Europaisches Patentamt

European Patent Office

© Publication number: 0 479 908 B1
Office europeen des brevets

© EUROPEAN PATENT SPECIFICATION

© Date of publication of patent specification: 08.03.95 © Int. CI.6: C1 1 D 3 / 4 3

© Application number: 90911174.2

@ Date of filing: 12.06.90

© International application number:

PCT/US90/03316

© International publication number:

WO 91/00336 (10.01.91 91/02)

The file contains technical information submitted

after the application was filed and not included in
this specification

© IMPROVED AQUEOUS CLEANER/DEGREASER COMPOSITIONS.

© Priority: 29.06.89 US 373813 Proprietor: BUCKEYE INTERNATIONAL, INC.

2700 Wagner Place
@ Date of publication of application: Maryland Heights, MO 63043-3471 (US)
15.04.92 Bulletin 92/16
Inventor: VANEENAM, Donald, N.
© Publication of the grant of the patent: 767 Oak Valley Drive
08.03.95 Bulletin 95/10 DesPeres, MO 63131 (US)

© Designated Contracting States:

AT BE CH DE DK ES FR GB IT LI LU NL SE Representative: Baverstock, Michael George
Douglas et al
References cited: BOULT, WADE & TENNANT
EP-A- 0 040 882 EP-A- 0 058 637 27 Furnival Street
EP-A- 0 171 122 US-A- 4 248 928 London, EC4A 1PQ (GB)
US-A- 4 264 466 US-A- 4 758 377
US-A- 4 861 512

00 HACKH's Chemical Dictionnary, Mc Graw-

Hill, p. 876
00
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Oi
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Note: Within nine months from the publication of the mention of the grant of the European patent, any person
may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition
shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee
has been paid (Art. 99(1) European patent convention).
Rank Xerox (UK) Business Services
(3. 10/3.09/3.3.3)
 EP 0 479 908 B1

Description

Background of the Invention

5 This invention relates to cleaner/degreaser compositions and, more particularly, to stable, aqueous
cleaner/degreaser compositions in the form of totally water soluble solutions which exhibit superior cleaning
and degreasing capability.
Heretofore, all of the conventional and available ready to use and concentrated water soluble, dilutable
cleaner/degreaser compositions have expediently contained infinitely or highly water soluble organic
io 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 together with anionic or nonionic surfactants and conventional adjuvants such chelants,
builders, perfumes, dyes, pH adjustors, etc., these components falling generally within the following
compositional wt.% ranges:
75 2-10% Water soluble solvent(s)
1-3% Anionic or nonionic surfactant
0.1-3% Adjuvants
QS Water
100.0%
20 Such conventional compositions are generally deficient in cleaning action and especially in heavy duty
grease, oil, wax, etc. cutting action, often smell objectionably strongly of volative solvent and can
sometimes present conbustability problems in concentrated form. They also tend to be harsh on the hands
and to defat the shin. Further, heavy scrubbing, mopping or other mechanical action is generally required to
attain the desired cleaning/degreasing action, especially where excessive soilant buildup has occurred.
25 Most, even in their concentrated form, are ineffective in their capability to remove graffiti or the like.
EP-A-0 171 122 describes liquid aqueous cleaners to produce high shine quality comprising benzyl
alcohol and ethylene diamine tetraacetate and also preferably containing a carbitol or cellusolve solvent and
a surfactant.
EP-A-0 040 882 describes aqueous liquid detergent compositions particularly for use as hard surface
30 cleaners, comprising a polar solvent, a surfactant and a mono- or sesquiterpene.
While not wishing to be held to any rigid theory as to the nature of the cleaning and degreasing action
of presently available compositions, it is believed that highly or infinitely water soluble organic solvents
presently used in both retail as well as industrial and institutional cleaner/degreaser compositions are too
hydrophilic in nature to function effectively in removing hydrophobic (oleophilic) soilants, especially in the
35 presence of diluting water. As the level of the latter is increased to bring conventional compositions to ready
to use strength, the solvating action of the organic solvent is drastically reduced with a consequent and
marked reduction in the cleaning/degreasing action required for effective cleaning and oily soilant removal.
There remains a need, therefore, for cleaner/degreaser compositions with improved cleaning and
degreasing capability and without the other deficiencies of presently available cleaner/degreaser composi-
40 tions.

Summary of the Invention

Among the several objects of the invention may be noted the provision of stable, aqueous clean-
45 er/degreaser compositions having superior cleaning/degreaser efficacy; the provision of such compositions
which may be formulated to have a low level of odor and low volatility or a high flash point; the provision of
compositions of this type which incorporate organic solvents with inherently limited aqueous solubility; the
provision of such compositions which are nontoxic and nonhazardous in use; and the provision of such
improved compositions which may be readily formulated from available components. Other objects and
50 features will be in part apparent and in part pointed out hereinafter.
Briefly, the present invention is directed to stable, aqueous cleaner/degreaser compositions which are
formulated in the form of totally water soluble solutions. The compositions comprise:
(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;
55 (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

2
 EP 0 479 908 B1

(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, the solubilizing additive being
present in an amount not exceeding approximately (twofold) that required to completely solubilize the
5 organic solvent; and
(c) water said composition containing neither 2-(2-butoxyethoxy)ethanol nor ethylene glycol monohexyl
ether. The compositions of the invention exhibit markedly superior cleaning/degreasing efficacy over that
achievable with compositions containing infinitely water soluble organic solvents such as butyl cellosolve
and butyl carbitol.
10
Description of the Preferred Embodiments

In accordance with the present invention, it has now been found that stable, totally water soluble,
aqueous cleaner/degreaser compositions having superior cleaning and degreasing capabilities can be
is formulated by combining at least one sparingly water soluble organic solvent having certain characteristics
and being present in an amount exceeding its aqueous solubility with a solubilizing additive and water, the
solubilizing additive being present in an amount not exceeding approximately (twofold) that required to
completely solubilize the organic solvent. Surprisingly, as demonstrated by the experimental data presented
hereinafter, it has been discovered that the optimum cleaning/degreasing efficacy is attained by utilizing an
20 organic solvent of inherently low or limited water solubility and rendering it just completely water soluble by
means of one or more solubilizing additives, i.e. by employing a sparingly water soluble organic solvent and
teasing it into complete solution by the addition of a minimum amount of one or are solubilizing additives.
Unexpectedly, it has also been found that the addition of an excess of a solubilizing additive over that
required to completely solubilize the sparingly soluble organic solvent somewhat lowers or detracts fro the
25 degreasing efficacy of the cleaner/degreaser composition as experimentally demonstrated hereinafter.
Further, the optimum cleaning/degreasing efficacy is achieved by utilizing organic solvents which have
limited water solubility in the range of approximately 0.2 to approximately 6 weight percent of the total
composition, organic solvents with water solubilities outside this range appearing to provide less effective
cleaning/degreasing action. Thus, it is critical to the present invention that a sparingly water soluble organic
30 solvent be optimally formulated with a solubilizing additive in order to maintain minimal aqueous solubility of
the solvent.
In the past, highly or infinitely water soluble solvents have been used in cleaner/degreaser composi-
tions, but such solvents are too hydrophilic to effectively remove hydrophobic or oleophilic soilants from
surfaces to which such compositions are applied. On the other hand, the present invention permits the
35 practical and effective use of normally hydrophobic (oleophilic) solvents which have great affinity for and
dissolving action against oleophilic soilants. It is believed that such sparingly water soluble organic solvents,
formulated in accordance with the present invention, lose less of their oily soilant solvency in aqueous
solution than their more hydrophilic counterparts because of their borderline aqueous solubility, attained and
maintained by the judicious use of solvating surfactants and couplers. Therefore, the solvents of limited
40 solubility used herein are better able to maintain their soilant dissolving, dispersing and suspending action
than highly or infinitely water soluble solvents. Consequently, when optimally formulated to maintain minimal
aqueous solubility as herein described, the totally aqueous cleaner/degreaser compositions of this invention
containing limited water soluble solvents exhibit truly superior oily soilant solvent action. Moreover, the
compositions of the invention are true aqueous solutions rather than emulsions or microemulsions as
45 evidenced by the fact that they exhibit no Tyndall effect.
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 approximately 0.2 to 6 weight percent; preferably
approximately 1 to 2.5 weight percent;
50 (b) it must not be a hydrocarbon or halocarbon;
(c) it must have one or more similar or dissimilar oxygen, 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 exceeding its limited aqueous solubility.
55 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

