ether, hydro~y groups), 4~-methosyacetophenone (ether, ketone groups), Q-nitrophenetole (nitro, ether groups), 2-heso~yethanol (hydrosy, ether groups), ethylcyano-acetoacetate (cyano, keto, ester groups), p-anisaldehyde (ether, aldehyde groups), polypropylene glycol 1200 (ether, hydro~yl groups), n-buto~y acetate (ether, ester groups), and 2-phenylthioethanol (thioether, hydrosyl groups).
In addition to the criteria listed above, it is also desirable but not essential that the organic solvent have a relatively low volatility or high flash point, e~hibit a low level of odor, be chemically stable, nonto~ic, nonhazardous and commercially available.
The sparingly water soluble organic solvents which may be employed in the practice of the present SUBSTITUTE SHEET--W O 91/00337 PC~r/US90/03317 ~ ~ ~ 7 ~ ~ ~ t invention (and comprising some of the solvents listed above) together with their aqueous ambient temperature solubility in wt.% include 2-pheno~yethanol (2.3) (marketed under the trade designation ~Dowanol EPh~), l-pheno~y-2-propanol (1.1) (marketed under the trade designation~Dowanol PPh~), -phenylethanol (1.6), acetophenone (0.5), benzyl alcohol (4.4), benzonitrile (1.0), n-butyl acetate (0.7), n-amyl acetate (0.25), benzaldehyde (0.3), N,N-di-ethylaniline (1.4), diethyl adipate (0.43), dimethyl-o-phthalate (0.43), n-amyl alcohol ~2.7), N-~h~ lmorpholine (1.0), n-buto~yethyl acetate (EB acetate) (1.1), cyclo-he~anol (4.Z), polypropylene glycol 1200 (2), 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 mi~ed succinic, glutaric and adipic acids (5.7) (mar~eted under the trade designation ~DBE ester~ by DuPont), diethyl glutarate (0.88), and diethyl malonate (2.08). As will be apparent to those s~illed in the art, the above-listed sparingly water soluble organic solvents are merely illus-trative and various other solvents meeting the criteria set out above may also be utilized in the practice of the inven-tion. Because of their performance characteristics, lack of odor, low volatility/high flash point, chemical stability and availability, 2-pheno~yethanol and l-pheno y-2-propanol are the preferred organic solvents of choice. N-buto~yethyl acetate (EB acetate) and the dimethyl esters of mi~ed succinic, glutaric and adipic acids are also among the pre-ferred organic solvents.
As indicated, a number of otherwise potent organic solvents having an aqueous solubility of less than appro~i-mately 0.2 weight percent such as 2-(2-ethylhe~o~y)ethanol (2-ethylhe~yl cellosolve) having an aqueous solubility of only 0.095 wt.%, and 2,6-dimethyl -4-heptanone (diisobutyl ketone) (aq. sol. 0.05 wt. %), and organic solvents having SUBSTITUTE SHEET

~an aqueous solubility in e~cess of appro~imately 6 weight g~percent such as propylene glycol monomethyl ether acetate (aq. sol. 16.5 wt.%), ethylene glycol diacetate (aq. sol.
14.3 wt.%), propylene carbonate (aq. sol. 19.6 wt.%) and N-methyl pyrrolidone (infinite aq. sol.) are not useful in the practice of the invention.
In formulating the stable, aqueous cleaner~
degreaser compositions of the invention in the form of microemulsions, an organic solvent meeting the required criteria is combined with a builder, a solubilizing additive and water. As is ~nown to those skilled in the art, a builder is a material that enhances or maintains the cleaning efficiency of surfactants and functions by inactivating water hardness, supplying al~alinity to assist cleaning, providing buffering to maintain al~alinity, pre-venting removed soil from redepositing during washing, and emulsifying oily and greasy soils. Any of the conventional builders known to the art may be used in the practice of the invention. These include silicates such as alkali metal silicates and metasilicates, alkali metal hydro~ides, alkali metal carbonates, bicarbonates and sesquicarbonates, phosphates such as alkali metal phosphates, pyrophosphates, tripolyphosphates, he~ametaphosphates and tetraphosphates, bora~ and alkali metal borates. Among specific builders which may be used in the practice of the invention may be mentioned sodium hydro~ide, sodium metasilicate, sodium silicate (Na2O:2SiO2 or Na2O:3SiO2), sodium carbonate, sodium sesquicarbonate, sodium bicarbonate, bora~, trisodium phosphate, tetrasodium pyrophosphate, sodium tripolyphos-phate, sodium he~ametaphosphate, sodium tetraphosphate, andsodium perborate. Other builders known to the art may also be used~ The builder component will generally constitute from appro~imately 0.25 to 10.0 wt.% of the total composition.
35The solubilizing additive component of the compositions of the invention consists of from SUBST~TUTE SHEET

W O 91/00337 PC~r/US90/03317 appro~imately 0.1 to appro~imately 100 weight percent of a surfactant and from 0 to appro~imately 99.9 weight percent of a coupler and the solubilizing additive is present in the formulated composition in an amount necessary to form a microemulsion, i.e. an amount not substantially e~ceeding the amount required to transform the combination of the organic solvent and builder components from the form of a true macroemulsion to the form of a microemulsion and less than that l~quired to form a true solution. Preferably, the amount of solubilizing additive employed is just suffi-cient to form a microemulsion. The amount of solubilizing additive (surfactants or surfactant plus coupler) required to e~fect the formation of a microemulsion will vary de~el.~ing upon the particular organic solvent and builder employed and can readily be determined by simple e~peri-mentation in each instance.
The solubilizing additive used in the practice of the invention may consist of a surfactant or a surfactant in combination with a coupler. As used herein, the term ~coupler~ is intended to mean a hydrotrope or a substance that increases the solubility in water of another material which is only partially water soluble, such as organic solvents or surfactants. In some instances, the use ~of a surfactant alone will suffice to render the organic solvent component of the compositions just completely (microcolloid-ally) soluble while in other instances the use of a surfac-tant in combination with a coupler may be utilized to achieve the desired microcolloidal solubilization of the organic solvent, i.e. microcolloidal solubilization meaning to transform the combination of the organic solvent and builder from a true macroemulsion to the form of a microemulsion. Whether or not a surfactant alone or the combination of a surfactant and coupler is to be used is dependent upon the particular organic solvent and surfactant employed and can readily be determined in each particular case by simple e~perimentation. The SUBSTITUTE SHEE~

