Note: Descriptions are shown in the official language in which they were submitted.
WO91/09104 PCT/US90/0~215
2070679
AQUEOUS CLEANER/DEGREASER
EMULSION COMPOSITIONS
Backaround o the Invention
This invention relat2s to cleaner/degreaser
compositions and, more particularly, to stable, aqueous
cleaner~d2g easer compositions in the form of emulsions
which e~hibit improved degreasing efficacies.
~ eretofor~, the conventional and available
cleaner/de~LeaseL emulsion compositions have been water in
oil or oil in water emulsions ln which the organic solvent
component is an inher2ntly ~later insoluble organic
solvent. Such available emulsion compositions include, for
e~ample, those marketed under the trade designations "Off"
asphalt remover which contains the water insoluble solvents
toluene and o-dichlorobenzene emulsified with a tall oil
amide. Other available emulsion compositions contain watér
insoluble aromatic solvents such as xylene, kerosene,
mineral spirits, benzene or naphthalene emulsified with
various surfactants to form oil in water emulsions.
Illustrative of such available emulsions are those marketed
under the trade designations "Brulin 512M", "Spartan
WRD-160", "Betco Emulsifiable Solvent Degreaser", "Amrep
Jel-Soi", and "DuBois Actusol". In the preparation of such
emulsions, an inherently water insoluble organic solvent,
typically a hydrocarbon solvent, is emulsified with one or
more surfactants soluble in the solvent component. When
this nonaqueous emulsion or solution is combined with
water, a true milky emulsion is formed in which essentially
none of the solvent component and only a relatively small
~` 30 amount of the surfactant component is dissolved in the
.~ , .
; aqueous phase. Thus, the cleaning/degreasing efficacy of
such emulsion compositions is almost entirely derived from
the nonaqueous or discontinuous phase of the emulsion
`' containing the solvent component necessary to remove
oleophilic (hydrophobic) soilants.
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-WO9l/09104 PCT/US90/07215
7 Q
While conventional cleaner/degreaser emuIsion
compositions possess some degree of efficacy, there is a
need for cleaner/degreaser 0mulsion compositions which
exhibit improved efficacy, particularly with respect to
grease and oil removing efficacy.
Summarv of the Invention
Among the several objects of the invention may be
- noted ~he provision of stable, aqueous cleaner/degreaser
emulsion composi~ions having improved cleaning/degreasing
-10 efficacyi the provision of such emulsion compositions which
; are 0rm~ll2ted o proYlde a portion of the organic solvent
content in ~otn the aqueous and nonaqueous phases of the
emulsions; the provision of emulsion compositions of this
type which may be formulated in various forms including
lot-ions, creams, and aerosol forms; the provision of such
emulsion compositions which have a low level of odor, are
nontoxic and nonhazardous in use; the provision of such
improved emulsion compositions which provide enhanced
degreasing capabilities; the provision of such emulsion
compositions which possess either a low order of
combustibility or are non-combustible, which have a high
flash point, which are safe to use and which are
biodegradable; and the provision of such improved emulsion
compositions which incorporate organic solvents with
inherently limited aqueous solubility and which may be
readily formulated from available components. Other
objects and features will be in part apparent and in part
pointed out hereinafter.
;~~ Briefly, the present invention is directed to
stable, aqueous cleaner/degreaser emulsion compositions
~which comprise:
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WO91/09104 PCT/US90/07215
2~706~9
(a) at least one sparingly soluble organic
solvent characterized by:
(i) having a water solubility in the range
of approximately 0.05 to approximately
-5 ~ weight percent;
(ii) not being a hydrocarbon or halocaroon;
naving one or more similar or
disslmilar oxygen, nitrogen, sulfur, or
phosphorous containing functional
groups;
~ beir.g a sol-tent for hydrophobic
soilants; and
(v) being present in an amount e~ceeding
its aqueous solubility;
(b) a solubilizing additive consisting of from
appro~imately 0.1 to appro~imately 100 weight percent of a
surfactant and from 0 to approximately 99.9 weight percent
of a coupler, said solubilizins additive being present in
an amount insufficient to solubilize all of the total
organic SO1V2nL content but sufEicient to emulsify the
unsolu~ilized portibn of the total organic solvent content;
~, and
.. (c) water.
The emulsion compositions of the-invention thus
: 25 contain a portion of the organic solvent component in the
` aqueous or continuous phase of the emulsions and the
: remainder of the organic solvent component in the emulsion
or discontinuous phase thereby providing enhanced
~ ~ degreasing efficacies.
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:~: SUBSTiTUTE SH~ET
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WO91/09104 PCT/US90/07215
Description of the Preferred Embodiments
In accordance with the present invention, it has now
been found that stable, aqueous cleaner/degreaser emulsion
compositions having improved degreasing capabilities can be
formulated by combining at least one sparingly water
soluble organic solvent having certain compositional and
solvency characteris~ics and being present in an amount
e~ceeding its aquaous solubility with a solubilizing
additive and water, the solubilizing additive being present
in an amount insufEicient to solubilize all of the total
organic solvent content but sufficient to emulsify the
unsolllbil~ ~o~ portion of the total organic solvent
content. ln ~he present invention, the solubilizing
additive performs a dual function, i.e., it solubilizes a
portion of the total content of the organic solvent
component above its inherent aqueous solubility limit and
it emulsifies the unsolubilized portion of the total
organic solvent content. The resulting emulsion thus
contains a portion of the sparingly water soluble organic
2Q solvent component in the aqueous or continuous phase of the
emulsion and the remainder of the organic solvent component
in the emulsified or oil phase of the emulsion. The latter
phase effectively constitutes an organic solvent reservoir
which provides enhanced degreasing efficacy over that
provided by the organic solvent in the aqueous phase alone.
`~ The enhanced degreasing efficacy derivad from the dual
function of the solubilizing additive in the present
invention is in contrast with the cleaning/degreasing
action of available emulsions in which essentially none of
the water insoluble hydrocarbon or halocarbon organic
solvent is present in the aqueous phase of the emulsions
and the cleaning/degreasing activity is wholly dependent
upon the presence of the wator insoluble organic solvent in
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WO9l/09104 PCT/US90/07215
207~579
~
the nonaqueous or discontinuous phase of the emulsions.
The emulsions of the present invention also provide greater
degreasiny efficacies at equal or equivalent organic
solvent levels over those provided by the aqueous
cleaner/degr2aser compositions disclosed in my copending,
coassigned application Serial No. 373,813, filed June 29,
1989, which are formulated in the orm o~ totally water
soluble compositions.