3
 EP 0 479 908 B1

desired similar 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
acetone (2 keto groups), diethylethylene diphosphonate (2 phosphonate ester groups), ethylenedipropionate
(2 ester groups), decylene glycol (2 hydroxyl groups), m-dimethoxybenzene (2 ether groups), adiponitrile (2
5 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-phenoxyethanol (hydroxy, ether groups), 1-phenoxy-2-propanol(hydroxy, ether groups), N-
phenylmorpholine(amino, ether groups), isopropylacetoacetate (keto, ester groups), o-methoxybenzyl al-
cohol (ether, hydroxy groups), 4'-methoxyacetophenone (ether, ketone groups), o-nitrophenetole (nitro, ether
io groups), 2-hexoxyethanol (hydroxy, ether groups), ethylcyanoacetoacetate (cyano, keto, ester groups), p-
anisaldehyde (ether, aldehyde groups), polypropylene glycol 1200 (ether, hydroxyl groups), n-butoxy
acetate (ether, ester groups), and 2-phenylthioethanol (thioether, hydroxyl groups).
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, exhibit a low level of odor, be chemically stable, nontoxic,
is nonhazardous and commercially available.
The sparingly water soluble organic solvents which may be employed in the practice of the present
invention (and comprising some of the solvents listed above) together with their aqueous ambient
temperature solubility in wt.% include 2-phenoxyethanol (2.3) (marketed under the trade designation
"Dowanol EPh"), 1-phenoxy-2-propanol (1.1) (marketed under the trade designation "Dowanol PPh"), /3 -
20 phenylethanol (1 .6), acetophenone (0.5), benzyl alcohol (4.4), benzonitrile (1 .0), n-butyl acetate (0.7), n-amyl
acetate (0.25), benzaldehyde (0.3), N,N-diethylaniline (1.4), diethyl adipate (0.43), dimethyl-o-phthalate
(0.43), n-amyl alcohol (2.7), N-phenylmorpholine (1.0), n-butoxyethyl acetate (EB acetate) (1.1), cyclohex-
anol (4.2), polypropylene glycol 1200 (2), cyclohexanone (2.3), isophorone (1.2), methylisobutyl ketone (2.0),
methylisoamyl ketone (0.5), tri-n-butylphosphate (0.6), 1-nitropropane (1.4), nitroethane (4.5), dimethyl
25 esters of mixed succinic, glutaric and adipic acids (5.7) (marketed under the trade designation "DBE ester"
by DuPont), diethyl glutarate (0.88), and diethyl malonate (2.08). As will be apparent to those skilled in the
art, the above-listed sparingly water soluble organic solvents are merely illustrative and various other
solvents meeting the criteria set out above may also be utilized in the practice of the invention. Because of
their performance characteristics, lack of odor, low volatility/high flash point, chemical stability and
30 availability, 2-phenoxyethanol and 1-phenoxy-2-propanol are the preferred organic solvents of choice. N-
butoxyethyl acetate (EB acetate) and the dimethyl esters of mixed succinic, glutaric and adipic acids are
also among the preferred organic solvents.
As indicated, a number of otherwise potent organic solvents having an aqueous solubility of less than
approximately 0.2 weight percent such as 2-(2-ethylhexoxy)ethanol (2-ethylhexyl cellosolve) having an
35 aqueous solubility of only 0.095 wt.%, and 2,6-dimethyl-4-heptanone (diisobutyl ketone) (aq. sol. 0.05 wt.
%), and organic solvents having an aqueous solubility in excess of approximately 6 weight percent such as
propylene glycol monomethyl ether acetate (aq. sol. 16.5 wt.%), ethylene glycol diacetate (aq. sol. 14.3
wt.%), propylene carbonate (aq. sol. 19.6 wt.%) and N-methyl pyrrolidone (infinite aq. sol.) are not useful in
the practice of the invention.
40 In formulating the stable, aqueous cleaner/degreaser compositions of the invention, an organic solvent
meeting the required criteria is combined with a solubilizing additive and water. The solubilizing additive
consists of from approximately 0.1 to approximately 100 weight percent of a surfactant and from 0 to
approximately 99.9 weight percent of a coupler and the solubilizing additive is preferably present in the
formulated composition in an amount not substantially exceeding that required to completely solubilize the
45 particular organic solvent being used, i.e. a minimum level of the solubilizing additive is used in order to
render the organic solvent "barely soluble" in the aqueous solution so as to achieve maximum or optimum
degreasing action. The amount of solubilizing agent (surfactant or surfactant plus coupler) required to
accomplish this objective will vary depending upon the particular organic solvent employed and can readily
he determined by simple experimentation in each instance.
50 It is highly preferred in formulating the compositions of the invention that the solubilizing additive be
present in an amount not substantially exceeding that required to completely solubilize the sparingly water
soluble organic solvent.
In order to obtain optimum results, the solubilizing agent is present in the minimum amount or up to
twofold the minimum amount necessary to just solubilize the organic solvent. As the amount of solubilizing
55 additive increases, the cleaning/degreasing efficacy tends to decrease.
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

4
 EP 0 479 908 B1

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 soluble while in other instances the use of a
surfactant in combination with a coupler may be utilized to achieve the desired complete aqueous
solubilization of the organic solvent. Whether or not a surfactant alone or the combination of a surfactant
5 and coupler is to be used is dependent upon the particular organic solvent and surfactant employed and
can readily be determined in each particular case by simple experimentation.
The surfactant used may be an anionic, nonionic, cationic or amphoteric surfactant, and the use of
anionic or nonionic surfactants is generally preferred, especially for hard surface cleaning/degreasing.
Illustrative anionic surfactants for use in the invention include dodecylbenzene sulfonic acid, sodium
io dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate,
morpholinium dodecylbenzene sulfonate, ammonium dodecylbenzene sulfonate, isopropylamine dodecyl-
benzene sulfonate, sodium tridecylbenzene sulfonate, sodium dinonylbenzene sulfonate, potassium
didodecylbenzene sulfonate, dodecyl diphenyloxide disulfonic acid, sodium dodecyl diphenyloxide disul-
fonate, isopropylamine decyl diphenyloxide disulfonate, sodium hexadecyloxypoly(ethyleneoxy)(10)ethyl
is sulfonate, potassium octylphenoxypoly(ethyleneoxy)(9)ethyl sulfonate, sodium alpha C12—h 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 diisobutylsulfosuccinate, disodium laurylsulfosuccinate,
20 tetrasodium N-laurylsulfosuccinimate, sodium decyloxypoly(ethyleneoxy(5)methyl)carboxylate, sodium
octylphenoxypoly(ethyleneoxy(8)methyl)carboxylate, sodium mono decyloxypoly(ethyleneoxy)(4)phosphate,
sodium di decyloxypoly(ethyleneoxy)(6)phosphate, and potassium mono/di octylphenoxypoly(ethyleneoxy)-
(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 octylphenoxypoly-
25 (ethyleneoxy)-(l 1)ethanol, nonylphenoxypoly(ethyleneoxy)(13)ethanol, dodecylphenoxypoly(ethyleneoxy)-
(10) ethanol, polyoxyethylene (12) lauryl alcohol, polyoxyethylene (14) tridecyl alcohol, lauryloxypoly-
(ethyleneoxy)(10)ethyl methyl ether, undecylthiopoly(ethyleneoxy)(12)ethanol, methoxypoly(oxyethylene(10)-
/(oxypropylene(20))-2-propanol block copolymer, nonyloxypoly(propyleneoxy)(4)/(ethyleneoxy)(1 6)ethanol,
dodecyl polyglycoside, polyoxyethylene (9) monolaurate, polyoxyethylene (8) monoundecanoate, polyox-
30 yethylene (20) sorbitan monostearate, polyoxyethylene (18) sorbitol monotallate, sucrose monolaurate,
lauryldimethylamine oxide, myristyldimethylamine oxide, lauramidopropyl-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, coconut diethanolamide, "modified", and
coconut diethanolamide, "long chain modified". Other known nonionic surfactants may likewise be used.
35 Illustrative useful cationic surfactants include a mixture of n-alkyl (such as C12 50%, C14 30%, Cig
17%, Cis 3%) dimethyl ethylbenzyl ammonium chlorides, hexadecyltrimethylammonium methosulfate,
didecyldimethylammonium bromide and a mixture of n-alkyl (such as 68% C12, 32% C14) dimethyl benzyl
ammonium chlorides. Similarly useful amphoteric surfactants include cocamidopropyl betaine, sodium
palmityloamphopropionate, N-coco beta-aminopropionic acid, disodium N-lauryliminodipropionate, sodium
40 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 dodecylbenzenesul-
fonic acid and the sodium, potassium, triethanolamine, morpholinium, ammonium and isopropylamine salts
thereof, and morpholinium tallate.
45 The couplers which may be utilized in the practice of the invention include sodium benzene sulfonate,
sodium toluene sulfonate, sodium xylene sulfonate, potassium ethylbenzene sulfonate, sodium cumene
sulfonate, sodium octane-1 -sulfonate, potassium dimethylnaphthalene sulfonate, ammonium xylene sul-
fonate, sodium n-hexyl diphenyoxide disulfonate, sodium 2-ethylhexyl sulfate, ammonium n-butoxyethyl
sulfate, sodium 2-ethylhexanoate, sodium pelargonate, sodium n-butoxymethyl carboxylate, potassium
50 mono/di phenoxyethyl phosphate, sodium mono/di n-butoxyethyl phosphate, triethanolamine trimethylol-
propane phosphate, sodium capryloamphopropionate, disodium capryloiminodipropionate, and sodium
capro imidazoline amphoglycinate. 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
55 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 mixed solubilizing surfactant system. For example, a combination of compatible