hard surface cleaning/degreasing. Illustrative anionic ~' surfactants for use in the invention include dodecylbenzene sulfonic acid, sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate,triethanolamine dodecylbenzene sulfonate, morpholinium dodecylbenzene sulfonate, ammonium dodecylbenzene sulfonate, isopropylamine dodecylbenzene sulfonate, sodium tridecylbenzene sulfonate, sodium dinonylbenzene sulfonate, potassium didodecylbenzene sulfonate, dodecyl diphenylo~ide disulfonic acid, sodium dodecyl diphenyloside disulfonate, isopropylamine decyl diphenylo~ide disulfonate, sodium hesadecylosypoly (ethyleneo~y)(l0)ethyl sulfonate, potassium octylpheno~y-poly(ethyleneo~y)(9)ethyl sulfonate, sodium alpha Cl2_l4 olefin sulfonate, sodium he~adecane-l sulfonate, sodium ethyl oleate sulfonate, potassium octadecenylsuccinate, sodium oleate, potassium laurate, triethanolamine myri-state, morpholinium tallate, potassium tallate, sodium lauryl sulfate, diethanolamine lauryl sulfate, sodium laureth (3) sulfate, ammonium laureth (2) sulfate, sodium nonylphenosypoly(ethyleneo~y)(4) sulfate, sodium diiso-butylsulfosuccinate, disodium laurylsulfosuccinate, tetrasodium N-laurylsulfosuccinimate, sodium decylo~ypoly-(ethyleneosy(5)methyl)carbosylate, sodium octylpheno~ypoly-(ethyleneosy(8)methyl)carbosylate, sodium mono decylo~ypoly-(ethyleneo~y)(4)phosphate, sodium di decylosypoly-(ethyleneosy)(6)phosphate, and potassium mono/di-octyl-pheno~ypoly(ethyleneosy)(9)phosphate. Other anionic surfactants known in the art may also be employed.
Among the useful nonionic surfactants which may be employed may be mentioned octylphe~ ~oly(ethyleneo~y)-(ll)ethanol, nonylphenosypoly(ethyleneosy)(13)ethanol, dodecylphenosypoly(ethyleneo~y)(l0)ethanol, polyo~yethylene (12) lauryl alcohol, polyo~yethylene (14) tridecyl alcohol, laurylo~ypoly(ethyleneo~y)(l0)ethyl methyl ether, undecyl-thiopoly(ethyleneosy)(l2)ethanol, metho~ypoly(o~yethylene-(10)~(o~ypropylene(20))-2-propanol block copolymer, SUBSTITUTE SHEET

. ~ ~ .--. :Y~

nonylo~ypoly(propyleneo~y)(4)/(ethyleneo~y)(16)ethanol, dodecyl polyglycoside, polyo~yethylene (9) monolaurate, polyo~yethylene (8) monoundecanoate, polyo~y~thylene (20) sorbitan monostearate, polyo~yethylene (18) sorbitol monotallate, sucrose monolaurate, lauryldimethylamine o~ide, myristyldimethylamine o~ide, lauramidopropyl -N,N-dimethylamine o~ide, 1:1 lauric diethanolamide, 1:1 coconut diethanolamide, 1:1 mi~ed fatty acid diethanol-amide, polyo~yethylene(6)1auramide, 1:1 soya diethanol-amidopoly(ethyle~_J~)(8) ethanol, coconut diethanolamide,~modified~, and coconut diethanolamide, ~long chain modified~. Other known nonionic surfactants may li~ewise be used.
Illustrative useful cationic surfactants include a mi~ture of n-al~yl (C12 50%, C14 30%~ C16 17~ 18 dimethyl ethylbenzyl ammonium chlorides, he~adecyltrimethyl-ammonium methosulfate, didecyldimethylammonium bromide and a mi~ture of n-al~yl (68% C12, 32% C14) dimethyl benzyl ammonium chlorides. Similarly useful amphoteric surfactants include cocamidopropyl betaine, sodium palmityloamphopro-pionate, N-coco beta-aminopropionic acid, disodium N-lauryl-iminodipropionate, sodium coco imidazoline amphoglycinate and coco betaine. Other cationic and amphoteric surfactants known to the art may also be utilized.
The preferred surfactants for general use in the practice of the invention include dodecylbenzenesulfonic acid and the sodium, potassium, triethanolamine, morpho-linium, ammonium and isopropylamine salts thereof, and morpholinium tallate.
The couplers which may be utilized in the practice of the invention include sodium benzene sulfonate, sodium toluene sulfonate, sodium ~ylene sulfonate, potassium ethylbenzene sulfonate, sodium cumene sulfonate, sodium octane-l-sulfonate, potassium dimethylnaphthalene sulfonate, ammonium ~ylene sulfonate, sodium n-he~yl diphenyo~ide disulfonate, sodium 2-et~ylhe~yl sulfate, ammonium SUBSTITUTE SHEET

W O 91/00337 PC~r/US90/03317 .
r~
/".~, -n-buto~yethyl sulfate, sodium 2-ethylhe~anoate, sodium pelargonate, sodium n-buto~ymethyl carbo~ylate, potassium mono/di pheno~yethyl phosphate, sodium mono/di n-buto~yethyl phosphate, triethanolamine trimethylolpropane phosphate, sodium capryloamphopropionate, disodium capryloiminodipro-pionate, and sodium capro imidazoline amphoylycinate.
Certain water-soluble solvents known to the art as couplers such as propylene glycol ethers (e.g. tripropyleneglycol monomethyl ether) can be used in the practice of the invention, but cannot be substituted for the sparingly water soluble organic solvent component. Additional couplers or hydrotropes known to the art may also be utilized.
In regard to the solubilizing additive component of the compositions of the invention, it will be understood that one or more surfactants from one or more compatible classes of surfactants may be employed or utilized in a mi~ed solubilizing surfactant system. For e~ample, a combination of compatible anionic and nonionic surfactants may be employed. Li~ewise, a combination of compatible couplers may also be used as may a combination of one or more compatible surfactants from different classes of surfactants together with one or more couplers. Thus, one may use a combination of blended surfactants and couplers to achieve the desired minimal sol~ent solubilization. ~he 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, but less preferably, a mi~ture of the sparingly soluble organic solvents may be employed in formulating the compositions of the invention. However, if a mi~ture of solvents is to be used, each of the solvents should have nearly the same appro~imate water solubility so that they will solubilize in water at appro~imately the same point upon addition of the solubilizing additive.
In addition to the organic solvent and solubiliz-ing additive components of the compositions of the invention, SUB~ I ~ I IJTE SHEE~

W O 91/00337 PC~r/US90/03317 ~ ~ ~ f ~ 13 various optional adjuvants can be incorporated. These include chelants such as the sodium salts of ethylenedi-aminetetraacetic acid (Hampene 100 or Versene 100), thickeners such as carbo~y acrylic polymers (Carbopol 940) or acrylic acid/alkyl methacrylate copolymers (Acrysol ICS-l), fragrances, dyes, pH adjustants, defoaming agents, anti-corrosion additives and anti-rust additives. To prevent flash rusting when the compositions are used to clean and~or degrease metal surfaces, an anti flash-rusting additive such as an alkanolamine (e.g., mono-, di- or triethanolamine) may be incorporated.
In formulating the compositions of the invention, the various components as brought together may first form an oily suspension which becomes an emulsion upon the addition of a surfactant/coupler, and is then finally transformed into a microemulsion through the addition of the final portion of the solubilizing coupler. For e~ample, 2.0 wt. %
sodium metasilicate, 7.5 wt. % 1-pheno~y-2-propanol, 2.5 wt.
% tripropyleneglycol monomethyl ether and 76.4 wt. % soft water are stirred to form an oily suspension having a pH of 13.3. 2.4 wt. % dodecylbenzenesulfonic acid is added with stirring to form a creamy white emulsion having a pH of 13.1 7.2 wt. % sodium ~ylene sulfonate (40~) is then added with stirring whereupon some slight lightening of the emulsion occurs. The addition of 1.8 wt. % sodium ~ylene sulfonate (40%) causes the emulsion to become still lighter but it remains opaque. Upon the final addition of 0.2 wt. %
sodium ~ylene sulfonate (40%) with stirring, the white emulsion is transformed into a bluish microcolloidal microemulsion having a pH of 13.05. The microemulsions of the invention can also be formulated by combining the various components together in different sequence to transform any emulsion formed into a microemulsion. The addition of an e~cess of the solubilizing additive to the formulation will cause the microemulsion to be converted SUBSTITUTE SHEET