The emulsion compositlons or the invention are
therefore characteri~ed by having the sparingly water
soluble organic solvent present in both the aqueous phase
and nonaqueous or o~l ~hase o~ 'he emulsions The aqueous
phase constitutes a saturated solution of the organic
solvent by reason of the portion of the solvent being
soluble in the aqueous phase to the extent of its inherent
aqueous solubility therein and the portion of the solvent
solubilized by the solubilizing additive into the aqueous
phase. The excess or remaining portion of the total
organic solvent content is emulsified into the nonaqueous
phase of the emulsions and constitutes the reservoir of
organic solvent chiefly responsible for the enhanced
degreasing accivicy e~hlbi'ced by the emulsions of the
invention.
For use in the present invention, the sparingly water
soluble organic solvent must have the following
characteristics: --
(a) it must have limited water solubility in therange of approximately 0.05 to 6 weight percent;
~b) it must not be a hydrocarbon or halocarbon,
(c) it must have one or more similar or
dissimilar o~ygen, nitrogen, sulfur or phosphorous
containing functional groups;
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W09l/~9l04 PCT/US9~/07215
(d) it must be a solvent for hydrophobic
: soilants; and
(e) it must be present in an amount exceeding
its limited aqueous solubility.
Preferably, the organ~c sol~ent has a water solubility in
the r2ngQ O r ~ppro~imately 0.05 to approximately 2.5 weight
percent, morQ 3rersraDly between 1 and 2.5 waight percent.
:;: Organic solYents meeting these criteria provide superior
~` clcaning~dDg easing action when formulated in accordance
with the invention.
The principal sla.sses o~ organic sol~ents from ~,7hich
useful o-ganic sol-~ents may be selècted include esters,
~ . alchohols, ketones, aldehydes, ethers and nitriles. These
: ~ . will generally contain one or more of the desired similar .
;` 15 or dissimilar functional groups listed above. Examples of
~: organic solvents containing similar functional groups from
among those listed above include diethyl gluterate (2 ester
~ groups), phenacyl aoetone (2 keto groups), diethylèthylene
;~ diphosphonate (2 phosphonate ester groups), ethylene-
dipropionate (2 ester groups), decylene glycol (2 hydroxyl
groups), m-dimetho~ybenzen2 (2 ethe:r groups), adiponitrile
(~2 nitrile groups), ethylene glycol dibutyl ether (2 ether
groups), and diethyl-o-phthalate (2 ester groups). Among
; organic solvents containing dissimilar functional groups `
;~ 25 from among those listed above may be mentioned
; 2-phenoxyethanol (hydroxy, ether groups),
l-phenoxy-2-propanol (hydro~y, ether groups),
N-phenylmorpholine (amino, ether groups), isopro-
: pylacetoacetate (keto, ester groups), o-methoxybenzyl
alcohol (ether, hydroxy groups), 4'-methoxyacetophenone
(ether, ketone groups), o-nitrophenetole (nitro, ether
~: groups), 2-hexoxyethanol (hydroxy, ether groups),
: : ethylcyano-acetoacetate (cyano, keto, ester groups),
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~Q~STIT~TE SHEET
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~ WO9l/09104 PCT/~S90/07215
2~7~67~
~-anisaldehyde ~ether, aldehyde groups), polypropylene
glycol 1200, 2000, and 4000 (ether, hydroxyl groups),
n-buto~y acetate (ether, ester groups), and
2-phenylthioethanol (thioether, hydro~yl groups).
In addition to the criteria listsd above, it is also
desirable but not essenti31 that the organic sol~ent have a
relatively lo~ volatility or hlsh ~lash point, e~hibit a
low level of odor, be chemically stable, nonto~.ic, non
hazardous, liquid or eas~ly liqui-ied at ambient
temperatures, and commercially availa~le.
The sparingly water soluble organic solvents which may
be employed in t'ne ?rac" c~ O~ Lhe p.rasen.t ~n'tent ' on ~znd
comprising some of tne solvents listad above) cogeclner with
their aqueous ambient temperature solubility in wt.%
include 2-pheno~yethanol (2.3) (marketed under the trade
designation HDowanol EPh"), ~-pheno~y-2-propanol (1.1)
(marketed under the trade designation "Dowanol PPh"),
~l phenylethanol (1.6), acetophenone (0.5), -benzyl alcohol
`l (4.4), benzonitrile (1.0), n-butyl acetate (0.7), n-amyl
acetate (0.25), benzaldehyde (0.3~, ~,N-diethylaniline
l (1.4), diethyl adipate (0.43), dimethyl-o-phthalate (0.43~,
! n-amyl alcohol (2.7), M-phenylmorpholine (1-0),
`! n-buto~yethyl acetate (EB acetate) (l.l), cyclohe~anol
` (4.2), polypropylene glycol 1200 (2), dipropylene glycol
mono-n-butyl ether (Dowanol DPnB) (5.0) cyclohe~anone
(2.3), isophorone (1.2), methylisobutyl ketone- ~-2.0),
methylisoamyl ketone (0.5), tri-n-butylphosphate (0.6),
l-nitropropane (1.4), nitroethane ~4.5), dimethyl esters of
mixed succinic, glutaric and adipic acids (5.7) (marketed
under the trade designation "DBE ester" by DuPont), diethyl
glutarate (0.88), diethyl malonate (2.08), poly-
;~ oxyalkylene polyols (e.g., polyoxypropylene diols and
: triols) such as the polypropylene glycols P1200, P2000 and
P4000 (Dow Chemical), polypropylene glycol monobutyl ether
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SI~STITUT~ S~FET
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W091/09104 PCT/US9G/07215
(Dow Polyglycol L-1150) and polyglycol copolymers
containing ethenoæy and propenoxy units (Dow 112-2). As
will be apparent to those skilled in the art, the
above-listed sparingly ~ater soluble organic solvents are
merely lllustr3tivQ and various oth~or solvents meeting the
criteria se-t OUL above may ~lso 'oe utilized in the practice
of the invantlon~ ~ecau~e of their performance
characteri~t1cs, lac~ of odor, low volatility/high flash
point, chemical stability and availa'oility,
2-phenoæ-y-ethanol and l-pheno~-1-2-propanol are the pre~erred
organic solvents of choice. N-butoæyethyl acetate (EB
acot~te~ -n~ tho dimQthiTl ~stors o' mi~oa succinic,
glutaric and adlplc 2C1dS aro also amor.g the prefer~ed
organic solvents. For emulsions of the invention in the
form of lotions and creams, the use of oligomeric,
hydrophobic solvents having limited aqueous solubility and
molecular weights of up to 5000, preferably b~low 4000, are
preferred since they also function as emollients,
lubricants, humectants, and skin conditioners and do not
defat the skin. Such solvents include polypropylene
glycols (e.g., Dow P2000, PPG-20, 26 and 30),
poly(1,2-buLylene glycol), poly(2,3-'outylene glycol),
' poly(norbornane o~ide glycol), poly(styrene oxide glycol),
poly(phenylglycidyl ether glycol), polytisobutylglycidyl
ether glycol), poly~methylglycidyl ether glycol),
phenoæypolypropylene glycol, butoæypolypropylene glycol
(PPG-1~ butyl ether), poiypropylene glycol butyl ether
~PPG-18 butyl ether), polyo~ypropylene n-butyl ether,
polytetramethylene ether glycol, poly(tetrahydrofuran),
poly(ethyl vinyl ether), poly(isobutyl vinyl ether),
poly(diallyl ether), polyoæypropylene (30)
trimethylpropanetriol, poly[propylene oæide
(lO)/phenylglycidyl ether (lO) glycol], and similar
solvents ~nown to the art.