5
 EP 0 479 908 B1

anionic and 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 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 solvent solubilization. The compatibility of the various
5 surfactants and of the various couplers with each other and in combination can be readily determined by
simple experimentation.
Similarly, but less preferably, a mixture of the sparingly soluble organic solvents may be employed in
formulating the compositions of the invention. However, if a mixture of solvents is to be used, each of the
solvents should have nearly the same approximate water solubility so that they will solubilize in water at
io approximately the same point upon addition of the solubilizing additive.
In addition to the organic solvent and solubilizing additive components of the compositions of the
invention, various optional adjuvants can be incorporated. These include chelants such as the sodium salts
of ethylenediaminetetraacetic acid (Hampene 100 or Versene 100), thickeners such as carboxy acrylic
polymers (Carbopol 940) or acrylic acid/alkyl methacrylate copolymers (Acrysol ICS-1), fragrances, dyes,
is pH adjustants, anti-corrosion additives and anti-rust additives. In general, it is preferred that the composi-
tions be formulated to have a pH of about 7.0 so as to be gentle to the hands and avoid defatting the skin.
While the various components comprising the resultant compositions may generally be brought
together in any prescribed order under mechanical mixing conditions at ambient temperatures, it is often
found expeditious to either add water slowly to the stirred, blended organic components or to add the
20 premixed organics to water with agitation. "Clearing" of the mixture, or transformation from heterogeneous
suspension to fully soluble aqueous solution, usually occurs within several minutes' stirring.
The concentration of the aqueous cleaner/degreaser solution, as indicated by the terms "total solids
content" and "total actives content" in the working examples provided hereinafter refers, respectively, to the
combined percentages of nonvolatile components and to the sum total of nonaqueous volatile and
25 nonvolatile components.
The term "cloud point" indicates the temperature below which the composition exists as a clear, single
phase solution and above which phase separation (heterogeneity) occurs. For practical reasons, a composi-
tion should preferably have a cloud point in excess of, for example 50 ° C, to have a viably safe, storage-
stable shelf life under hot, summertime warehouse conditions.
30 It is to be expected that, as the concentration of a given organic solvent is increased (with necessary
concomitant increase in solubilizing additive), the rate at which cleaning/degreasing is accomplished
likewise increases and improved cleaning/degreasing efficacy can be realized. Conversely, as the organic
solvent concentration is lowered, either by diluting a given composition with water or through changes made
in formulating the cleaner/degreaser composition, the cleaning/degreasing rate is generally lowered and
35 efficacy can be said to diminish or lessen. Thus, the concentration, as measured by "total solids content"
and "total actives content" can be adjusted to any given or desired level within the parameters, criteria, and
constraints imposed on the practice of the invention, and within the normal, viable operational limits
encountered in formulating the components of said compositions. Thus, it is possible to formulate water
soluble solution concentrates provided enough solubilizing additive is used to completely solubilize the
40 organic solvent, and that upon dilution, the cleaning/degreasing efficacy is only gradually diminished by
reason of the larger volume of water present (see results set forth in Examples 3 and 6 hereinafter).
As shown by the experimental degreasing test data presented below, the compositions of the invention
provide superior cleaning/degreasing efficacy over that achievable with commercially available clean-
er/degreasing compositions. Thus, the commercial product "Fantastik"(Trade Mark) (Texize/Dow) required 9
45 hours to achieve 100% removal of grease by the degreasing test method hereinafter described whereas the
compositions of the present invention achieve 100% removal of grease in a matter of several minutes.
The following examples illustrate the practice of the invention.

Example 1
50
In the following examples 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. 14-51 1-1 A) provided with a vaned disc magnetic
55 stir bar (22 mm (7/8") (diameter) x 15 mm (5/8") (height),) Fisher Scientific Co., Catalog No. 14-511-98C)
was used. In each instance, pre-cleaned, borosilicate glass microslides (76 mm (3") x 25 mm (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 25 mm (1.0") from the bottom edge to provide a 25 mm (1.0") x 25 mm (1.0") coated area.

6
 EP 0 479 908 B1

The test cleaner/degreaser solutions were employed at full strength unless otherwise indicated and in an
amount sufficient to fill a 50 ml Pyrex beaker containing the vaned disc magnetic stirrer bar to a level of 40
ml. Each test solution and surrounding air were maintained at 21 ± 0.5 °C and the test solution stirring rate
was determined by a setting of "3" on the stirrer dial of the magnetic stirrer. The stirring disc was
5 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 approximately 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 beaker containing the stirrer bar was filled to 40 ml. with the test cleaning/degreasing
io solution at the indicated concentration, placed atop the magnetic stirrer plate, and positioned off-center to
accomodate the glass microslide, and yet allow the vaned disc stirrer bar to rotate or spin freely. The stirrer
was turned on, the dial adjusted manually to the "3" stirring rate setting and the Vaseline thin film coated
glass microslide was introduced into the test solution bath in such a manner that the coated side faced
upward and was positioned away from the stirrer bar. The time "0" was noted immediately on a watch or
is 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 25 mm (1.0") x 25 mm (1.0")
treated area", an objective determination, after which the microslide was immediately returned to the stirred
aqueous cleaner/degreaser bath. The duration of the degreasing test is determined by the time needed for
20 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.

Example 2
25
An aqueous cleaner/degreaser formulation was prepared having the following composition:

Component Parts by weight

30 2-Phenoxyethanol (Dowanol EPh) 8.0
Dodecylbenzenesulfonic acid 1.2
Sodium hydroxide (50%) 0.3
Chelant (Hampene 100)(Trade Mark) 0.6
Water soluble dye blend 0.002
35 SoftH20 189.9
200.0

The composition was a clear, aqueous solution having a pH of 7.0, a total solids content of 0.80 wt.%, a
total actives content of 4.80 wt.% and a cloud point in excess of 100°C.
This composition was subjected to the degreasing test method described in Example 1 with the
following results:
1st attack on greased slide at 5 sec.
25% removal of grease at 20 sec.
50% removal of grease at 30 sec.
85% removal of grease at 1.0 min.
100% removal of grease at 1.25 min.
The composition exhibited very superior cleaning/degreasing action on grease, oil, smudges, black Magic
Marker markings, ballpoint pen markings, pencil markings, etc. found on any washable surface.

55

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 EP 0 479 908 B1

Example 3

An aqueous cleaner/degreaser concentrate formulation was prepared having the following composition:

Component Parts by weight

2-Phenoxyethanol (Dowanol EPh)(Trade Mark) 30.0
Sodium xylene sulfonate (40%) 30.0
Dodecylbenzenesulfonic acid 3.6
Chelant (Hampene 100)(Trade Mark) 2.0
Sodium hydroxide (50%) 0.7
Water soluble dye blend 0.002
SoftH20 133.7
200.00

The concentrate was a clear, aqueous solution having a pH of 7.0, a total solids content of 8.375%, a total
actives content of 23.4% and a cloud point in excess of 100°C.
This concentrate, at the various dilutions with water indicated below, was subjected to the degreasing
test method of Example 1 with the following results:

At a dilution of 1 part concentrate : 3 parts H2Q

1st attack on greased slide at 7 sec.

60% removal of grease at 30 sec.
80-85% removal of grease at 1.0 min.
100% removal of grease at 2.0 min.

At a dilution of 1:4

1st attack on greased slide at 10 sec.

50% removal of grease at 30 sec.
70-75% removal of grease at 1.0 min.
100% removal of grease at 2.25 min.

At a dilution of 1:5

1st attack on greased slide at 12 sec.

25% removal of grease at 30 sec.
40% removal of grease at 1.0 min.
65% removal of grease at 2.0 min.
85-90% removal of grease at 3.0 min.
100% removal of grease at 4.0 min.

At a dilution of 1:10
45
1st attack on greased slide at 15 sec.
15-20% removal of grease at 1.0 min.
30% removal of grease at 2.0 min.
50-55% removal of grease at 3.0 min.
80-85% removal of grease at 4.0 min.
100% removal of grease at 5.25 min.

At a dilution of 1:20

1st attack on greased slide at 22 sec.

10-15% removal of grease at 1.0 min.
25% removal of grease at 2.0 min.
40% removal of grease at 3.0 min.

8
 EP 0 479 908 B1

65-70% removal of grease at 4.0 min.

85% removal of grease at 5.0 min.
100% removal of grease at 6.0 min.

5 Example 4

An agueous cleaner/degreaser formulation was prepared having the following composition.

Component Wt.%
2-Phenoxyethanol (Dowanol EPh)(Trade Mark) 4.0
Tall oil carboxylic acids 0.70
Morpholine 0.60
Soft H20 94.7
100.0

The tall oil carboxylic acids and morpholine form morpholinium tallate, an amine salt or soap which
functions as an anionic surfactant/coupler. The composition was a clear, essentially colorless, low foaming,
aqueous solution having a pH of 8.83, a total solids content of 1.3%, a total actives content of 5.3% and a
cloud point in excess of 100°C.
This composition was subjected to the degreasing test method of Example 1 with the following results:
1st attack on greased slide at about 1 sec.
80% removal of grease at 10 sec.
100% removal of grease at 15 sec.
The composition very easily and readily effects the total removal of the following markings from alkyd
enameled metal surfaces: black Magic Marker felt pen, blue and black indelible ballpoint pen and #1
hardness pencil.

Example 5
30 ~
An aqueous cleaner/degreaser formulation was prepared having the following composition:

Component Wt.%
1-Phenoxy-2-propanol (Dowanol PPh)(Trade Mark) 4.0
Dodecylbenzenesulfonic acid 1.5
Sodium hydroxide (50%) 0.4
Soft H20 94.1
100.0

The composition was a clear, colorless, aqueous solution having a pH of 7.0, a total solids content of 1.7%,
a total actives content of 5.7% and a cloud point in excess of 100°C. The composition exhibited no flash
point (extinguishes flame) and was essentially odorless.
45 The composition was subjected to the degreasing test method of Example 1 with the following results.
1st attack on greased slide at 4 sec.
35% removal of grease at 15 sec.
60% removal of grease at 30 sec.
80% removal of grease at 45 sec.
50 90-95% removal of grease at 1.0 min.
100% removal of grease at 1.20 min.
The composition easily and fully removed the following markings from alkyd enameled metal surfaces:
black Magic Marker felt pen, blue and black indelible ballpoint pen, #1 hardness pencil, and red (wax)
crayon.