W O 91/00337 PClr/US90/03317 into a solution and is to be avoided if optimum cleaning/
degreasing efficacy of the builder-containing formulations is to be achieved.
The concentration of the aqueous cleaner~deqreaser solution, as indicated by the terms ~total solids content~
and ~total actives content~ in the working e~amples provided hereinafter refers, respectively, to the combined percentages of nonvolatile components and to the sum total of nonaqueous volatile and nonvolatile components.
The term ~cloud point' indicates the temperature below which the composition e~ists as a clear, single phase microemulsion and above which phase separation (hetero-geneity) occurs. ~or practical reasons, a composition should preferably have a cloud point in e~cess of, for e~ample 50~C, to have a viably safe, storage-stable shelf life under hot, summertime warehouse conditions.
As shown by the e~perimental degreasing test data presented below, the compositions of the invention provide enhanced cleaning/degreasing efficacy over that achievable with compositions containing no builder or with available builder-containing compositions formulated in the form of total solutions.
The following e~amples illustrate the practice of the invention.

E~ample 1 In the following e~amples of illustrative cleaner/
degreaser compositions of the present invention, the compositions were subjected as indicated to the definitive, semiquantitative degreasing test method described below in order to measure their cleaning/degreasing efficacy.
A magnetic stirrer (Fisher Scientific Co., Catalog No. 14-511-lA) provided with a vaned disc magnetic stir bar (7~8- (diameter) ~ 5~8- (height), 22 mm ~ 15 mm, Fisher Scientific Co., Catalog No. 14-511-98C) was used In each instance, pre-cleaned, borosilicate glass microslides (3 SUBST~TUTE SHEET

~ 15 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~ ~
1.0~ coated area. The test cleaner~degreaser solutions were employed at full strength unless otherwise indicated and in an amount sufficient to fill a 50 ml Pyre~ he~r containing the vaned disc magnetic stirrer bar to a level of 40 ml.
Each test solution and surrounding air were maintained at 21 + 0.5~C and the test solution stirring rate was determined by a setting of ~3~ on the stirrer dial of the magnetic stirrer. The stirring disc was positioned off-center to accomodate each microslide, touching neither the beaker walls nor the microslide and rotating freely when in use.
The microslide, in each test, rested upright on the beaker bottom, was allowed to lean against the 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 bar.
For each test, the bea~er containing the stirrer bar was filled to 40 ml. with the test cleaning/degreasing solution at the indicated concentration, placed atop the magnetic stirrer plate, and positioned off-center to accomo-date the glass microslide, and yet allow the vaned disc stirrer bar to rotate or spin freely. The stirrer was turned on, the dial adjusted manually to the ~3~ stirring rate setting and the Vaseline thin film coated glass micro-slide was introduced into the test solution bath in such a manner that the coated side faced upward and was positioned away from the stirrer bar. The time ~0~ was noted immediately on a wat~h or clock with a sweep second hand.
At appropriate time intervals, the glass microslide was briefly removed from the cleaner~degreaser solution bath and immediately ~read~ for ~% Vaseline removed from the 1.0~ ~ 1.0~ treated area~, an objective determina-tion, after which the microslide was immediately returned to SUB~ ~ JTE SHEET

WO9l/00337 PCT/US90/03317 ~ 16 i~ the stirred agueous cleaner/degreaser bath. The duration of the degreasing test is determined by the time needed for complete, 100% removal of the Vaseline film from the glass microslide surface.
The accuracy of the above-described test method is of the order of ~ 5% as determined by replicate run averaging.

E~amPle 2 An aqueous, cleaner/degreaser formulation in the form of a microemulsion was prepared having the following composition:
Component Wt.
l-Pheno~y-2-propanol (Dowanol PPh) 3.0 Monoethanolamine 1.8 Sodium metasilicate 1.5 Dodecylbenzenesulfonic acid 1.0 Soft H20 92.7 100 .0 The sodium metasilicate was dissolved in water with stirring.
The monoethanolamine, l-pheno~y-2-propanol and dodecyl-benzenesulfonic acid were added and stirring of the resultant emulsion/suspension was continued until the emulsion gradu-ally cleared to produce an irridescent (blue) microemulsion.
The microemulsion had a pH of 12.65, a total solids content of 2.5% and a total actives content of 7.3%. Upon heating, the microemulsion remained irrides~ent to 50OC, then devel-oped more turbidity up to 75~C and became a clear, colorless aqueous solution above about 75~C. It e~hibited no cloud point to 100~C.
The composition readily removed the following soilant markin~s from alkyd enameled metal surfaces: black SUBSTITUTE SHEET

17 ~- ~~ ~ r~ rl Magic Marker, black and blue indelible ballpoint pen, #l hardness pencil, red (wa~y) crayon, and automotive grease smearings. Some trace smudge was left on the surface. The composition readily removed four coats of floor finish ~trade designation ~Buckeye Citation~ by The Davies-Young Company) from vinyl tile upon 5 minutes contact time at room temperature, followed by swabbing action, a water rinse and air drying.
This composition was subjected to the degreasing test method of E~ample 1 with the following results:
1st attac~ on greased slide at 2-3 sec.
30% removal of grease at 30 sec.
60-65% removal of grease at 1.0 min.
100% removal of grease at 1.5 min.

E~amPle 3 E~ample 2 was repeated in formulating an aqueous cleaner~degreaser microemulsion having the following composition:
Comvonent Wt. %
1-Pheno~-2-propanol (Dowanol PPh) 3.5 Monoethanolamine 0.5 Sodium Metasilicate 1.2 Dodecylbenzenesulfonic acid 1.2 Sodium ~lene sulfonate (40%) 5.0 Soft H2O 88.6 100 . 00 The composition was a bluish, irridescent microemulsion having a pH of 12.5, a total solids content of 4.4% and a total actives content of 8.4%. Upon heating, the composi-tion remained an irridescent microemulsion to 48~C, became a turbid emulsion between 48-59~C and a clear, colorless solution above about 60~C.

SUBST~TUTE SHEET

W O 91/00337 PC~r/US90/03317 ; 18 , The composition effected 100% removal of the markings set forth in E~ample 2 and also effected 100%
removal of four coats of ~Buckeye Citation~ floor finish as in E~ample 2.
This composition was subjected to the degreasing test method of E~ample 1 with the following results:
1st attack on greased slide at Z sec.
33% removal of grease at 15 sec.
60% removal of grease at 30 sec.
80-85% removal of grease at 45 sec.
100% removal of grease at 1.0 min.

E~ample 4 E~ample 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following composition:
ComPonent Wt. %
l-Pheno~y-2-propanol (Dowanol PPh) 3.5 Monoethanolamine 0.5 Sodium metasilicate 1.2 Dodecylbenzenesulfonic acid 1.2 Sodium cumene sulfonate (45%) 3.5 Soft H2O 90.1 100 . O
The composition was a bluish, irridescent microemulsion haviny a pH of 12.6, a total solids content of 3.98% and a total actives content of 7.98%. Upon heating, the composition remained an irridescent microemulsion to 39~C
and became a clear, colorless solution above about 39~C. It e~hibited no cloud point to 100~C.