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WO91/0~104 PCT/US90/07215
2~7~79
9. - .
As indicated, a number of otherwise potent organic
solvents having an aqueous solubility of less than
approximately 0.05 weight percent, and organic solvents
having an aqueous solubility in excess of approximately 6
weight percent such as propylene glycol monomethyl ether
acetate (aq. sol. 16.5 wt.~), ethylene glycol diacetate
(aq. sol. l4.3 wt.-5), propylene carbonate (a~. sol. l9.6
wt.%j and N-methyl pyrrolidone (ininite aq. sol.) are not
useful in the practice of the invention.
In formulating the stable, aqueous cleaner/desreaser
emulsion compositions of the invention, an organic solvent
meeting the required cr~ terl a s combin~d wlth a
solubilizing additive and water. The solu~ilizing additi~e
consists of from approximately O.l to appro~imately lO0
weight percent of a surfactant and from 0 to approx-
imately 99.9 weight percent of a coupler and, as stated,
the solubilizing additive is present in the formulated
~j compositions in an amount insufficient to solubilize all of
the total organic solvent content but sufficient to
emulsify the unsolubilized portion of the total organic
solvent content. The amount of solubilizing additive
(surfactant or surfactan~ plus coupl2r) required to
accomplish this objective will vary depending upon its
solubilizing efficacy and upon the particular organic
solvent employed; it can readily be determined by simple
e~perimentation in each instance. In s2neral, it is
desirable to formulate the emulsion compositions of the
invention with as little of the solubilizing additivè as
possible while achieving the desired solubilization and
emulsification of the organic solvent stated above since
emulsions so formed will tend to remain in emulsion form
- even upon being diluted many times with water.
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WO9l/~9104 PCT/US90/07215
S
Further, it has been found that the best results are
achieved when the emulsion compositions are formulated with
organic solvents whose aqueous solubility is between
approzimately 0.05 and appro~imately 2.5 weight percent.
Also, it has be~n ~ound that ~lhen an organic solvent is
employed having a water so:!ubility in the upper portion of
the ov~rall r2nge 0.05 to ~ 7~i~ight percent, it is
preferabls co uti7i~e a solubili~1ng addiciYe which is a
. relatiYely b~ttQr emulsirving agent than a solubilizing
agent ror the organic sol;enL. On th2 other hand, ~7hen
employing an organic solvent whose solubility is in the
Iower portlon^ of th~ oY~r~ll -?.~ 0.05 to 2.5
weight parc2nL) ~ i L is pr~fe~able to use 3 solubilizing
agent (such as dodecylbenzenesulfonic acid) which is a
relatively better solubilzing agent than an emulsifying
agent for the organic solvent of limited aqueous solubility.
The solubilizing additive used in the practice of the
invention may consist of one or more compatible surfactants
or surfactant(s) in combination with a coupler. As used
herein, the term "coupler" is intended to mean a hydrotrope
or a substance that increases t~e solubility in water of
another matQrial ~,lhich is onl~ partially water soluble,
such as organic solvents or surfactants. In some
instances, the use of a surfactant alone will suffice to
achieve the desired solubilization and emulsification of
the organic solvent component while in other instances the
- use of a surfactant or compa-tible surfactant blend in
combination with a coupler may be utilized to achieve the
desired dual function of the solubilizing additive
component. Whether or not a surfactant alone or the
combination of a surfactant and coupler is to be used is
dèpendent upon the particular organic solvent and
surfactant employed and can readily be determined in each
partlcular case by simple e~perimentation.