9
 EP 0 479 908 B1

Example 6

An aqueous cleaner/degreaser high concentrate formulation was prepared having the following composi-
tion:
5
Component Wt.%
2-Phenoxyethanol (Dowanol EPh)(Trade Mark) 60.0
Dodecylbenzenesulfonic acid 10.0
Sodium hydroxide (50%) 2.7
Sodium xylene sulfonate (40%) 12.3
SoftH20 15.0
100.0

The concentrate was a clear, pale yellow, aqueous solution having a pH of 7.0, a total solids content of
16.27%, a total actives content of 76.27% and a cloud point in excess of 100 °C. The concentrate exhibited
no flash point up to 93 ° C (200 ° F) and had a very bland odor.
A clear, colorless, aqueous solution was formed by diluting 1 part of the concentrate with 15 parts of
water. The diluted solution was subjected to the degreasing test method of Example 1 with the following
results:
1st attack on greased slide at 4 sec.
33% removal of grease at 30 sec.
65% removal of grease at 1.0 min.
85% removal of grease at 1.5 min.
100 % removal of grease at 2.0 min.
The diluted solution easily and totally removed the following markings from alkyd enameled metal surfaces:
black indelible Magic Marker felt pen, blue and black indelible ballpoint pen, #1 hardness pencil and red
(wax) crayon.

Example 7

An aqueous cleaner/degreaser concentrate formulation was prepared having the following composition:

Component Wt.%
1-Phenoxy-2-propanol (Dowanol PPh)(Trade Mark) 15.0
Dodecylbenzenesulfonic acid 4.0
Sodium hydroxide (50%) 1.0
Sodium xylene sulfonate (40%) 19.0
SoftH20 61.0
100.0

The concentrate was a very clear, slightly straw colored, aqueous solution having a pH of 7.0, a total solids
45 content of 12.1%, a total actives content of 27.1% and a cloud point in excess of 100°C. The concentrate
exhibited no flash point and had essentially no odor.
Upon diluting 1 part of the concentrate with 5 parts of water, a faint bluish microemulsion was formed.
The diluted concentrate was subjected to the degreasing test method of Example 1 with the following
results:
50 1st attack on greased slide at 5 sec.
15-20% removal of grease at 30 sec.
33% removal of grease at 1.0 min.
55% removal of grease at 2.0 min.
80-85% removal of grease at 3.0 min.
55 90% removal of grease at 3.5 min.
100% removal of grease at 4.25 min.
The diluted composition easily and fully removed the following markings from alkyd enameled metal
surfaces: black indelible Magic Marker felt pen, blue and black indelible ballpoint pen, #1 hardness pencil

10
 EP 0 479 908 B1

and red (wax) crayon.

Example 8

An aqueous cleaner/degreaser formulation was prepared having the following composition:

Component Wt.%
1-Phenoxy-2-propanol (Dowanol PPh)(Trade Mark) 15.0
10 Dodecylbenzenesulfonic acid 5.4
Sodium xylene sulfonate (40%) 8.0
Sodium hydroxide (50%) 1.4
Soft H20 70.2
100.0
15
The concentrate was a clear, very pale straw colored, aqueous solution having a pH of 7.0, a total solids
content of 9.3%, a total actives content of 24.3% and a cloud point in excess of 100 °C. The concentrate
exhibited no flash point and was essentially odorless.
Upon diluting 1 part of the concentrate with 3 parts of water, a bluish microemulsion was formed. The
20
diluted concentrate was subjected to the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 5-6 sec.
20-25% removal of grease at 30 sec.
35% removal of grease at 1.0 min.
50% removal of grease at 1.5 min.
25
70% removal of grease at 2.0 min.
80-85% removal of grease at 2.5 min.
90-95% removal of grease at 3.0 min.
100% removal of grease at 3.5 min.
The diluted composition easily and fully removed the same markings as were removed by the diluted
30
composition of Example 6.

Example 9

An aqueous cleaner/degreaser formulation was prepared having the following composition:

35

Component Wt.%
2-Phenoxyethanol (Dowanol EPh)(Trade Mark) 4.0
Dodecylbenzenesulfonic acid 6.0
40
Sodium hydroxide (50%) 1.6
Chelant (Hampene 100)(Trade Mark) 0.3
Water soluble dye blend 0.001
Soft H20 88.1
100.00
45

The composition was a clear, aqueous solution having a pH of 7.0, a total solid content of 6.9%, a total
actives content of 10.9% and a cloud point in excess of 100°C.
The above composition is similar to that of Example 2 except that it contains a tenfold increase in the
50 amount of the solubilizing additive, dodecylbenzenesulfonic acid. While the composition of Example 2
exhibited very superior cleaning/degreasing action on grease, oil, smudges, black Magic Marker markings,
ballpoint pen markings, pencil markings, etc. involving their complete 100% removal, the above composition
gave the following cleaning/degreasing results:

55

11
 EP 0 479 908 B1

% Soilant Removal
Soilant % Removed
Graphite pencil 100
black Magic Marker felt pen 10-15
blue ballpoint pen (indelible) 5
black ballpoint pen (indelible) 5
automotive grease 50
red (waxy) crayon 100
"Takilube" (Trade Mark) outside gear lubricant 40

The above results were obtained upon 10 seconds light rubbing with a Kimwipe (Trade Mark) tissue wetted
with the above composition. Thus, while not as effective as the composition of Example 2, the above
75 composition nevertheless functions well in removing greasy, waxy, oily soils from surfaces and is
comparable in many respects to ready to use industrial and retail grade cleaner/degreaser compositions.
The composition was subjected to the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 25 min.
5% removal of grease at 1.0 hr.
20 5-10% removal of grease at 2.0 hr.
15-20% removal of grease at 3.5 hr.
33% removal of grease at 5.0 hr.
45% removal of grease at 6.5 hr.
60% removal of grease at 8.0 hr.
25 75% removal of grease at 10.5 hr.
85-90% removal of grease at 12.0 hr.
95% removal of grease at 14.5 hr.
100% removal of grease at 15.0 hr.

30 Example 10

An aqueous cleaner/degreaser aerosol formulation was prepared having the following composition:

Component Wt.%
35
2-Phenoxyethanol (Dowanol EPh)(Trade Mark) 3.0
Sodium pelargonate (45%) (Monatrope 1250)(Trade Mark) 7.2
Octylphenol ethoxylate (Triton X-45)(Trade Mark) 0.2
Sodium nitrite 0.2
40 Ammonium hydroxide (28% NH3) 0.05
Deionized H20 89.35
100.00

The composition was a clear, colorless aqueous solution having a pH of 10.24.

The above composition was aerosolized in a 170g (6 oz.) aerosol can using 8.32 g (15.8 ml) of a
propane-isobutane blend propellant (sold under the trade designation A-55) through an AR-75 valve. The fill
ratio equaled 87/13. The valve was fitted with a Marc-18-1525 actuator.
It was found that the resulting aerosol formulation very easily and quickly removed all of the following
markings from alkyd enameled metal surfaces: black, indelible Magic Marker felt pen, blue and black
indelible ballpoint pen, red (wax) crayon and automotive grease smearings.

55

12
 EP 0 479 908 B1

Example 11

An aqueous cleaner/degreaser formulation was prepared having the following composition:

5
Component Wt.%
Benzaldehyde 3.0
Dodecylbenzenesulfonic acid 3.0
Sodium hydroxide (50%) 0.75
w Sodium 1-octanesulfonate (Bio Terge PAS-8S)(Trade Mark) 3.0
Chelant (Hampene 100)(Trade Mark) 0.3
Soft H20 89.95
100.00

The composition was a clear, aqueous solution having a pH of 7.0, a total solids content of 4.7%, a total
actives content of 7.70% and a cloud point in excess of 100°C.
The composition was subjected to the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 5 sec.
20% removal of grease at 30 sec.
35-40% removal of grease at 1.0 min.
60% removal of grease at 2.0 min.
75-80% removal of grease at 3.0 min.
100% removal of grease at 5.0 min.

Example 12

An aqueous cleaner/degreaser formulation was prepared having the following composition:

Component Wt.%
Methyl isobutyl ketone 3.5
Dodecylbenzenesulfonic acid 2.25
Sodium hydroxide (50%) 0.6
Sodium 1-octanesulfonate (Bio Terge PAS-8S)(Trade Mark) 3.0
Chelant (Hampene 100)(Trade Mark) 0.3
Soft H20 90.35
100.00

40 The composition was a clear, aqueous solution having a pH of 7.0, a total solids content of 3.8%, a total
actives content of 7.37% and a cloud point in excess of 100°C.
The composition was subjected to the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 4 sec.
25% removal of grease at 15 sec.
45 45-50% removal of grease at 30 sec.
70% removal of grease at 1.0 min.
85% removal of grease at 2.0 min.
100% removal of grease at 3.5 min.

55

13
 EP 0 479 908 B1

Example 13

An aqueous cleaner/degreaser formulation was prepared having the following composition:

5
Component Wt.%
Benzonitrile 3.5
Dodecylbenzenesulfonic acid 3.6
Sodium hydroxide (50%) 1.0
w Sodium 1-octanesulfonate (Bio Terge PAS-8S)(Trade Mark) 3.6
Chelant (Hampene 100)(Trade Mark) 0.3
Soft H20 88.0
100.0

The composition was a clear, aqueous solution having a pH of 7.0, a total solids content of 5.66%, a total
actives content of 9.16% and a cloud point in excess of 100°C.
The composition was subjected to the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 6 sec.
10% removal of grease at 30 sec.
15% removal of grease at 1.0 min.
30% removal of grease at 2.0 min.
40% removal of grease at 3.0 min.
50% removal of grease at 4.0 min.
65% removal of grease at 6.0 min.
80-85% removal of grease at 8.0 min.
100% removal of grease at 10 min.