SUBST~TUTE SHEET

~O91/00337 PCT/US90/03317 The composition effected 100% removal of the markings set forth in E~ample 2 with no smudging, and also effected 100% removal of four coats of ~Buckwye Citation~
floor finish as in E~ample 2.
This composition was subjected to the degreasing test method of E~ample 1 with the following results:
10% removal of grease at 15 sec.
25% removal of grease at 30 sec.
45-50% removal of grease at 1.0 min.
70% removal of grease at 1.5 min.
85-90% removal of grease at 2.0 min.
100% removal of grease at 2.5 min.

E~amPle 5 E~ample 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following compo-sitlon:
Component Wt.
l-Pheno~y-2-propanol (Dowanol PPh) 3.5 Monoethanolamine 0.5 Sodium metasilicate 1.2 Dodecylbenzenesulfonic acid 1.2 Sodium Capryloamphopropionate, 50% Monateric CY-Na-50 2.0 Soft H2O 91.6 100.00 The composition was a pale yellow, irridescent microemulsion having a pH of 12.5, a total solids content of 3.4% and a total actives content of 7.4%. Upon heating, the composi-tion remained an irridescent microemulsion to 50~C andbecame a clear solution at temperatures above 50~C. It e~hibited no cloud point.

SUBSTITUTE SHEE~

W O 91/00337 PC~r/US90/03317 ~, The composition effected 100% removal of the markings set forth in E~ample 2 with no to very slight smudging, and also effected 95-100% removal of four coats of ~Bucke~e Citation~ floor finish as in E~ample 2.
This composition was subjected to the degreasing test method of E~ample 1 with the following results:
1st attack on greased slide at 3 sec.
20-25% removal of grease at 15 sec.
50% removal of grease at 30 sec.
85-90% removal of grease at 45 sec.
100% removal of grease at 1.0 min.

E~ample 6 E~ample 2 was repeated in formulating an aqueous, cleaner~degreaser microemulsion having the following composition:
Comvonent Wt. %
l-Pheno~y-2-propanol (Dowanol PPh) 4.0 Sodium metasilicate 1.0 20 Sodium hydro~ide (50%) 0.2 Dodecylbenzenesulfonic acid 1.5 Sodium ~ylene sulfonate (40%) 5.0 Monoethanolamine 0.5 Soft H2O 87.8 100.00 The composition was a bluish, irridescent microemulsion having a pH of 12.65, a total solids content of 4.6% and a total actives content of 9.1%. Upon heating, the composition remained an irridescent microemulsion to 51.5~C, was turbid in the range 50-60~C, and was a clear, colorless solution above about 60~C.

SUBSTITUTE SHEE~

W O 91/00337 PC~r/US90/03317 ~ ~ Il~ f,? r~J
2 ~ 7 ~ 21 , .

The composition effected 100~ removal of the markings set forth in E~ample 2 with slight smudging and also effected 100% removal of four coats of ~Buckeye Citation~ floor finish as in E~ample 2.
The composition was subjected to the degreasing test method of E~ample 1 with the following results:
20~ removal of grease at 30 sec.
35% removal of grease at 1.0 min.
60% removal of grease at 2.0 min.
90% removal of grease at 3.0 min.
100% removal of grease at 3.33 min.

E~am~le 7 A control composition was prepared by combining the following components in the amounts indicated:
ComPonent Wt.
l-Pheno~y-l-propanol (Dowanol PPh) 4.0 Dodecylbenzenesulfonic acid 1.7 Sodium hydro~ide (50%)0.5 Monoethanolamine 1.5 Soft H2O 92.~
100 . O
The composition was a clear, essentially colorless solution containing no builder component. It had a pH of 11.7, a total solids content of 1.844% and a total actives content of 7.344%. It e~hibited no cloud point to 100~C.
The composition quite easily removed the following percentages of the markings set forth in E~ample 2 from alkyd enameled metal surfaces:
85-90% removal of black Magic Marker felt pen 80% removal of black indelible ballpoint pen 100% removal of blue indelible ballpoint pen SUBSTITUTE SHEET

~L

90% removal of #1 pencil 95% removal of red (wa~y) crayon ,, 100% removal of automobile grease smearings There was slight smudging with the black Magic Marker and black indelible ballpoint pen markings. The composition also effected 100% removal of four coats of ~Buckeye Citation~ floor finish as in E~ample 2.
The composition was subjected to the degreasing test method of E~ample 1 with the following results:
10-15% removal of grease at 15 sec.
25% removal of grease at 30 sec.
45% removal of grease at 1.0 min.
70-75% removal of grease at 2.0 min.
90% removal of grease at 3.0 min.
100% removal of grease at 3.5 min.

E~am~le 8 An aqueous, cleaner/degreaser formulation in the form of a microemulsion was prepared having the following composition:
ComPonent Wt.
l-Pheno~y-2-propanol (Dowanol PPh) 4.0 Dodecylbenzenesulfonic acid 1.7 Sodium hydro~ide (50%)0.4 Monoethanolamine 0.9 Soft H20 92.6 Sodium metasilicate 0.4 100 . O
All of the above components e~cept the sodium metasilicate were stirred together to form an aqueous solution. The sodium metasilicate was then added as granules and upon dissolving in the solution, a microemulsion was formed having a bluish, irridescent appearance. The microemulsion SUBSTITUTE SHEET

W O 91/00337 PC~r/US90/03317 ~ 7 ~ 23 had a pH of 12.1, a total solids content of 2.22% and a total actives content of 7.12%. Upon heating, the microemulsion remained irridescent to 37~C. and became a clear, colorless solution above about 37~C. It e~hibited no cloud point.
The composition effe~ted 100% removal of the markings set forth in E~ample 2 with no smudging and also effected 100% removal of four coats of ~Buckeye Citation~
floor finish as in Esample 2.
This composition was subjected to the degreasing test method of E~ample 1 with the following results 33% removal of grease at 15 sec.
60% removal of grease at 30 sec.
85-90% removal of grease at 45 sec.
100% removal of grease at 1.0 min.

Esample 9 An aqueous, cleaner/degreaser formulation in the form of a microemulsion was prepared having the following composition:
ComPonent Wt. %
l-Pheno~y-2-propanol 4.0 (Dowanol PPh) Dodecylbenzenesulfonic acid 1.7 Sodium Hydro~ide (50%) 0.5 Monoethanolamine 1.5 Soft H20 91.9 Sodium metasilicate0.4 100 . O
All of the above components e~cept the sodium metasilicate 3~ were stirred together to form a clear, aqueous solution.
The sodium metasilicate was then added as granules and upon dissolving in the solution, a microemulsion was formed SUB~ ~ JTE SHEE~

-~ 24 ~3 ~, "o ~~ having a bluish, irridescent appearance. The microemulsion had a pH of 12.3, a total solids content of 2.24% and a total actives content of 7.74%. Upon heating, the micro-emulsion remained irridescent to 41~C. Above about 41~C it became a clear, colorless solution. It eshibited no cloud point.
The composition effected 100% removal of the markings set forth in Esample 2 with very slight tendency to smudge and also effected 100% removal of four coats of ~Buc~eye Citation~ floor finish as in Esample 2.
This composition was subjected to the degreasing test method of Esample 1 with the following results:
25-30% removal of grease at 15 sec.
60-65% removal of grease at 30 sec.
85-90% removal of grease at 45 sec.
100% removal of grease at 50 sec.
By comparison with the results set forth in Esample 7, the above results show the enh~nced degreasing activity achieved throught the incorporation of a builder.