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WO91/09104 PCT/'JS90/07215
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11 2~0~79
The surfactants employed in the practice of thisinvention may be nonionic, anionic, cationic or amphoteric
in character. The use of nonionic surfactants is generally
preferred to avoid the formation or presence of ionic
surfactant salts which tend to break emulsions. Preferred
nonionic surfactants include alkylphenozypoly(etheno~y)
alkanols, alkoxypolytetheno~y~alkanols and fa~ty acid
alkanolamides. Specific illustrative nonionic surfact3ncs
; useful in the practic0 of the invention include octylphe-
no~ypoly(ethyleneoxy)(4)ethanol, nonylpheno~ypoly(ecnylene-
oxy)(5~ethanol, dodecylphenoxypoly(ethyleneo~y)(8)ethanol,
polyo~yethylene (7) lauryl alcohol, polyo~yethylene (4)
i tridecyl alcohol, laurylo~ypoly(ethyleneo~y)(8)ethyl m2thyl
ether, undecylthiopoly(ethyleneoxy)(6)ethanol,
metho~ypoly(o~yethylene(10)/(o~ypropylene(20))-2-propanol
block copolymer, nonylosypoly(propyleneosy)(4)/(ethyl-
eneosy)(lO)ethanol, dodecyl polyglycoside, polyoxyethylene
(9) monolaurate, polyoxyethylene (8) monoundecanoate,
polyoxyethylene (20) sorbitan monostearate, polyoxyethylene
(18) sorbitol monotallate, sucrose monolaurate,
lauryldimethylamine o~ide, myristyldimethylamine oxide,
lauramidopropyl-N,N-dimethylamine o~ide, ~:1 lauric
diethanolamide, 1:1 coconut diethanolamide,
polyo~yethylene(6)1auramide, 1:1 soya diethanolamidopoly-
(ethyleneo~y)(8) ethanol, 1:1 coconut diethanolamide,"modified", and 1:1 coconut diethanolamide, "long chain
; modified". The fatty acid alkanolamides are a class of
, nonionic surfactants derived from a 1:1 or 2:1 molar
reaction between alkanolamines such as diethanolamine and
varying chain length fatty acids such as stearic or oleic
acid. For use in the present invention, the fatty acid
alkanolamides resulting from a 1:1 catalyzed reaction
bFtween an alkanolamine and a fatty acld (known to those
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W~91/09104 PCT/US90/07215
~ ` 12
skilled in the art as "superamides") are preferred since
these predominantly consist of the desired nonionic
dialkanolamide without apPreciable amounts of ionic amine
soaps. Among the illustrative fatty acid alkanolamides
(with their respective molar ratios) which may be used may
be mentioned soyamidz diet;qanolamide (l:l) (MacXamide S,
McIntyre Group Ltd., ~hica~o, Tl1inols), linoleamide
diethanolamide ~ ilonainid 1~-70-,1, L~1Ona ~ndustries,
Inc., Paterson, ~;lew Je{say3, oleamide diathanolamide (l:l)
(Clindrol lO0-0, and ~roduc- ~S l-~, Clint-,~ood Chemical
Company, Chicago, IIlinois)~ ricinoleamide diethanolamide
(l:l) (Mac3~amide ~! ~c~nt~Tre Grou? T-cd.) isostearamide
diethanolamide (l:l)(~onamid l,0-IS, ~qcna Industries, Inc.
and Mackamide ISA, McIn~yre Group Ltd.), oleamide
diethanolamide (2:l) (Mackamide O, McIntyre Group Ltd.),
soyamide diethanolamide (2:l) (Mackamide SD, McIntyre Group
Ltd.), and tail oil diethanolamide (l:l). In addition to
those specifically listed above, other ~nown nonionic
surfactants may likewise be used.
; 20 Illustrative anionic surfactants ~or use in the
invention include dodecylbenzene sulfonic acid,
monoethanolamine dodecylben2eresulfonate, sodium
dodecylbenzene sulfonate, potassium dodecylbenzene
sulfonate, triethanolamine dodecylbenzene sulfonate,
morpholinium dodecylbPnzene sulfonate, ammonium
dodecylbenzene sulfonate, isopropylamine dodecylbenzene
sulfonate, sodium tridecyl- benzene sulfonate, sodium
dinonylbenzene sulfonats, potassium didodecylbenzene
sulfonate, dodecyl diphenyIo~ide disulfonic acid, sodium
dodecyl diphenylo~ide disulfonate, isopropylamine decyl
diphenylo~ide disulfonate, sodium he~adecyl-
oxypoly(ethyleneo~y)(lO~ethyl sulfonate, potassium
octylphenozypoly(ethyleneo~y)(9)ethyl sulfonate, sodium
alpha Cl2_l4 olefin sulfonate, sodium hexadecane-l
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WO91/09104 PCT/U~90/07~15
13
sulfonate, sodium ethyl oleate sulfonate, potassium
octadecenyl-succinate, sodium oleate, potassium laurate,
triethanolamine myristate, morpholinium ~allate, potassium
tallate, sodium lauryl sulfate, diethanolamine lauryl
sulfate, sodium laureth (3) sulfate, ammonium laureth (2)
sulfate, sodium nonylpheno~ypoly(ethyleneoxy)(43 sulfate,
sodium diisobutylsulfosuccinate, disodium
laurylsulfosuccinate, tetrasodium N-laurylsulfosuccinima'ce,
sodium decylo~ypoly~ethyl-eneoxy(5)methyl)caroosylat2,
sodium octylphenoxypoly(ethyl- eneoxy(8)methyl)carbo~ylate,
sodium mono decyloxypoly(ethyl eneoxy)(~)phosphace, sodium
didecyloxypoly(ethyleneoxy)- (6)phosphate, and pocassium
mono/di octylpheno~ypoly(ethyl- eneo~y)(9)phosphato. Other
anionic surfactants known in the art may also be employed.
Illustrative useful cationic surfactants include a
mixture of n-alkyl (Cl2 50%, Cl4 30%, Cl6 17%~ Cl8 3%)
dimethyl ethylbenzyl ammonium chlorides,
hexadecyltrimethyl-ammonium methosulfate,
,~ didecyldimethylammonium bromide and a mi~ture of n-alkyl
(68% Cl2, 32% Cl4) dimethyl benzyl ammonium chlorides.
Similarly useful amphoteric surfactants include
cocamidopropyl betaine, sodium palmityloamphopro- pionate,
N-coco beta-aminopropionic acid, disodium
N-lauryliminodipropionate, sodium coco imidazoline
amphoglycinate and coco betaine. Other cationic and
amphoteric surfactants known to the art may also be
utilized.
As mentioned, the preferred surfactants for use in the
practice of the invention are the alkylphenoxy
poly(ethenoxy) alkanol and fatty acid alkanolamide nonionic
; surfactants.
The couplers which may be utilized in the practice of
the invention include sodium benzene sulfonate, sodium
toluene sulfonate, sodium xylene sulfonate, potassium
3S ethylbenzene sulfonate, sodium cumene sulfonate, sodium
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WO91/09104 PCT/US90/0/215
~,~q~9
octane-l-sulfonate, potassium dimethylnaphthalene
sulfonate, ammonium ~ylene sulfonate, sodium n-hexyl
diphenyo~ide disulfonate, sodium ~-ethylhe:r~yl sulfate,
ammonium n-buto~yethyl sulra~P, sodium 2-echylnexanoate,
sodium pelargonate, sodium n-buto~methyl carbo~ylate,
pot:assium mono/di pheno~yethyl pnospnate, sodium mono/di
n-buto~yethyl phosphate, triethanolamine t imathylolpropane
phosphate, sodium capryloa~pho?.o~iona~e, disodi~m
capryloimincdipro- pionace, sodium
10 isodecylo.~ypropyliminodip opiona'c3, so,-lium c~pro
imidazoline amphoglycinata, and caprylamide D~A/capramide
U -DEA. Cartain watar-solubls sol~7ent5 Xnown to the art ~s
couplers such ~s Prop~rl~n~ g~vcol ~th.~rs (o.~.
tripropyleneglycol monomethyl ether) can be used in the
;15 practice of the invention. Additional couplers or
hydrotropes known to the art may also be utilized.