Example 14

An aqueous cleaner degreaser formulation was prepared having the following composition:

Component Wt.%
Cyclohexanone 5.0
Alkylpolyglycoside (Nonionic surfactant -APG-300) 1.0
Sodium 1-octanesulfonate (Bio Terge PAS-8S)(Trade Mark) 2.5
Chelant (Hampene 100)(Trade Mark) 0.3
Citric acid 0.05
SoftH20 91.15
100.00

The composition was a clear, aqueous solution having a pH of 7.0, a total solids content of 1.67%, a total
actives content of 6.67% and a cloud point in excess of 100°C.
45 The composition 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 15 sec.
75% removal of grease at 30 sec.
100% removal of grease at 1.25 min.
50 The composition partially removes black Magic Marker markings from enameled metal surfaces.

55

14
 EP 0 479 908 B1

Example 15

An aqueous cleaner/degreaser formulation was prepared having the following composition:

5
Component Wt.%
Isophorone 3.6
Dodecylbenzenesulfonic acid 1.8
Sodium hydroxide (50%) 0.45
w Chelant (Hampene 100, 40%)(Trade Mark) 0.3
Sodium 1-octanesulfonate (Bio Terge PAS-8S)(Trade Mark) 3.0
Soft H20 90.85
100.00

The composition was a clear, aqueous solution having a pH of 7.0, a total solids content of 3.345%, a total
actives content of 6.945% and a cloud point in excess of 100°C.
The composition was subjected to the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 1 sec.
65-70% removal of grease at 15 sec.
85-90% removal of grease at 30 sec.
100% removal of grease at 1.0 min.
The composition easily removed Magic Marker markings from enameled metal surfaces and very
readily removed smeared automotive grease from forklift truck bodies.

Example 16

An aqueous cleaner/degreaser formulation was prepared having the following composition:

Component Wt.%
Butoxyethyl acetate (butyl cellosolve acetate) 5.0
Dodecylbenzenesulfonic acid 3.3
Sodium hydroxide (50%) 0.85
Chelant (Hampene 100, 40%)(Trade Mark) 0.3
Sodium 1-octanesulfonate (Bio Terge PAS-8S)(Trade Mark) 4.0
Soft H20 86.55
100.00

40 The composition was a clear, aqueous solution having a pH of 7.0, a total solids content of 5.445%, a total
actives content of 10.44% and a cloud point in excess of 100°C.
The composition was subjected to the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 2 sec.
33% removal of grease at 15 sec.
45 60-70% removal of grease at 30 sec.
85-90% removal of grease at 1.0 min.
100% removal of grease at 1.5 min.
The composition removed Magic Marker markings from enameled metal surfaces with slight difficulty.

50 Example 17

A formulation was prepared using as the potent organic solvent 2-(2-ethylhexyloxy) ethanol (2-
ethylhexyl cellosolve or Ektasolve EEH (Trade Mark)) whose aqueous solubility is only 0.095 wt.%. The
formulation had the following composition:
55

15
 EP 0 479 908 B1

Component Wt.%
2-(2-Ethylhexyloxy) ethanol 4.0
Dodecylbenzenesulfonic acid 6.0
Sodium hydroxide (50%) 1.5
Sodium cumene sulfonate (45%) 6.0
Soft H20 82.5
100.0

The composition was an opalescent formulation and not quite a clear solution. The high levels of
dodecylbenzenesulfonic acid and sodium cumene sulfonate failed to fully solubilize the organic solvent
component. The composition had a pH of 7.0, a total solids content of 9.45%, a total actives content of
13.45% and a cloud point in excess of 100°C.
The composition was subjected to the degreasing test of Example 1 with the following result:
1st attack on greased slide at 10 min.
The composition effected only very slight removal of black Magic Marker markings from enameled metal
surfaces and had no effect at all on black ballpoint pen markings.
The organic solvent 2-(2-ethylhexyloxy) ethanol alone very easily removes black Magic Marker and blue
and black indelible ballpoint pen, etc. markings from alkyd enameled metal surfaces.

Example 18

A formulation was prepared using an amount of surfactant in excess of that required to just aqueous
solubilize the organic solvent component of the formulation. The formulation had the following composition:
25

Component Parts by weight

2-Phenoxyethanol (Dowanol EPh)(Trade Mark) 8.0
Dodecylbenzenesulfonic acid 4.0
Sodium hydroxide (50%) 1.0
Chelant (Hampene 100)(Trade Mark) 0.6
Water soluble dye blend (1 :1 BG/S-545) 0.002
SoftH20 196.4
200.0

The composition was a clear, aqueous solution having a pH of 7.0, a total solids content of 2.371%, a total
actives content of 6.371% and a cloud point in excess of 100°C.
The composition was subjected to the degreasing test method of Example 1 with the following results:
40 1st attack on greased slide at 10 sec.
15% removal of grease at 30 sec.
25% removal of grease at 1.0 min.
35-40% removal of grease at 1.5 min.
45-50% removal of grease at 2.0 min.
45 55% removal of grease at 3.0 min.
70% removal of grease at 5.0 min.
80-85% removal of grease at 8.0 min.
90% removal of grease at 10.0 min.
100% removal of grease at 12.0 min.
50 The results may be compared with those obtained with the composition of Example 2 which effected 100%
removal of grease at 1.25 min. The composition of Example 2 contained an amount of surfactant not
substantially exceeding that required to aqueous solubilize the organic solvent component.
The composition of this example totally failed to remove any black Magic Marker markings or black as
well as blue ballpoint pen markings from enameled metal sufaces.

16
 EP 0 479 908 B1

Example 19

An aqueous cleaner/degreaser formulation was prepared having the following composition:

5
Component Wt.%
1-Phenoxy-2-propanol (Dowanol PPh)(Trade Mark) 4.0
Sodium 1-octanesulfonate (Bio Terge PAS-8S, 40%)(Trade Mark) 4.0
Dodecylbenzenesulfonic acid 1.0
70 Sodium hydroxide (50%) 0.25
Chelant (Hampene 100) 0.3
Soft H20 90.45
100.00

The composition was a clear, aqueous solution having a pH of 7.0, a total solids content of 2.85%, a total
actives content of 6.85% and a cloud point in excess of 100°C.
The composition was subjected to the degreased test method of Example 1 with the following results:
1st attack on greased slide at 2 sec.
50% removal of grease at 15 sec.
90% removal of grease at 30 sec.
100% removal of grease at 45 sec.
The composition very easily removed black Magic Marker markings from enameled metal surfaces.

Example 20

Example 19 was repeated except that the composition contained 10.0 wt.% of the coupler sodium 1-
octanesulfonate and 84.45 wt.% of soft H20, with the other components being present in the same amounts
shown in Example 19. The amount of surfactant/coupler components employed in Example 19 did not
substantially exceed that required to aqueous solubilize the organic solvent component while the increased
amount of the coupler utilized in this example greatly exceeded the amount necessary to aqueous solubilize
the organic solvent component.
The resulting composition was subjected to the degreasing test method of Example 1 with the following
results:
1st attack on greased slide at 25 sec.
10% removal of grease at 1.0 min.
15% removal of grease at 2.0 min.
20-25% removal of grease at 4.0 min.
40% removal of grease at 7.0 min.
60% removal of grease at 10.0 min.
75-80% removal of grease at 15.0 min.
90-95% removal of grease at 20.0 min.
100% removal of grease at 25.0 min.
The composition smudged or smeared rather than removed black Magic Marker markings and blue and
black ballpoint pen markings.

Example 21

An aqueous cleaner/degreaser formulation was prepared which contained an organic solvent whose
aqueous solubility exceeded 6 weight percent. The organic solvent employed was propylene glycol
monomethyl ether acetate having a water solubility of approximately 16.5 wt.%. The formulation had the
following composition:

55

17
 EP 0 479 908 B1

Component Wt.%
Propylene glycol monomethyl ether acetate 4.0
Nonylphenoxypoly(ethyleneoxy) (8.5) ethanol (nonionic surfactant-T-Det N-9.5)(Trade Mark) 0.35
Chelant (Hampene 100)(Trade Mark) 0.3
Citric acid 0.05
Soft H20 95.3
100.00

The composition was a clear, aqueous solution having a pH of 7.0, a total solids content of 0.52%, a total
actives content of 4.52% and a cloud point of 54 ° C.
The composition was subjected to the degreased test method of Example 1 with the following results:
1st attack on greased slide at 17 sec.
10% removal of grease at 30 sec.
15-20% removal of grease at 1.0 min.
30% removal of grease at 2.0 min.
40% removal of grease at 3.0 min.
45-50% removal of grease at 4.0 min.
55-60% removal of grease at 5.0 min.
70% removal of grease at 6.0 min.
75-80% removal of grease at 7.0 min.
85-90% removal of grease at 9.0 min.
100 % removal of grease at 11.5 min.
The composition was totally ineffective in attempted removal against the following markings from
enameled metal surfaces: black Magic Marker; blue and black indelible ballpoint pen; and #1 hardness
pencil. The organic solvent propylene glycol monomethyl ether acetate alone easily removes the above
markings from enameled metal surfaces.

Example 22
30 ~
An aqueous cleaner/degreaser formulation was prepared using as-the organic solvent 2-butoxyethanol
(Butyl Cellosolve (Trade Mark)) which has an infinite aqueous solubility. The formulation had the following
composition:

Component Wt.%
2-Butoxyethanol 4.0
Dodecylbenzenesulfonic acid 0.60
Sodium hydroxide (50%) 0.15
Chelant (Hampene 100)(Trade Mark) 0.3
Soft H20 94.95
100.00

45 The composition was a clear, colorless, aqueous solution having a pH of 7.0, a total solids content of
0.795%, a total actives content of 4.795% and a cloud point in excess of 100°C.
The composition was subjected to the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 20 sec.
10% removal of grease at 40 sec.
50 20% removal of grease at 1.0 min.
33% removal of grease at 2.0 min
40-45% removal of grease at 3.0 min.
50% removal of grease at 4.0 min.
60% removal of grease at 6.0 min.
55 70% removal of grease at 8.0 min.
75-80% removal of grease at 11.0 min.
85-90% removal of grease at 15.0 min.
100% removal of grease at 20.5 min.