E~am~le 10 Esamples 8 and 9 were repeated in preparing a microemulsion cleaner~degreaser formulation having the following composition:
Component Wt.%
1-Pheno~y-2-propanol 4.0 (Dowanol PPh) Dodecylbenzenesulfonic acid 1.6 Soduim hydroside (50%)0.4 Monoethanolamine 1.5 Soft H2O 92.1 Sodium metasilicate 0.4 100 . O

SUBSTITUTE SHEET

.J

The microemulsion had a bluish, irridescent appearance, a pH of 12.3, a total solids content of 2.12% and a total actives content of 7.62%. Upon heating, the microemulsion remained irridescent to 44~C and above which it formed a clear, colorless solution. It eshibited no cloud point.
The composition effected 100% removal of all markings including auto grease as set forth in E~ample 2 and also effected 100% removal of four coats of ~Buckeye Citation~ floor finish as in E~ample 2.
The composition was subjected to the degreasing test method of E~amplel with the following results:
1st attack on greased slide at 1-2 sec.
40% removal of grease at 15 sec.
70-75% removal of grease at 30 sec.
100% removal of greease at 45 sec.

E~amPle 11 Esamples 8 and 9 were repeated in preparing a microemulsion cleaner~degreaser formulation having the following composition:
Component Wt. %
l-Pheno~y-2-propanol (Dowanol PPh) 4.0 Dodecylbenzenesulfonic acid 1.6 Sodium hydroside (50%)0.4 Monoethanolamine 1.5 Soft H2O 92.0 Sodium metasilicate 0.5 100 . O

The microemulsion had a bluish, irridescent appearance, a pH
of 12.4, a total solids contents of 2.22% and a total actives content of 7.72% Upon heating, the microemulsion remained irridescent to 52.5~C and became a clear solution above 57.~~C I~ e~hibi~ed n~ cl~ud p~int SUBSTITUTE SHEET

.~ ~, , ~
f,~ The composition effected 100% removal of all ~u markings set forth in E~ample 2 with no smudging and also ;~ effected 100% removal of four coats of ~Buckeye Citation~
~f floor finish as in Esample 2.
This composition was subjected to the degreasing test method of E~ample 1 with the following results:
20-25~ removal of grease at 15 sec.
50% removal of grease at 30 sec.
75% removal of grease at 1.0 min.
85-90% removal of grease at 1.5 min.
100% removal of grease at 2.0 min.

Esamp_e 12 An aqueous, cleaner/degreaser formulation in the form of a microemulsion was prepared having the following composition:
ComPonent Wt. %
l-Pheno~y-2-propanol (Dowanol PPh) 4.0 Dodecylbenzenesulfonic acid 1.5 Sodium hydro~ide (50%)0.4 Soft H2O 93.7 Tetrapostassium pyrophosphate 0.4 100 . O
All of the above components e~cept tetrapotassium pyro-phosphate were stirred together and the pH adjusted to 7.0 with a trace of sodium sesquicarbonate to obtain a clear, colorless a~ueous solution. The tetrapotassium pyrophos-phate was then added as granules and the solution immedi-ately changed to a bluish, irridescent microemulsion. The microemulsion had a pH of 9.11, a total solids content of 2.11% and a total actives content of 6.115%. Upon heating, the microemulsion remained irridescent to 42~C. It exhibited no cloud point to 100~C and no flash point.

SUBST~TUTE SHEET

W O 91/00337 PC~r/US90/03317 7 -~ 27 The composition effected 100%, easy and fast removal of all markings set forth in E~ample 2.
This composition was subjectea to the degreasing test method of E~ample 1 with the following results:
1st attack on greased slide at 2 sec.
45~ removal of grease at 15 sec.
90-95% reemoval of grease at 30 sec.
100% removal of grease at 35 sec.

E~ample 13 E~ample 12 was repeated in preparing a microemulsion cleaner~degreaser formulation having following composition:
ComPonent Wt. %
l-Pheno~y-2-propanol 4.0 Dodecylbenzenesulfonic acid 1.5 Sodium hydro~ide (50%)0.4 Soft H2O 93.7 Bora~ 0.4 100 . O
The microemulsion formed upon the addition of bora~
granules to the other components and the slow dissolution of the bora~ produced a gradual change from a clear, a~ueous solution to a bluish, irridescent microemulsion.
The microemulsion had a pH of 8.93, a total solids content of 2.115% and a total actives content of 6.115%. Upon heating, the microemulsion remained irridescent to 38~C, clearing at 38.5~C and becoming a clear, colorless solution above about 39~C. It e~hibited no cloud point to 100~C and no flash point.

SUBSTITUTE SHEET

~ ~ 3 ~é~

The composition effected 100% facile removal of all markings set forth in E~ample 2.
This composition was subjected to the degreasing test method of E~ample 1 with the following results:
1st attack on greased slide at 1-2 sec.
50-55% removl of grease at 15 sec.
80% removal of grease at 30 sec.
100% removal of grease at 40 sec.

E~amDle 14 E~ample lZ was repeated in preparing a microemul-sion cleaner/degreaser formulation having the following composition:
Compon~nt Wt. %
l-Pheno~y-2-propanol 4.0 (Dowanol PPh) ~odecylbenzenesulfonic acid 1.5 Sodium hydro~ide (50%)0.4 Soft H20 93.6 Sodium carbonate 0.5 100.0 The addition of the sodium carbonate in powder form to a clear, colorless agueous solution of the other components produced the instantaneous development of a bluish, irridescent microemulsion. The microemulsion had a pH of 10.75, a total solids content of 2.215% and a total actives content of 6.215%. The microemulsion, unlike those of E~amples 12 and 13, was slightly viscous and had a Brookfield viscosity of 37 cps. at 21~C. Upon heating, the microemulsion remained irridescent to 60.5~C and became a clear, colorless aqueous solution above about 61~C. It e~hibited no cloud point to 100~C.
The composition effected 100%, fast removal of all markings set forth in E~ample 2.

SUBSTITUTE SHEE-r W O 91/00337 PC~r/US90/03317 e~ 2 9 ~ ~ ~ ~s c-~ ~3 r ~

This composition was subjected to the degreasing test method of E~ample 1 with the following result:
1st attack in greased slide at 2 sec.
30-35% removal of grease at 15 sec.
60% removal of grease at 30 sec.
85-90~ removal of grease at 40 sec.
100% removal of grease at 50 sec.

E~amDle 15 E~ample 2 was repeated in formulating an aqueous, cleaner~degreaser microemulsion having the following compo-sition:
ComPonent Wt. %
2-Pheno~yethanol 6.4 (Dowanol EPh) Dodecylbenzenesulfonic acid 2.S
Anhydrous sodium 3.5 metasilicate Chelating agent 2 ~ 0 (Hampene 100, 40%) Sodium ~ylene sulfonate (40%) 7.5 Soft H20 78.1 100 . O
The composition was a faint bluish, microemulsion having a pH of 12.86, a total solids content of 9.8% and a total actives content of 16.2%. It e~hibited no cloud content of point to 100~C and no flash point.
At a 1:5 dilution with water, the composition effected 75% removal of black Magic Marker markings from an alkyd enameled steel panel.
This composition at a 1:2 dilution with water was sub~ected to the degreasing test method of E~ample 1 with the following results:

SUB~ 111 ~JTE SHEEl W O 91/00337 PC-r/US9OtO3317 ' 30 ~ '~
1st attack on greased slide at 8 sec.
~' 10% removal of grease at 30 sec.
30% removal of grease at 1.0 min.
55% removal of grease at 2.0 min.
80-85% removal of grease at 4.0 min.
100% removal of grease at 6.0 min.