In regard to the solubilizing additive component of
the emulsion compositions of the invention, it will be
understood that one or more surfactants from one or more
compatible classes of surfactants may be employed or
utilized in a mi~ed solubilizing surfactant system. For
example, a combination of com~atiole anionic and/or
nonionic surfactants may be employed. Likewise, a
combination of compatible couplers may also be used as may
a combination of one or more compatible surfactants f rom
different classes of surfactants together with~ one or more
couplers. -Thus, one may use a combination of blended
surfactants and couplers to achieve the desired solvent
; solubilization and emulsification. The compatibility of
the various surfactants and of the various couplers with
each other-and in combination can be readily determined by
simple e~perimentation. Similarly, a mi~ture of the
sparingly soluble organic solvents may be employed in
formulating the emulsion compositions of the invention.
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. .. .
.~
WO91/09104 PCT/US~0/07215
2070~79
In addition to the sparingly water soluble organic
solvent and solubilizing additive components of the
emulsion compositions of the invention, a viscosifying
thickener or thickening agent may be incorporated to
improve the long term stability of the emulsion
compositions.
Thus, thickened emulsion compositions often retard or
totally prevent droplet coalescence, overcome phase
separation caused by settling or rising droplet mobility
tendencies, and often ameliorate the emulsion destabilizing
effects o certain ionic components present in an emulsion
composition. The judicious employment of one or more
thickening agents may, in fact, allow the propitious use of
ionic, but otherwise emulsion destabilizing, solubilizing
additives in the practice of this invention.
Excessive foaming may occur when certain compositions,
viscosified with thickeners, are agitated to the extent
that accumulating air bubbles are trapped in the emulsion.
Should this occur, or likely occur, the use of suitable
`i 20 defoamers (e.g., perfluoroalkyl phosphate esters or
~i silicone) or antifoaming agents may need to be incorporated
into the emulsion compositions.
Among the viscosifying thickeners useful in the
practice of the invention may be mentioned acrylic
acid/alkyl methacrylate copolymers, carboxy acrylic
polymers, guar gums, ~anthan gums, hydro~yethyl cellulose,
hydroxypropyl cellulose, carboxymethyl cellulose, bentonite
clays, organicallly modified magnesium aluminum silicates,
polyethylene glycols, polyethylene oxide, fumed silica,
polyacrylic acid crosslinked with polyalkenyl polyethers,
polyacrylamide, polyvinyl alcohol, poly(methylvinyl
~ether/maleic) anhydride and sodium alginate. Other
viscosifying thickeners known to the art may also be used.
;~ When the viscosifying thickener is anionic in nature such
... .
',.
SUBST~TUIE ~ E~
,.. ~ ~ . . . .
... .
.;. .
. ,
. .
... ~ ,
~ ~.
W091/09104 PCT/USgO/07215
~ 3
16
as the thickener acrylic acid/al~syl methacrylate copolymer
(Acrysol ICS-l by Rohm & Haas), an amine such as
triethanolamine or other neutralizing base s'nould also be
incorporated to neutralize any free carboxylic acid groups
and thereby cause enhanced thicl.iening. ~,`lith tho use of
nonionic thickeners such as guar gums, nydro~yQthyl
cellulose and hydro~ypropyl cellulosa, the lnclusion o
such an amine is unnecessary.
Various optional adjuvants can also be ~ncorporaced
into the emulsion composi-tlons OL th2 int/-nt 1 on These
include chelants such as tne sodium salts of etnylenedia-
minetetraacetic acid (Hampene 100 or ~'7er.5Qne 100~,
defoamers and foam controlling ~gonts, fr3s~ances, ~yes,
preservatives, lubricants, emollients, pH adjustants,
dispersants, abrasives, anti-corrosion additives and
anti-rust additives. To prevent flash rusting when the
emulsion compositions are used to clean and/or degrease
metal surfaces, an anti flash-rusting additive such as an
alkanolamine (e.g., monoethanolamine) or sodium nitrite may
be incorporated. In general, it is preferred that the
compositions be formulated to have a pH within a range of
about 6.5-10 so as to be gent~o lo the hands and a~Joid
defatting the skin.
The emulsion compositions of the invention may be
prepared by combining the various components together under
mechanical mi~ing conditions to form the desired
emulsions. Thus,- for example, the solubilizing additive
may first be dispersed in water with stirring followed by
the addition of the sparingly soluble organic solvent with
stirring over a period of time to achieve complete
emulsification. Other viable, proven techniques involving
;formation of either O~W or W/O emulsions or emulsion
concentrates, optionally followed by phase inversions, may
also be employed. In forming emulsions in the form of
S~eS~ TE S~EET
. .
. . . .. .
.
. ,. - . . ; . . ..
..
. , . . .. .-. .
. . . . .
- . . .
: ,
WO~ltO9104 PCT/US90/0~215
2~7~6~9
; 17
,i
lotions or creams for use as hand cleaners, the organic
solvent and solubilizing additive components may be
pre-emulsified in water with stirring and a thickening
agent added to form the final emulsion in semipaste or
thickened form.
Upon sufficient dilution with water, the emulsions of
the invention will first be transformed into microemulsion
form and then into solution form with an accompanying
decrease in the degreasing efficacy of the composition as
shown by the e~perimental test data prasented hereinafter.
-~ As shown by the working examples set forth
hereinafter, the invention may be practiced to pr~are
emulsion compositions having varying concentrations of
components, especially solvent level, depending upon the
end use for the emulsions and, thus, emulsion concentrate
compositions and ready-to-use strength emulsion
compositions can be prepared. In either case, the desired
stabilities for the various emulsions of the invention can
~e achieved by observing the following principles.
Generally speaking, emulsion concentrate compositions
(such as described in E~amples 2-4 hereinafter) are more
susceptible to destabilization (or "brea~ing") with
; increasing ionic strength than their less concentrated,
more dilute counterparts. For this reason the use of, e.g.
ionic surfactants and couplers, ionic builders, and ionic
anti-flash rust/anti-corrosion additives, etc. in
formulating concentrates must be kept at a minimum or, if
possible, wholly avoided or eliminated. This can often be
accompIished simply by substituting equivalent nonionic
replacements for ionic ones. On the other hand,
ready-to-use strength emulsion compositions (such as
described in Example 27 hereinafter) can often safely
accommodate modest levels of ionic components, additives,
etc. (such as solubilizing additives, thickeners, chelants,
and anti-flash rust/corrosion additives) without
' ' .