18
 EP 0 479 908 B1

The composition was totally ineffective in removing the following markings from enameled metal
surfaces: black Magic Marker, black and blue indelible ballpoint pen, and #1 hardness pencil, while the
organic solvent per se readily removed all of these markings.
The results may be compared with those obtained with the composition of Example 2, and clearly
5 indicate the unsuitability of 2-butoxyethanol in practicing the invention.

Example 23

An aqueous cleaner/degreaser formulation was prepared using as the organic solvent N-methylpyr-
io rolidone which has an infinite water solubility. The formulation had the following composition:

Component Wt.%
N-methylpyrrolidone 4.0
Dodecylbenzenesulfonic acid 0.6
Sodium hydroxide (50%) 0.15
Chelant (Hampene 100)(Trade Mark) 0.3
Soft H20 94.95
100.00

The composition was a clear, colorless, aqueous solution having a pH of 7.0, a total solids content of
0.795%, a total actives content of 4.795% and a cloud point in excess of 100°C.
The composition was subjected to the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 15 sec.
about 5% removal of grease at 30 sec.
33% removal of grease at 1.0 min.
55% removal of grease at 2.0 min.
70% removal of grease at 4.0 min.
80% removal of grease at 6.0 min.
85% removal of grease at 8.0 min.
90% removal of grease at 10.0 min.
95% removal of grease at 13.0 min.
100% removal of grease at 18.0 min.
The composition showed only very slight removal of pencil markings and was ineffective in removing
black Magic Marker and blue and black indelible ballpoint pen markings. N-methylpyrrolidone alone is very
effective in removing all of these markings from enameled metal surfaces.

Example 24

A series of compositions was prepared, each containing 4.0 wt.% of 2-phenoxyethanol (Dowanol EPh)-
(Trade Mark) and varying amounts of the anionic surfactant/coupler dodecylbenzenesulfonic acid (DDBSA)
from 0.4 wt.% to 3.4 wt.%. These compositions also contained the same relative proportions of sodium
hydroxide (50%), chelant and water soluble dye blend. The compositions were subjected to the degreasing
test method of Example 1, and the results are summarized in the following table.

19
 EP 0 479 908 B1

TABLE 1

DDBSA Wt.% Total Actives % (theory) Degreasing Time at 21 ° C, Minutes* Comments

5 0.4 4.57 Not run Cloudy, Turbid
0.6 4.80 1.25 Clear Solution
0.9 5.13 3.33 Clear Solution
1.3 5.58 6.75 Clear Solution
2.0 6.37 12.0 Clear Solution
w 2.7 7.16 22.75 Clear Solution
3.4 7.95 50.0 Clear Solution
'Time for complete, 100% degreasing of slide.

15 These results demonstrate that optimum degreasing efficacy (minimum degreasing time) occurs when the
lowest level of solubilizing surfactant and/or coupler are employed so as to minimally but fully solubilize the
organic solvent component in the aqueous cleaner/degreaser solution.

Example 25
20
A series of compositions was prepared, each containing 4.0 wt.% of 1-phenoxy-2-propanol (Dowanol
PPh)(Trade Mark) and varying amounts of the coupler sodium 1-octanesulfonate (Bio Terge PAS-8S)(Trade
Mark) from 2.0 wt.% to 15.0 wt.%. These compositions also contained the same relative proportions of
dodecylbenzenesulfonic acid (1.0 wt.%), sodium hydroxide (50%) and chelant. The compositions were
25 subjected to the degreasing test method of Example 1, and the results are summarized in the following
table.

TABLE 2

Bio Terge PAS-8S Wt.% Total Actives % (theory) Degreasing Time at 21 ° C, Minutes* Comments
2.0 6.05 Not run Cloudy, Turbid
4.0 6.85 0.75 Clear Solution
6.0 7.65 8.0 Clear Solution
8.0 8.45 17.5 Clear Solution
10.0 9.25 25.0 Clear Solution
15.0 11.25 44.0 Clear Solution
'Time for complete, 100% degreasing of slide.
40
These results are consistent with the results obtained in Example 24.

Example 26

45 An aqueous cleaner/degreaser formulation was prepared having the following composition:

Component Wt.%
2-Phenoxyethanol (Dowanol EPh)(Trade Mark) 4.0
Sodium coco imidazoline amphoglycinate (Monateric CM-36S, 40%)(Trade Mark) 2.0
Sodium cumene sulfonate (45%) 3.3
Citric acid 0.10
Soft H20 90.6
100.00
55
The composition was a clear, colorless, aqueous solution having a pH of 7.02, a total solids content of
2.39%, a total actives content of 6.39% and a cloud point in excess of 100 °C.

20
 EP 0 479 908 B1

The composition was subjected to the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 9 sec.
15% removal of grease at 30 sec.
25% removal of grease at 1.0 min.
5 40% removal of grease at 1.5 min.
65-70% removal of grease at 2.5 min.
90% removal of grease at 3.5 min.
100% removal of grease at 4.25 min.
The composition readily and fully removed the following markings from alkyd enameled metal surfaces:
io black indelible Magic Marker, blue and black indelible ballpoint pen, #1 graphite pencil and red (wax)
crayon.

Example 27

is An aqueous cleaner/degreaser formulation was prepared having the following composition:

Component Wt.%
2-Phenoxyethanol (Dowanol EPh)(Trade Mark) 4.0
Dodecylbenzenesulfonic acid, isopropylamine salt (Witconate P10-59)(Trade Mark) 0.90
Soft H20 95.1
100.0

The composition was a clear, colorless, aqueous solution having a pH of 7.0, a total solids content of
0.84%, a total actives content of 4.84% and a cloud point in excess of 100°C.
The composition was subjected to the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 5 sec.
60% removal of grease at 30 sec.
75-80% removal of grease at 50 sec.
90% removal of grease at 70 sec.
100% removal of grease at 1.5 min.
The composition very easily and completely removed black Magic Marker markings, blue and black
indelible ballpoint pen markings and #1 hardness pencil markings from enameled metal surfaces.

Example 28

An aqueous cleaner/degreaser formulation was prepared having the following composition:

40 Component Wt.%
2-Phenoxyethanol (Dowanol EPh)(Trade Mark) 4.0
Tall Oil carboxylic acids 0.7
Triethanolamine 1.0
Soft H20 94.3
45
100.0

The tall oil carboxylic acids and triethanolamine formed an amine soap which functioned as an anionic
surfactant/coupler. The composition was a clear, essentially colorless, low foaming, aqueous solution with a
so faint characteristic tall oil odor. It had a pH of 8.21, a total solids content of 1.7%, a total actives content of
5.7% and a cloud point in excess of 100°C.
The composition was subjected to the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 1-2 sec.
90% removal of grease at 15 sec.
55 100% removal of grease at 20 sec.
The composition very easily, completely and readily removed the following markings from enameled
metal surfaces: black Magic Marker, blue and black indelible ballpoint pen and #1 hardness pencil
markings.

21
 EP 0 479 908 B1

Example 29

The commercial product "Fantastik" (Trade Mark) All-Purpose Cleaner was analyzed and found to have
the following composition:

Component Wt.%
Ethylene glycol monobutyl ether (Butyl Cellosolve Trade Mark) 10 ± 2
Sodium salt of dodecylbenzene sulfonic acid 3.0
10 Chelant (Versene 100 or Hampene 100)(Trade Mark) 0.8
Fragrance & colorant trace
Water Q. S.
100.0

15
The composition had a pH of 12.15, a total solids content of 2.98% and a cloud point in excess of 100°C.
The composition was subjected to the degreasing test method of Example 1 with the following results:
1st attack on greased slide at 13 min.
10% removal of grease at 30 min.
11-15% removal of grease at 1 hr.
20
20% removal of grease at 1.5 hrs.
25% removal of grease at 2.0 hrs.
30-35% removal of grease at 3.0 hrs.
40-45% removal of grease at 3.5 hrs.
55-60% removal of grease at 4.0 hrs.
25
70% removal of grease at 5.0 hrs.
80% removal of grease at 6.0 hrs.
90% removal of grease at 7.5 hrs.
100% removal of grease at 9.0 hrs.
The composition removed grease/oil buildup on walls, metal surfaces, etc. with comparative ease but
30
required a good scrubbing action.
In view of the above, it will be seen that the several objects of the invention are achieved and other
advantageous results attained.

Claims
35
A stable, aqueous cleaner/degreaser composition in the form of a true aqueous solution rather than an
emulsion or microemulsion, as evidenced by exhibiting no Tyndall effect, said solution 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;
40
(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 aunt exceeding its aqueous solubility;
45
(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 not exceeding approximately twofold that required to completely
solubilize said organic solvent; and
(c) water
50
said composition containing neither 2-(2-butoxyethoxy)ethanol nor ethylene glycol monohexyl ether.

2. A stable, aqueous cleaner/degreaser composition as claimed in claim 1 wherein said solubilizing

additive is present in an amount not substantially exceeding that required to completely solubilize said
organic solvent.
55
3. A stable, aqueous cleaner/degreaser composition as claimed in claim 1 or claim 2 wherein said organic
solvent has a water solubility in the range of approximately 1 to approximately 2.5 weight percent.

22
 EP 0 479 908 B1

4. A stable, aqueous cleaner/degreaser composition as claimed in any one of claims 1 or 2 wherein said
organic solvent is selected from 2-phenoxyethanol, 1-phenoxy-2-propanol, /3-phenylethanol, acetophe-
none, benzyl alcohol, butoxyethyl acetate, isophorone and the dimethyl esters of mixed succinic,
glutaric and adipic acids.
5
5. A stable, aqueous cleaner/degreaser composition as claimed in any one of the preceding claims
wherein said surfactant is selected from anionic, nonionic, cationic and amphoteric surfactants.