EsamPle 16 E~ample 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following composition:
ComPonent Wt. %
Anhydrous sodium 3. 6 metasilicate Dodecylbenzenesulfonic2.80 acid Chelating Agent 2.00 (Hampene 100) Propyleneglycol 2.00 monomethyl ether Dipropyleneglycol 0.95 monomethyl ether Tripropyleneglycol 0. 70 monomethyl ether l-Pheno~y-2-propanol 6.35 (Dowanol PPh) Sodium ~ylene sulfonate8.50 Soft H2O 73.l0 100 . 00 The composition was a faint, bluish, colloidal microemulsion having a pH of 13.23, a total solids content of 10.6% and a total actives content of 20.6%. It e~hibited no cloud point and no flash point.

SUBSTITUTE SHEEl' W O 91/00337 PC~r/US90/03317 At a 1:5 dilution with water, the composition effected 90% removal of black Ma~ic Marker markings from an al~yd enameled steel panel.
This composition at a 1:2 dilution with water was subjected to the degreasing test method of E~ample 1 with the following results:
1st attack on greased slide at 5 sec.
15% removal of grease at 30 sec.
35% removal of grease at 1.0 min.
70% removal of grease at 2.0 min.
90% removal of grease at 3.0 min.
100% removal of grease at 3.75 min.

E~amDle 17 E~ample 2 was repeated in formulating an aqueous having the following composition:
ComPonent Wt. %
Anhydrous sodium 5.50 metasilicate Dodecylbenzenesulfonic acid 5.00 Chelating agent 2.00 (Hampene 100) Propyleneglycol 2.00 monomethyl ether Dipropyleneglycol 0.95 monomethyl ether Tripropyleneglycol 0.70 monomethyl ether l-Pheno~y-2-propanol 6.35 (Dowanol PPh) Sodium ~ylene sulfonate (40%) 8.5 Soft H20 69.0 100 . O

SUB~ 111 ~JTE SHEET

W O 91/00337 PC-r/~'S90/03317 The components formed a clear, aqueous solution rather than a microemulsion because the composition included an e~cess of solubilizing additive over that required to form a micro-emulsion.
At a 1:5 dilution with water, the solution effected 0% removal of black Magic ~ar~er markings from an alkyd enameled steel panel.
The solution at a 1:2 dilution with water was subjected to the degreasing test method of Esample 1 with the following results:
1st attack on greased slide at 2.5 min.
10% removal of grease at 4.5 min.
20-25% removal of grease at 10 min.
50% removal of grease at 20 min.
70% removal of grease at 30 min.
90-95% removal of grease at 50 min.
100% removal of grease at 65 min.

E~ample 18 E~ample 2 was repeated in formulating an aqueous microemulsion having the following composition:
ComPonent Wt. %
Anhydrous sodium 4.0 metasilicate Dodecylbenzenesulfonic acid 2.0 Propylene glycol mono-t-butyl 9.5 ether (Arcosolve PTB) Chelating agent ~Hampene 100) 3.0 Soft H20 81.5 100 . O
The organic solvent component, propylene glycol mono-t-butuyl ether, has an aqueous solubility of 13.9 wt. % at 21~C. The composition was a very faint bluish, SUBST~TUTE SHEET

33 _~
f ~

colloidal microemulsion having a pH of 13.73, a total solids content of 7.2% and a total actives content of 16.7%. It had a cloud point of 28~C.
At a 1:5 dilution with water, the composition effected 60% removal of black Magic Mar~er markings from an al~yd enameled steel surface.
This composition at a 1:2 dilution with water became solution and was subjected to the degreasing test method of E~ample 1 with the following results:
1st attack on greased slide at 7 sec.
20-25% removal of grease at 1.0 min.
33% removal of grease at 2.0 min.
40% removal of grease at 3.0 min.
45-50% removal of grease at 4.0 min.
60% removal of grease at 5.0 min.
65-70% removal of grease at 6.0 min.
75% removal of grease at 7.0 min.
80% removal of grease at 8.0 min.
85% removal of grease at 9.0 min.
90% removal of grease at 10.0 min.
95% removal of grease at 12.0 min.
100% removal of grease at 13.5 min.

E~amPle 19 E~ample 2 was repeated in formulating an aqueous, cleaner~degreaser microemulsion having the following composition:
Component Wt. %
Anhydrous sodium 2.0 metasilicate Nonylphenol etho~ylate3.5 (T-Det N-14) Chelating agent 2.0 (Hampene lOQ, 40%) Dipropylenegycol 3.5 monometh~l ether SUB~ 111 ~JTE SHEET

W O 91/00337 PC~r/US90/03317 ~ 34 ~' .
j*,.
'~ l-Pheno~y-2-propanol 6.5 (Dowanol PPh) ~~
Sodium ~ylene sulfonate (40%) 11.0 Soft H20 71.5 100.0 The composition was a slightly bluish, colloidal micro-emulsion having a pH 13.62, a total solids content of 10.7%
and a total actives content of 20.7%. It had a cloud point of 26~C and no flash point.
At a 1:5 dilution with water, the composition effected 100~ removal of black Magic Marker markings from an al~yd enameled steel panel.
This composition at a 1:2 dilution with water was subjected to the degreasing test method of E~ample 1 with the following results:
1st attack on greased slide at 5 sec.
25% removal of grease at 20 sec.
60% removal of grease at 40 sec.
85-90% removal of grease at 1.0 min.
100% removal of grease at 1.5 min.

EsamPle 2_ E~ample 2 was repeated in formulating an aqueous, cleaner~degreaser microemulsion having the following composition:
2 5 Com~onent Wt. %
Anhydrous sodium 2.0 metasilicate Dodecylbenzenesulfonic acid 1.5 Chelating agent 5.0 (Hampene 100, 40%) Benzyl acohol 9.0 Tripropyleneglycol 1.0 monomethyl ether SUBSTITUTE SHEET

W O 91~00337 PC~r/US90/03317 ~ ~ 6~ , '7 ', 35 Sodium ~ylene sulfonate (40%) 9. 5 Soft H20 7.2 100. 0 The composition was faint bluish microemulsion having a pH
of 13.19, a total solids content of 9. 3% and a total actives content of 19.3%. It had a cloud point in escess of 100~C
and no flash point.
At a 1:5 dilution with water, the composition effected 50% removal of black Magic Mar)~er markings from an alkyd enameled steel panel.
This composition at a 1:2 dilution with water was subjected to the degreasing test method of E~ample 1 with the following results:
1st attack on greased slide at 4 sec.
35% removal of grease at 30 sec.
60% removal of grease at 1.0 min.
75-80% removal of grease at 1. 5 min.
85-90% removal of grease at 2.0 min.
95% removal of grease at 2. 5 min.
100% removal of grease at 2. 75 min.