SUBSTIIUTE SHEEI
..
.. ~ . .
, . . .
. . . ` . . .
-;. . -
:~ . . >
WO91/09104 PCT/US90/07215
9 18
experiencing serious emulsion destabilization and resultant
shelf life shortening. In the latter case thicXeners often
; play an important role in promoting long-term emulsion
stability. In any case, in practicing the above
guidelines, the restrictions placed upon the ract~.ce of
the invention must be strictly adhered co.
The concantration of the aqueous cleanar~dasreasel
solution, as indicated by the terms "'cotal soli,is concenc"
and "total actives content" in the working zxam ies
provided hereinafter refers, respectiY~ly, to ~he corn~s~d
percentages of nonvolatile components and ~o tne surn cotal
of nonaqueous volatile and nonvolatila componsnts
The following examples illustrato the pract ce of Lhe
inventlon.
.
Example 1
In the following examples of illustrative cleaner/
degreaser emulsion compositions of the present invention,
the compositions were subjected as indicated to the
definitive, semiquantitative degreasing test method
~ 20 described below in order to measure their cleaning/
;~ degreasing efficacy.
A magnetic stirrer (Fisher Scientific Co., Catalog No.
14-511-lA) provided with a vaned disc magnetic stir bar
(7~8" (diameter) x 5/8" (height), 22 mm x 15 mm, Fisher
Scientific Co., Catalog No. 14-511-98C) was used. In each
instance, pre-cleaned,`borosilicate glass microslides (3"
1", 1.0 mm thickness) were thinly smeared/rub-on coated
with Vaseline brand white petroleum jelly on one side only
to a distance of 1.0" from the bottom edge to provide a
1.0" x 1.0" coated area. The test cleaner/degreaser
emulsions or solutions were employed at the strength
indicated and in an amount sufficient to fill a 50 ml Pyrex
.
~ .
S~B'~'TIIU~E SH~ET
. ,
... -` ' ~ . ;. : . ~ :
~ . . ; ~ . .`.
~ -:
- :
....,...~.
...... .
.
.
.
WO9l/09104 2 o 7 ~ 6 7 9 ~CT/US90/07215
19
bea~er containing the vaned disc magnetic stirrer bar to a
level of 40 ml. Each test material and surrounding air
were maintained at 21 + 0.5C and the test material
stirring rate was determined by a setting of "3" on the
stirrer dial of the magnetic stirrer. The stirring disc
was positioned off-center to accomodate each microslide,
touching neither the beaker walls nor the microslide and
rotating freely when in use. The microslide, in each test,
rested upright on the beaker bottom, was allowed to lean
agains-t tha lip of the beaker at an appro~imately 75 angle
and was positioned with the Vaseline coated face or area
facing upward away from the vaned disc magnetic stirrer ~ar.
~ er each test, the beaker containing the stirrer bar
was filled to 40 ml. with the test cleaning/degreasing
emulsion or solution at the indicated concentration, placed
atop the magnetic stirrer plate, and positioned off-center
to accomodate the glass microslide, and yet allow the vaned
disc stirrer bar to rotate or spin freely. The stirrer was
turned on, the dial ad~usted manually to the "3~ stirring
~0 rate setting and the Vaseline thin film coated glass
microslide was introduced into the test material bath in
such a manner that the coated side faced up~ard and ~as
positioned away from the stirrer bar. The time "0" was
noted immediately on a watch or clock with a sweep second
hand.
At appropriate time intervals, the glass microslide
was briefly removed from thè cleaner/degreaser material
bath and immediately "read" for "% Vaseline removed from
the l.0" x l.0" treated area", an objective determination,
after which the microslide was~immediately returned to the
stirred aqueous cleaner/degreaser bath. The duration of
the degreasing test is determined by the time needed for
;
complete, 100% removal of the Vaseline film from the glass
microslide surface.
SII~SIIIU~E S,~EEI
~ . . ~ ,,
~. . .
WO~1/09104 PCT/~S90/07215
The accuracy of the above-described test method is of
the order of ~ 5% as determined by replicate run averaging.
Example 2
An aqueous cleaner/degreaser emulsion was prePar2d
having the following composition:
ComPonent
l-Pheno~y-2-propanol 20.0
(Dowanol PPh~
Isostearamide diethanolamide (1:1~ 3.0
(Monamide 150 IS)
Soft H20 177.0
200.0
The isostearamide diethanolamide and water were
stirred until the former was dispersed. The
1-phenoxy-2-propanol solvent was then stirred into the
dispersion at room temperature for 45 minutes to achieve
`~ complete emulsificationO The resulting composition was an
intensely bluish/white emulsion having a pH of 8.85, a
Brookfield viscosity (L~-#2 spindle, 60 rpm) of 4.0
centipoise, a total solids content ttheory) of 1.50%, and a
total actives content (theory) of 11.50%. The emulsion
e~hibited no flash point and was found to be storage stable
for greater than ~ive months at room temperature. If
forced to slowly separate or oil out, e.g., in freeze/thaw
cycling, the composition is easily redispersed into
~ emulsion form by agitation.
;- At a 1:5 dilution with water, a bluish/white
-~ microemulsion formed. The microemulsion very readily and
~ completely removed the following markings from alkyd
::
,
.~ .
':
~, .
SU~STIIUTE S~EET
- ,
-. . , . , . i .
.
. ~ ,. ~,,........ . , , ., , ..
WO91/09104 PC~/US90/07215
2 ~
21
enameled metal surfaces: black, indelible Magic Marker
felt pen, blue and black indelible ballpoint pen, #l
hardness pencil, red (waxy) crayon and smeared automotive
grease.
Th~ above-formed microemulsion was subjected to the
degreasing test method of E~ample 1 with the following
results:
ls~ attack on greased slide at 1 sec.
60% re~oval of grease at 10 sec.
100% removal of grease at 17 sec.
~ ExamPle 3
:: .