6. A stable, aqueous cleaner/degreaser composition as claimed in claim 5 wherein said surfactant is an

io anionic surfactant selected from 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 didodecyl-
benzene sulfonate, dodecyl diphenyloxide disulfonic acid, sodium dodecyl diphenyloxide disulfonate,
is isopropylamine decyl diphenyloxide disulfonate, sodium hexadecyloxypoly-(ethyleneoxy)(10)ethyl sul-
fonate, potassium octylphenoxypoly(ethyleneoxy)(9)ethyl sulfonate, sodium alpha C12—h olefin sul-
fonate, 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)
20 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.

25 7. A stable, aqueous cleaner/degreaser composition as claimed in claim 5 wherein said surfactant is a

nonionic surfactant selected from octylphenoxypoly(ethyleneoxy) (11) ethanol, nonylphenoxypoly-
(ethyleneoxy) (13) ethanol, dodecylphenoxypoly(ethyleneoxy)(10)ethanol, polyoxyethylene (12) lauryl
alcohol, polyoxyethylene (14) tridecyl alcohol, lauryloxypoly(ethyleneoxy)(10)ethyl methyl ether,
undecylthiopoly(ethyleneoxy)(12)ethanol, methoxypoly(oxyethylene(10)/(oxypropylene(20))-2-propanol
30 block copolymer, nonyloxypoly(propyleneoxy)(4)/(ethyleneoxy)(16)ethanol, dodecyl polyglycoside,
polyoxyethylene (9) monolaurate, polyoxyethylene (8) monoundecanoate, polyoxyethylene (20) sorbitan
monostrearate, polyoxyethylene (18) sorbitol monotallate, sucrose monolaurate, lauramidopropyl-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, and
35 coconut diethanolamide.

8. A stable, aqueous cleaner/degreaser composition as claimed in claim 5 wherein said surfactant is a

cationic surfactant selected from a mixture of n-alkyl dimethyl ethylbenzyl ammonium chlorides,
hexadecyltrimethylammonium methosulfate, didecyldimethylammonium bromide and a mixture of n-
40 alkyl dimethyl benzyl ammonium chlorides.

9. A stable, aqueous cleaner/degreaser composition as claimed in any one of the preceding claims
wherein said coupler is selected from sodium benzene sulfonate, sodium toluene sulfonate, sodium
xylene sulfonate, potassium ethylbenzene sulfonate, sodium cumene sulfonate, sodium octane-1-
45 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, and sodium n-butoxymethyl carboxylate.

10. A stable, aqueous cleaner/degreaser composition as claimed in any one of the preceding claims
50 wherein said organic solvent is 2-phenoxyethanol.

11. A stable, aqueous cleaner/degreaser composition as claimed in any one of claims 1 to 9 wherein said
organic solvent is 1-phenoxy-2-propanol.

55 Patentanspruche

1. Stabile waBrige Reinigungs/Entfettungs-Zusammensetzung in Form einer echten waBrigen Losung

anstatt einer Emulsion oder Mikroemulsion, was sich daran zeigt, dal3 sie keinen Tyndall-Effekt

23
 EP 0 479 908 B1

aufweist, die enthalt:

a) mindestens ein in Wasser schwerlosliches organisches Losungsmittel, das dadurch charakterisiert
ist, daB es
i) eine Wasserloslichkeit in dem Bereich von etwa 0,2 bis etwa 6 Gew.-% aufweist;
5 ii) kein Kohlenwasserstoff oder Halogenkohlenwasserstoff ist;
iii) eine oder mehr ahnliche oder unahnliche (verschiedene), Sauerstoff, Stickstoff, Schwefel oder
Phosphor enthaltende funktionelle Gruppen aufweist;
iv) ein Losungsmittel fur hydrophobe Schmutzstoffe ist; und
v) in einer Menge vorliegt, die seine Wasserloslichkeit ubersteigt;
io b) ein solubilisierendes Additiv (Zusatz), das besteht aus etwa 0,1 bis etwa 100 Gew.-% eines
oberflachenaktiven Agens und 0 bis etwa 99,9 Gew.-% eines Kupplers, wobei das genannte
solubilisierende Additiv in einer Menge vorliegt, die das Zweifache der Menge nicht ubersteigt, die
zur vollstandigen Solubilisierung des genannten organischen Losungsmittels erforderlich ist; und
c) Wasser,
is wobei die Zusammensetzung weder 2-(2-Butoxyethoxy)ethanol noch Ethylenglycolmonohexylather ent-
halt.

2. Stabile waBrige Reinigungs/Entfettungs-Zusammensetzung nach Anspruch 1, worin das solubilisierende

Additiv in einer Menge vorliegt, welche die Menge nicht wesentlich ubersteigt, die erforderlich ist, urn
20 das organische Losungsmittel vollstandig zu solubilisieren.

3. Stabile waBrige Reinigungs/Entfettungs-Zusammensetzung nach Anspruch 1 oder 2, worin das organi-

sche Losungsmittel eine Wasserloslichkeit in dem Bereich von etwa 1 bis etwa 2,5 Gew.-% hat.

25 4. Stabile waBrige Reinigungs/Entfettungs-Zusammensetzung nach einem der Anspruche 1 oder 2, worin

das organische Losungsmittel ausgewahlt wird aus 2-Phenoxyethanol, 1-Phenoxy-2-propanol, /3-Pheny-
lethanol, Acetophenon, Benzylalkohol, Butoxyethylacetat, Isophoron und den Dimethylestern von ge-
mischten Bernstein-, Glutar- und Adipinsauren.

30 5. Stabile waBrige Reinigungs/Entfettungs-Zusammensetzung nach einem der vorhergehenden Anspru-

che, worin das oberflachenaktive Agens ausgewahlt wird aus anionischen, nicht-ionischen, kationischen
und amphoteren oberflachenaktiven Agentien.

6. Stabile waBrige Reinigungs/Entfettungs-Zusammensetzung nach Anspruch 5, worin das oberflachenakti-

35 ve Agens ein anionisches oberflachenaktives Agens ist, das ausgewahlt wird aus Dodecylbenzolsulfon-
saure, Natriumdodecylbenzolsulfonat, Kaliumdodecylbenzolsulfonat, Triethanolamindodecylbenzolsulfo-
nat, Morpholiniumdodecylbenzolsulfonat, Ammoniumdodecylbenzolsulfonat, Isopropylamindodecylben-
zolsulfonat, Natriumtridecylbenzolsulfonat, Natriumdinonylbenzolsulfonat, Kaliumdidodecylbenzolsulfo-
nat, Dodecyldiphenyloxiddisulfonsaure, Natriumdodecyldiphenyloxiddisulfonat, Isopropylamindecyldi-
40 phenyloxiddisulfonat, Natriumhexadecyloxypoly(ethylenoxy)(1 0)ethylsulfonat, Kaliumoctylphenoxypoly-
(ethylenoxy)(9)ethylsulfonat, Natriuma-Ci 2-1 4-olefinsulfonat, Natrium-hexadecan-1 -sulfonat, Natriume-
thyloleatsulfonat, Kaliumoctadecenylsuccinat, Natriumoleat, Kaliumlaurat, Triethanolaminmyristat, Morp-
holiniumtallat, Kaliumtallat, Natriumlaurylsulfat, Diethanolaminlaurylsulfat, Natriumlaureth(3)sulfat,
Ammoniumlaureth(2)sulfat, Natriumnonylphenoxypoly(ethylenoxy)(4)sulfat, Natriumdecyloxypoly-
45 (ethylenoxy(5)methyl)carboxylat, Natriumoctylphenoxypoly(ethylenoxy(8)methyl)carboxylat,
Natriummonodecyloxypoly(ethylenoxy(4)phosphat, Natriumdidecyloxypoly(ethylenoxy)(6)phosphat und
Kaliummono/dioctylphenoxypoly(ethylenoxy)(9)phosphat.

7. Stabile waBrige Reinigungs/Entfettungs-Zusammensetzung nach Anspruch 5, worin das oberflachenakti-

50 ve Agens ein nicht-ionisches oberflachenaktives Agens ist, das ausgewahlt wird aus Octylphenoxypoly-
(ethylenoxy)(1 1)ethanol, Nonylphenoxypoly(ethylenoxy)(1 3)ethanol, Dodecylphenoxypoly(ethylenoxy)-
(1 0)ethanol, Polyoxyethylen(1 2)laurylalkohol, Polyoxyethylen(1 4)tridecylalkohol, Lauryloxypoly-
(ethylenoxy)(1 0)ethylmethylather, Undecylthiopoly(ethylenoxy)(1 2)ethanol, Methoxypoly(oxyethylen(1 0)/-
(oxypropylen(20)-2-propanol-Block-Copolymer, Nonyloxypoly(propylenoxy)(4)/(ethylenoxy)(16)ethanol,
55 Dodecylpolyglycosit, Polyoxyethylen(9)monolaurat, Polyoxyethylen(8)monoundecanoat, Polyoxyethylen-
(20)sorbitanmonostearat, Polyoxyethylen(1 8)sorbitolmonotallat, Saccharosemonolaurat, Lauramidopro-
pyl-N,N-dimethylaminoxid, 1:1-Laurinsaurediethanolamid, 1:1-KokosnuBdiethanolamin, 1:1 gemischtes
Fettsaurediethanolamid, Polyoxyethylen(6)lauramid, 1:1 -Soja-diethanolamidopoly(ethylenoxy)(8)ethanol

24
 EP 0 479 908 B1

und KokosnuBdiethanolamid.