E~ample 21 E~ample 2 was repeated in formulating an a~ueous, cleaner/degreaser microemulsion having the following composition:
ComPonent Wt.
Anhydrous sodium 2.0 metasilicate Dodecylbenzenesulfonic acid 2. 5 Chelating agent 1. 5 (Hampene 100, 40%) Tripropyleneglycol 2.5 monomethyl ether l-Pheno~y-2-propanol 7.0 (Dowanol PPh) SUBSTITUTE SHEET

W O 91/00337 PC~r/US90/03317 3~
,~ Sodium ~ylene sulfonate (40%) 9.O
Soft H20 75.5 10 0 ~ O
The composition was a faint bluish microemulsion having a pH of 13.05 a total solids content of 8.7% and a total actives content of 18.2%. It had a cloud point of appro~i-mately 75~C and no flash point.
At a 1:5 dilution with water, the composition effected appro~imately 95% of black Magic Marker markings from an alkyd enameled steel panel.
This composition at a 1:2 dilution with water was subjected to the degreasing test method of E~ample 1 with the following results:
1st attack on greased slide at 4 sec.
45% removal of qrease at 30 sec.
65-70% removal of grease at 1.0 min.
80~ removal of grease at 1.5 min.
90% removal of grease at 2.0 min.
100% removal of grease at 2.5 min.

E~ample 22 E~ample 21 was repeated in formulating an aqueous microemulsion containing no builder component and having the following composition:
ComPonent Wt.
25 Dodecylbenzenesulfonic acid 2.5 Sodium hydro~ide (50%) 0.4 Chelating agent 1.5 (Hampene 100, 40%) Tripropyleneglycol 2.5 monomethyl ether l-~heno~y-2-propanol 7.0 (Dowanol PPh) SUBSTITUTE SHEET

~ 37 Sodium ~ylene sulfonate (40%) 6.5 Soft H2O 7.96 100.O
The small amount of sodium hydro~ide was included to partially neutralize the dodecylbenzenesulfonic acid and cause salt formation. The composition was a faint opalescent microemulsion having a pH of 7.0, a total solids content of 5.9% and a total actives content of 15.4%. It had a cloud point in e~cess of 100~C and e~hibited no flash point.
At a 1:5 dilution with water, the composition effected only 0-5% removal of black Magic Marker markings from an alkyd enameled steel panel.
The composition at a 1:2 dilution with water was subjected to the degreasing test method of E~ample 1 with the following results:
1st attack on greased slide at 11 sec.
5-10% removal of grease at 30 sec.
30% removal of grease at 1.0 min.
55-60% removal of grease at 1.5 min.
70% removal of grease at 2.0 min.
85-90% removal of grease at 3.0 min 95% removal of grease at 4.0 min.
100% removal of grease at 4.5 min.
Thus, by comparison with the composition of Esample 21, the composition of this e~ample containing no builder component was less effective than the builder-containing composition of E~ample 21.

E~amPle 23 E~ample 2 was repeated in formulating an aqueous, cleanerfdegreaser microemulsion having the following composition:

SUB~ I ~ I ~JTE SHEET

~' .
~' ComPonent Wt. %
~"
Sodium tripolyphosphate 2.0 Dodecylbenzenesulfonic acid 2.5 Chelating agent (Hampene 100, 40%) 1.5 Tripropyleneglycol monomethyl ether 2.5 l-Pheno~y-2-propanol (Dowanol PPh) 7.0 Sodium ~ylene sulfonate (40%) 7.5 Soft H2O 76.4 100.O
The composition was a bluish, opalescent microemulsion having a pH of 11.27, a total solids content of 8.4% and a total actives content of 17.9%. It had a cloud point in e~cess of 100~C and e~hibited no flash point.
At a 1:5 dilution with water, the composition effected 60% removal of black Magic Mar~er markings from an al~yd enameled steel panel.
The composition at a 1:2 dilution with water was subjected to the degreasing test method of E~ample 1 with the following results:
1st attack on greased slide at 6 sec.
25% removal of grease at 30 sec.
40-45% removal of grease at 1.0 min.
65-70% removal of grease at 1.5 min.
80% removal of grease at 2.0 min.
90% removal of grease at 2.5 min.
100% removal of greast at 3.0 min.

E~ample 24 E~ample 2 was repeated in formulating an aqueous, cleaner/degreaser microemulsion having the following composition:

SUBSTITUTE SHEE~

W O 91/00337 PC~r/US90/03317 39 ~ .

ComPonent Wt. %
Anhydrous sodium metasilicate 2.2 Dodecylbenzenesulfonic acid 2.5 Polyglycol llZ-2(Dow) 10.0 Block ethylene o~ide/
propylene o~ide copolyol, terminated by glycerol) Soft H2O 85.3 100 . O
The composition was a very faint microemulsion having a pH
of 12.73, and a total solids and total acti~es content of 14.7%. It had a cloud point of 40~C and e~hibited no flash point.
At a 1:5 dilution with water, the composition effected 100% removal of black Magic Marker markings from an alkyd enameled steel panel.
The composition at a 1:2 dilution with water was subjected to the degreasing test method of Esample 1 with the following results:
1st attack on greased slide at 4 sec.
20% removal of grease at 30 sec.
55-60% removal of grease at 1.0 min.
80% removal of grease at 1.5 min.
100% removal of greast at 2.0 min.

E~amPle 25 E~ample 2 was repeated in preparing the following composition containing a highly water soluble organic solvent instead of a sparingly water soluble organic solvent:
ComPonent Wt.
Anhydrous sodium metasilicate 2.0 Dodecylbenzenesulfonic acid 2.4 SUBSTITUTE SHEET

Ethylene glycol monobutyl ether (Butyl Cellosolve) 10.0 ~7 Soft H2O 85.6 100.0 The composition was a clear, very pale yellow solution having a pH of 12.53, a total solids content of 4.4% and a total actives content of 14.4%. It had a cloud point in e~cess of 100~C.
At a 1:5 dilution with water, the composition effected less than 5% removal of black Magic Marker mark-ings from an alkyd enameled steel panel.
The composition at a 1:2 dilution with water was subjected to the degreasing test method of Esample 1 with the following results:
1st attack on greased slide at 20 sec.
15% removal of grease at 1.0 min.
25-30% removal of grease at 20 min.
35-40% removal of grease at 3.0 min.
45% removal of grease at 4.0 min.
50-55% removal of grease at 6.0 min.
65% removal of grease at 10.0 min.
75% removal of grease at 15.0 min.
80% removal of grease at 20.0 min.
85% removal of grease at 25.0 min.
90% removal of grease at 30.0 min.
95% removal of grease at 35.0 min.
100% removal of grease at 39.0 min.

E~amPle 26 E~ample 2 was repeated in formulating an aqueous, cleaner~degreaser microemulsion having the following composition:

SUBSTITUTE SHEET

W O 91/00337 PC~r/US90/03317 7 ~;

ComPonent Wt. %
Anhydrous sodium metasilicate 2.3 Dodecylbenzenesulfonic acid 2.8 Tripropyleneglycol monomethyl ether 5.0 Acetophenone 5.0 Soft H20 84.9 100.O
The composition was a bluish, irridescent microemulsion having a pH of 12.61, a total solids content of 5.1% and a total actives content of 15.1%. It had a cloud point in e~cess of 100~C and eshibited no flash point.
At a 1:5 dilution with water, the composition effected 100% removal of black Magic Mar~er markings from an alkyd enameled steel panel.
The composition at a 1:2 dilution with water was subjected to the degreasing test method of Esample 1 with the following results:
1st attack on greased slide at 5 sec.
25-30~ removal of grease at 30 sec.
70% removal of grease at 1.0 min.
100% removal of grease at 1.5 min.