E~ample 2 was repeated in preparing an aqueous
cleaner/degreaser emulsion having the following composition:
Com~onent Wt.%
15 1-Phenoxy-2-propanol 20.0
(Dowanol PPh)
Isostearamide diethanolamide (1:1) 5.0
(Monamide 150 IS)
Monoethanolamine ~0.2
20 Soft H20 174.8
200.0
The resulting composition was an intensely
bluish~white emulsion having a pH of 10.07, a Brookfield
viscosity (LV-#2 spindle, 60 rpm) of 5.S centipoise, a
total solids content (theory) of 2.S0%, and a total actives
` ~ content (iheory) of 12.60%. The emulsion exhibited no
v~ flash point and was found to be storage stable for in
; excess of five months at room temperature. Upon very
slight, slow oiling out, the composition was readily
redispersed on shaking.
~ .
SUBSTIIU~E SHEET
~..
WO91/~9104 PCT/US90/07215
~ ~6~9 22
~ t a 1:5 dilution with water, a bluish/white
microemulsion formed. The microemulsion very easily,
readily and completely removed the following markings from
alkyd enameled metal surfaces: black, indelible Magic
Marker felt pen, blue and black indelible ballpoint pen, ~1
hardness pencil, red (wa~y) crayon and smeared automotive
grease.
The abova-formed microemulsion was subjected co the
degreasing test method of Example 1 with the following
results:
1st attack on greased slide at 1 sec.
70-7S% removal of grease at 10 52C.
100~ removal of grease at 14 sec.
; .
ExamPle 4
., ,
lS Example 2 was repeated in preparing an aqueous
cleaner/degreaser emulsion having the following composition:
Component Wt.~
Phenoxy-2-propanol 20.0
~Dowanol PPh)
20 Isostearamide diethanolamide (1:1) 6.0
(Monamide 150 IS)
Monoethanolamine 0.2
. .
Soft H20 173.8
~; 200.0
The resulting composition was an intensely
bluish/white émulsion having a pH of 9.76, a Brookfield
viscosity (LV-#2 spindle, 60 rpm) of 6.5 centipoise, a
total solids content (theory) of 3.00%, and a total actives
content (theory) of 13.10%. The emulsion exhibited no
,
~UBSIIIUTE SHEEI
. . . ..
:: :
: . .
. .
WO91/09104 PCT/US90/07215
207 0~79
23
flash point and was found to have e~cellent storage
stability for at least two months- at room temperature with
no separation occurring.
At a 1:5 dilution with water, a bluish/white
microemulsion formed. The microemulsion very easily,
readily and completely rsmoved the following workings from
alkyd enameled me~al surfaces: black, indelible Magic
Marke~ ~21t ~en, ~lue and Dlack indelible ballpoint pen, #l
hardness pencil, red (~axy) crayon and smeared automotive
grease.
The a~ove microemulsion was subjected to the
~; degreasing test method of RxamDle l ~ith the following
- results:
~` 1st attack on greased slide at l sec.
;~ 15 60% removal of grease at lO sec.
`~ 100% removal of grease at 18 sec.
.
Esample 5
Example 2 was repeated in preparing an aqueous
cl~ane-~degreaser emulsion having the following composition:
' .
Component - Wt.~%
.~
`;~`t l-Pheno~y-2-propanol 20.0
(Dowanol PPh)
Isostearamide diethanolamide (l:l) 7.0
(Monamide 150 IS)
25 Monoethanolamine 0.2
... .
Soft H20 172.8
` 200.0
~ .
.
. ~ :
::
ITllTE S5~T
,. . .
.
.
.... ..
WO91/0~104 PCT/US90/07215
9~ QJ
24
The resulting composition was an intensely
bluish/white emulsion having a pH of 9.72, a Brookfield
viscosity (LV-~2 spindle, 60 rpm) of 4.8 centipoise, a
total solids content (theory) of 3.5%, and a total actives
content (theory) of 13.6%. The emulsion exhibited no flash
point and was found to have e~cellent storage stability for
at least two months at room temperature with no separakion
occurring.
At a 1:5 dilution with water, a bluish/white
microemulsion formed. The microemulsion very quickly and
completely removed all of the markings set forth in
E~amples 2-4 from alkyd enameled metal surfaces.
; ~ The microemulsion was subjected to the degreasing test
method of E~ample l with the following r~sults:
1st attack on greased slide at l sec.
.
~ 75-80% removal of grease at lO sec.
; ~ 100% removaI o~ grease at 13 sec.
.
~ E2amPle 6
.,
~ ~ EYample 2 was repeated in preparing an aqueous
! 20 cleaner/degreaser emulsion having the following composition:
,
Component Wt.%
l-Pheno~y-2-propanol 20.0
(Dowanol PPh)
Isostea~ramide diethanolamide (l:l) 3.0
(Monamide 150 IS)
Lauramide diethanolamide (l:l) 3.0
(Superamide)(Clindrol LL-136)
Monoethanolamine - 0.2
Soft H20 173.8
- 200.0
. ~ ,
. ' .
~STIT~T~ â~d~ET
.
.
.
.
WO91/09104 PCTtUS90/07215
2~70~79
;
The resulting composition was a bluish/white emulsion
having a pH of 9.92, a Brookfield viscosity (LV-~2 spindle,
60 rpm) of 4.0 centipoise, a total solids content (theory)
of 3.0%, and a total actives content (theory) of 13.1%.
5 The emulsion e~hibited no flash point and was found to have
good/e~ceil~nt stor~ge staoili~y lor in excess of two
months at room temperature.
~ t a 1:5 dilution wit~ watar, a bluish/white
microemuision formed. ~he microemulsion ver~ easily and
completely remo~led all or the markings set forth in
Examples 2-~ from alkyd enameled metal surfaces.
he microemlllslon was su~jected to the degreasing test
method o~ am~le 1 with the following results:
: .
:
1st attac~ on greased slide at 1 sec.
60% removal of grease at 10 sec.
85% removal of grease at 15 sec.
100% removal of grease at 17 sec.