8. Stabile waBrige Reinigungs/Entfettungs-Zusammensetzung nach Anspruch 5, worin das oberflachenakti-

ve Agens ein kationisches oberflachenaktives Agens ist, das ausgewahlt wird aus einer Mischung von
5 n-Alkyldimethylethylbenzylammoniumchloriden, Hexadecyltrimethylammoniummethosulfat, Didecyldi-
methylammoniumbromid und einer Mischung von n-Alkyldimethylbenzylammoniumchloriden.

9. Stabile waBrige Reinigungs/Entfettungs-Zusammensetzung nach einem der vorhergehenden Anspru-

che, worin der Kuppler ausgewahlt wird aus Natriumbenzolsulfonat, Natriumtoluolsulfonat, Natriumxylol-
io sulfonat, Kaliumethylbenzolsulfonat, Natriumcumolsulfonat, Natrium-octan-1-sulfonat, Kaliumdimethyl-
naphthalinsulfonat, Ammoniumxylolsulfonat, Natrium-n-hexyl-diphenyloxiddisulfonat, Natrium-2-ethylhex-
ylsulfat, Ammonium-n-butoxyethylsulfat, Natrium-2-ethylhexanoat, Natriumpellargonat und Natrium-n-
butoxymethylcarboxylat.

is 10. Stabile waBrige Reinigungs/Entfettungs-Zusammensetzung nach einem der vorhergehenden Anspru-

che, worin das organische Losungsmittel 2-Phenoxyethanol ist.

11. Stabile waBrige Reinigungs/Entfettungs-Zusammensetzung nach einem der Anspruche 1 bis 9, worin
das organische Losungsmittel 1-Phenoxy-2-propanol ist.
20
Revendicatlons

1. Composition nettoyante/degraissante aqueuse, stable, sous la forme d'une solution aqueuse veritable
plutot que d'une emulsion ou d'une microemulsion, ainsi qu'il est mis en evidence par le fait qu'elle ne
25 montre pas d'effet Tyndall, cette solution comprenant :
(a) au moins un solvant organique faiblement soluble dans I'eau, caracterise par le fait que :
(i) il a une solubilite dans I'eau de I'ordre d'environ 0,2 a environ 6 % en poids,
(ii) il n'est pas un hydrocarbure ou un halocarbure,
(iii) il presente un ou plusieurs oxygenes, azotes, soufres ou phosphores contenant des groupes
30 fonctionnels, semblables ou dissemblables,
(iv) il est un solvant pour des souillures hydrophobes, et
(v) il est present en une quantite qui depasse sa solubilite aqueuse,
(b) un additif solubilisant constitue d'environ 0,1 a environ 100 % en poids d'un agent tensioactif et
de 0 a environ 99,9 % en poids d'un agent de couplage, cet additif solubilisant etant present en une
35 quantite qui ne depasse pas environ deux fois ce qui est necessaire pour solubiliser completement
le solvant organique, et
(c) de I'eau,
ladite composition ne contenant ni 2-(2-butoxyethoxy)ethanol ni ether monohexylique d'ethyleneglycol.

40 2. Composition nettoyante/degraissante aqueuse, stable, suivant la revendication 1, caracterisee en ce

que I'additif solubilisant est present en une quantite qui ne depasse sensiblement pas celle necessaire
pour solubiliser completement le solvant organique.

3. Composition nettoyante/degraissante aqueuse, stable, suivant I'une des revendications 1 et 2, caracteri-

45 see en ce que le solvant organique presente une solubilite dans I'eau de I'ordre d'environ 1 a environ
2,5 % en poids.

4. Composition nettoyante/degraissante aqueuse, stable, suivant I'une ou I'autre des revendications 1 et 2,

caracterisee en ce que le solvant organique est choisi parmi du 2-phenoxyethanol, du 1-phenoxy-2-
50 propanol, du /3-phenylethanol, de I'acetophenone, de I'alcool benzylique, de I'acetate de butoxyethyle,
de I'isophorone et les esters dimethyliques d'acides succinique, glutarique et adipique mixtes.

5. Composition nettoyante/degraissante aqueuse, stable, suivant I'une quelconque des revendications

precedentes, caracterisee en ce que I'agent tensioactif est choisi parmi des agents tensioactifs
55 anioniques, non ionogenes, cationiques et amphoteres.

6. Composition nettoyante/degraissante aqueuse, stable, suivant la revendication 5, caracterisee en ce

que I'agent tensioactif est un agent tensioactif anionique choisi parmi de I'acide dodecylbenzenesulfoni-

25
 EP 0 479 908 B1

que, du dodecylbenzenesulfonate de sodium, du dodecylbenzenesulfonate de potassium, du dodecyl-

benzenesulfonate de triethanolamine, du dodecylbenzenesulfonate de morpholinium, du dodecylbenze-
nesulfonate d'ammonium, du dodecylbenzenesulfonate d'isopropylamine, du tridecylbenzenesulfonate
de sodium, du dinonylbenzenesulfonate de sodium, du didodecylbenzenesulfonate de potassium, de
I'acide dodecyl-diphenyloxyde-disulfonique, du dodecyl-diphenyloxyde-disulfonate de sodium, du de-
cyldiphenyloxyde-disulfonate d'isopropylamine, de l'hexadecyloxypoly(ethyleneoxy)(10)ethyl-
sulfonatede sodium, de l'octylphenoxypoly(ethyleneoxy)(9)ethyl-sulfonate de potassium, de I'alpha-
Ci2-i+-olefine-sulfonate de sodium, de l'hexadecane-1 -sulfonate de sodium, de I'ethyloleate-sulfonate
de sodium, de I'octadecenyl-succinate de potassium, de I'oleate de sodium, du laurate de potassium,
du myristate de triethanolamine, du tallate de morpholinium, du tallate de potassium, du laurylsulfate de
sodium, du laurylsulfate de diethanolamine, du laureth-(3)-sulfate de sodium, du laureth-(2)-sulfate d'
ammonium, du nonylphenoxypoly(ethyleneoxy)(4)-sulfate de sodium, du decyloxypoly(ethyleneoxy(5)-
methyl)carboxylate de sodium, de l'octylphenoxypoly(ethyleneoxy(8)methyl)carboxylate de sodium, du
mono-decyloxypoly(ethyleneoxy)(4)phosphate de sodium, du didecyloxypoly-(ethyleneoxy)(6)phosphate
de sodium, et du mono/dioctylphenoxypoly(ethyleneoxy)(9)phosphate de potassium.

. Composition nettoyante/degraissante aqueuse, stable, suivant la revendication 5, caracterisee en ce

que I'agent tensioactif est un agent tensioactif non ionogene choisi parmi de I'octylphenoxypoly-
(ethyleneoxy)(11)ethanol,du nonylphenoxypoly(ethyleneoxy)(13)ethanol, du dodecylphenoxypoly-
(ethyleneoxy)(10)ethanol, de I'alcool laurylique de polyoxyethylene (12), de I'alcool tridecylique de
polyoxyethylene (14), de Tether lauryloxypoly(ethyleneoxy)(10)ethylmethylique, du undecylthiopoly-
(ethyleneoxy)(12)ethanol, un copolymere bloc de methoxypoly(oxyethylene(10)/(oxypropylene(20))-2-
propanol, du nonyloxypoly(propyleneoxy)(4)/(ethyleneoxy)(16)ethanol, du dodecyl-polyglycoside, du
monolaurate de polyoxyethylene (9), du monoundecanoate de polyoxyethylene (8), du monostearate de
polyoxyethylene (20) sorbitane, du monotallate de polyoxyethylene (18) sorbitol, du monolaurate de
saccharose, du lauramidopropyl-N,N-dimethylamine-oxyde, du 1/1 diethanolamide laurique, du 1/1
diethanolamide de noix de coco, du 1/1 diethanolamide d'acides gras mixtes, du polyoxyethylene(6)-
lauramide, du 1/1 diethanolamidopoly(ethyleneoxy)(8)ethanol de soja et du diethanolamide de noix de
coco.

. Composition nettoyante/degraissante aqueuse, stable, suivant la revendication 5, caracterisee en ce

que I'agent tensioactif est un agent tensioactif cationique choisi parmi un melange de chlorures de n-
alkyl-dimethyl-ethylbenzyl-ammonium, du methosulfate d'hexadecyltrimethylammonium, du bromure de
didecyldimethylammonium et un melange de chlorures de n-alkyldimethyl-benzyl-ammonium.

. Composition nettoyante/degraissante aqueuse, stable, suivant I'une quelconque des revendications

precedentes, caracterisee en ce que I'agent de couplage est choisi parmi du benzenesulfonate de
sodium, du toluenesulfonate de sodium, du xylenesulfonate de sodium, de I'ethylbenzenesulfonate de
potassium, du cumenesulfonate de sodium, de l'octane-1 -sulfonate de sodium, du dimethylnaphtalene-
sulfonate de potassium, du xylenesulfonate d'ammonium, du n-hexyl-diphenyoxyde-disulfonate de
sodium, du 2-ethylhexyl-sulfate de sodium, du n-butoxyethyl-sulfate d'ammonium, du 2-ethylhexanoate
de sodium, du pelargonate de sodium et du n-butoxymethyl-carboxylate de sodium.

0. Composition nettoyante/degraissante aqueuse, stable, suivant I'une quelconque des revendications

precedentes, caracterisee en ce que le solvant organique est du 2-phenoxyethanol.

1. Composition nettoyante/degraissante aqueuse, stable, suivant I'une quelconque des revendications 1 a

9, caracterisee en ce que le solvant organique est du 1-phenoxy-2-propanol.

26