E~ample 27 E~ample 2 was repeated in formulating an aqueous Z5 cleaner~degreaser microemulsion having the following composition:
ComPonent Wt. %
Anhydrous sodium metasilicate 2.0 Dodecylbenzenesulfonic acid 2.5 Cyclohe~anol 8.5 SUBSTITUTE SHEET

W O 91/00337 PC~r/US90/03317 g~
.

~G Tripropyleneglycol monomethyl ether 1.5 Sodium ~ lene sulfonate ( 4096) 5. 4 Soft H20 80.1 100.0 The composition was a faint bluish microemulsion having a pH of 12.74, a total solids content of 6.66% and a total actives content of 16.66%. It had a cloud point of 65~C.
At a dilution of 1:5 with water, the composition effected appro~imately 65~ removal of black Magic Mar~er markings from an al~yd enameled steel panel.
The composition at a 1:2 dilution with water was subjected to the degreasing test method of Esample 1 with the following results:
1st attack on greased slide at 1.5 sec.
5-10% removal of grease at 30 sec.
15% removal of grease at 1.0 min.
20% removal of grease at 2.0 min.
30% removal of grease at 3.0 min.
40% removal of grease at 4.0 min.
50-55% removal of grease at 5.0 min.
70% removal of grease at 6.0 min.
85% removal of grease at 7.0 min.
100% removal of grease at 8.0 min.

E~ample 28 E~ample Z was repeated in formulating an aqueous, cleaner~degreaser microemulsion having the following compositlon:
Com~onent Wt. %
Anhydrous sodium metasilicate 2.0 2-Pheno~yethanol (Dowanol EPh) 9.0 SUBSTITUTE SHEET

Coco betaine (30%) 4.0 Sodium ~ylene sulfonate (40%) 9.6 Soft H2O 75~4 lO0.0 The composition was a light bluish, irridescent micro-emulsion having a pH of 13.42, a total solids content of 7.04 and a total actives content of 16.04%. It had a cloud point above 100~C and no flash point.
At a dilution of l:5 with water, the composition effected 100% removal of black Magic Marker markings from an alkyd enameled steel panel.
The composition at a 1:2 dilution with water was subjected to the degreasing test method of E~ample l with l~ the following results:
1st attack on greased slide at 3 sec.
25-30% removal of greast at 30 sec.
65-70% removal of grease at l.0 min.
lO0~ removal of grease at l.5 min.

Z~ E~ample 29 An aqueous, cleaner/degreaser formulation in the form of a microemulsion was prepared having the following composition:
ComPonent Wt. %
Monoethanolamine 0.5 Sodium Metasilicate 2.0 l-Pheno~y-2-propanol 7.0 (D~wanol PPh) Tripropyleneglycol monomethyl 3.0 ether Doodecylbenzenesulfonic acid 3.0 Soft HzO 8Z.4 SUBSTITUTE SHEET

W O 91/00337 PC~r/US90/03317 ~' ~,6 Isodecylo~ypropylimino- 2.0 dipropionic acid (~Alkali Surfactant~, Tomah Products, 35%) Defoaming agent (Atsurf F-12) 0.1 100.O
The sodium metasilicate was dissolved in water with stirring The monoethanolamine was added followed by the addition of the 1-pheno~y-2-propanol, tripropyleneglycol monomethyl ether and dodecylbenzenesulfonic acid with stirring Stirring was continued until a homogeneous emulsion formed. The Alkali Surfactant was then added and the emulsion was transformed into a microemulsion after which the defoaming agent was added. The resulting micro-emulsion had a slightly bluish, irridescent appearance, a pH of 12.42, a total solids content of 5.7% and a total actives content of 16.2%. It e~hibited a cloud point in e~cess of 100~C.
The composition at a 1:2 dilution with water was subjected to the degreasing test method of E~ample 1 with the following results:
1st attack on greased slide at 1 sec.
40% removal of grease at 15 sec.
75% removal of grease at 30 sec.
100% removal of grease at 65 sec.
In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.
As various changes could be made in the above compositions without departing from the scope of the invention, it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.

SUBSTlTUTE SHEET'

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A stable, aqueous cleaner/degreaser composition in the form of a microemulsion comprising:
(a) at least one sparingly water soluble organic solvent characterized by:
(i) having a water solubility in the range of approximately 0.2 to approximately 6 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) from approximately 0.25 to 10.0 wt. %, based on the total composition, of a builder;
(c) 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 not substantially exceeding the amount required to transform the combination of said organic solvent and said builder from the form of a -45a-true macroemulsion to the form of a microemulsion and less than that required to form a true solution; and (d) water.

2. A stable, aqueous cleaner/degreaser composition as set forth in claim 1 wherein said organic solvent has a water solubility in the range of approximately 1 to approximately 2.5 weight percent.

3. A stable, aqueous cleaner/degreaser 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.

4. A stable, aqueous cleaner/degreaser composition as set forth in claim 1 wherein said organic solvent is selected from the group consisting of 2-phenoxyethanol, 1-phenoxy-2-propanol, .beta.-phenylethanol, acetophenone, benzyl alcohol, butoxyethyl acetate, isophorone and the dimethyl esters of mixed succinic, glutaric and adipic acids.

5. A stable, aqueous cleaner/degreaser composition as set forth in claim 1 wherein said builder is selected from the group consisting of alkali metal hydroxides, alkali metal silicates and metasilicates, alkali metal carbonates, bicarbonates and sesquicarbonates, borax, alkali metal phosphates, pyrophosphates, tripolyphosphates, hexametaphosphates and tetraphosphates, and alkali metal perborates.

6. A stable, aqueous cleaner/degreaser composition as set forth in claim 1 wherein said builder is sodium metasilicate.

7. A stable, aqueous cleaner/degreaser composition as set forth in claim 1 wherein said surfactant is selected from the group consisting of anionic, nonionic, cationic and amphoteric surfactants.

8. A stable, aqueous cleaner/degreaser composition as set forth in claim 1 wherein said surfactant is an anionic surfactant selected from the group consisting of dodecylbenzene sulfonic acid, sodium dodecylbenzene-sulfonate, potassium dodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate, morpholinium dodecylbenzene sulfonate, ammonium dodecylbenzene sulfonate, isopropylamine dodecylbenzene sulfonate, sodium tridecylbenzene sulfonate, sodium dinonylbenzene sulfonate, potassium didodecylbenzene sulfonate, dodecyl diphenyloxide disulfonic acid, sodium dodecyl diphenyloxide disulfonate, isopropylamine decyl diphenyloxide disulfonate, sodium hexadecyloxypoly(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/dioctylphenoxypoly(ethyleneoxy)(9)phosphate.

9. A stable, aqueous cleaner/degreaser 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, and sodium capro imidazoline amphoylycinate.

10. A stable, aqueous cleaner/degreaser composition as set forth in claim 1 wherein said organic solvent is 2-phenoxyethanol.

11. A stable, aqueous cleaner/degreaser composition as set forth in claim 1 wherein said organic solvent is 1-phenoxy-2-propanol.