:
:~ E~ample 7
E~ample 2 ~as repeated in preparing an aqueous
cleaner/degreaser emulsion having the following composition:
Component Wt.%
l-Pheno2y-2-propanol 20.0
(Dowanol PPh)
Ricinoleamide diethanolamide (~:1) 7.0
~Superamide)(Mac~amide R)
Monoethanolamine 0.2
Soft H20 172.8
200.0
T~TUT~ SHET
WO91/09104 PCT/US90/07~15
6rl 9 26
The latter three components were stirred until fully
dispersed and the l-phenoxy-2-propanol was then stirred
into the dispersion for one hour to form an emulsion. The
resulting composition was a white, colorless emulsion with
a slightly bluish cast, having a pH of 9.93, a Brookfield
viscosity (LV-~2 spindle, 60 rpm) of 4.6 centipoise, a
total solids content (theory) of 3.5%, and a total actives
content (~h20LY) of 13.~%. The emulsion exhibited no flash
point, and ~as iound to have good storage stability for in
e2cess of -two months at room temperature.
A'c a 1:5 dilution with water, a white to bluish/white
emulsion ~as formed. The emulsion completely removed all
of the markings set forth in E2amples 2-4 from alkyd
enameled metal surfaces.
The emulsion was subjected to the degreas-ing test
method of Example l with the following results:
~ 1st attack on greased slide at l sec.
'~ 75% removal of grease at 10 sec.
~i lO0~ removal of grease at 12 sec.
.'. : .
E~ample 8
E~ample 2 was repeated in preparing an aqueous
cleaner/degreaser emulsion having the following composition:
Component Wt.%
l-Phenoxy-2-propanol 20.0
(Dowanol PPh)
Oleamide diethanolamide (l:l) 6.0
~Superamide)(Mackamide MO)
Monoe~thanolamine 0.2
Soft H20 173.8
200.0
''`" ~ ' .
. .
,,
iZT~TE ~IE~T
, . . ~.
~ . :
;,'~ . .
"
,. - .... :
WO91/09104 PCT/US90/07215
-
, .,:
27 ~ 6~
The resulting composition was a white emulsion having
a pH of 10.21, a Brookfield viscosity (LV-~2 spindle, 60
rpm) of 4.5 centipoise, a total solids content (theory) of
3.0%, and a total actives content (theory) of 13.1%. The
emulsion e~hibited no flash point, and was found to have
good/excellent scorage staoilicy ror cwo moncns at room
temperature.
At a 1:5 dilution Witil ~at2r, a -~hice colored emulsion
was formed. The emulsion smudsed bu-c complecely removed
all of th2 markings SQt forth in ~xamples 2-4 ~rom alkyd
enameled metal surraces.
The emulslon ~7as suojected to ,.hs degx~asing test
method of Example 1 ~ith the follow-lng results:
`:
- 1st attack on greased slide at 1 sec.
70-75% removal of grease at 10 sec.
100~ removal of grease at 14 sec.
.
ExamPle 9
E~ample 2 was repeated in preparing an aqueous
cleaner~degreaser smulsion having the following composition:
ComPonent Wt.%
l-Pheno~y-2-propanol 20.0
(Dowanol PPh)
Isostearamide diethanolamide (1~ 7.0
(Mackamide ISA)
25 Monoethanolamine 0.2
~ Soft H20 172.8
:~ 200.0
'
~STITDTrr SHE~T
WO91/09l04 PCT/US90/07215
~9 ~
; 28
The resulting composition was an intensely
bluish/white emulsion having a pH of 9.79, a Brookfield
viscosity (LV-#2 spindle, 60 rpm) of 6.2 centipoise, a
total solids contant (theory) of 3.5%, and a total actives
content (theory) of 13.6%. The emulsion exhi~ited no flash
point, and was found ~o be very sta~le over e~tended
periods at room temperature.
At a 1:5 dilutlon with. water, a ~luish-white
microemuision ~/as formed. The microemulsion readily and
complet^-ly -emov2d âll 0_ tlle marXings set forth in
E~amples 2-~ from alkyd enarneled metal suraces.
~I The microemulsicn was subjected to the dsgreasing test
method sst for'h in ~__mple 1 with the -Eollowing results:
1st attac~ on greased slide at 1 sec.
70% removal of grease at 10 sec.
100% removal of grease at 15 sec.
,, ExamPle 10
:, .
E~ample 2 was repeated in preparing an àqueous
cleaner/degreaser emulsion having the follo~ing composition:
1 20 ComPonent Wt.%
l-Pheno~y-2-propanol 20.0
(Dowanol PPh~
Linoleamide diethanoIamide (1:1) 7.0
(soyamide DEA-
Clindrol LT-15-73-1)
Monoethanolamine- 0.2
Soft H20 172.8
200.0
;~ .
TITUT~ SHtET
. ~ .
.. . .
, "~
,
,
. ,
` .
~, .
WO91/09104 PCT/US90/07215
o~79
29
The resulting composition was an intensely white
emulsion with a slight bluish cast and having a pH of
10.42, a Brookfield viscosity (LV-#2, spindle, 60 rpm) of
5.0 centipoise, a total solids content (theory) of 3.5%,
and a total actives content (theory) o 13.6~,. The
emulsion was quite stable at room temperatur~ for 1-2
months.
At a 1:5 dilution with water, a ~luisn/white
microemulsion was formed. The microemulsion readily and
completely removed all of the markings s~t Lorth in
E~amples 2-4 from alkyd enameled metal surfaces.
The microemulsion was subjected to the degreasing test
method of ~xample 1 with the followins ,esults:
1st attack on greased slide at 1 sec.
~;~ 15 100% removal of grease at 13 sec.
~ E~amPle 11
Example 2 was repeated in preparing an aqueous
cleaner/degreaser emulsion having the following composition:
ComPonent r~l,.,,;
20 1-Phenoxy-2-propanol 30.0
(Dowanol PPh)
Isostearamide diethanolamide (1:1) 10.0
~Mackamide ISA)
Monoethanolamine 0.3
25 Soft H20 159.7
200.0
.
The resulting composition was an intensely
bluish/white emulsion having a pH of 9.63, a Brookfield
viscosity (~V-#2 spindle, 60 rpm) of 7.0 centipoise, a
~ .
S~T~TUTE SHE!ET
:
.
,.
WO91/09104 PCT/US90/07215
~9 30
total solids content ~theory) o 5.0%~ and a total actives
content (theory) or 20~15~o~ The emulsion exhibited
excellent stability over an extended period at room
temperature.
At a 1:8 dilution ~ith water, a bluish/white
microemulsion ~as lormed wnich had a 1.67% conceniration of
l-phenoxy-2-~ropanol. The microemulsion vary easily and
completely remov2d aLl O:L ~'ne ~nar';inys 3eJC for~h in
Examples 2-~ rrom aixyd enam21ed metal surraces.
- 10 The microeml~lsio7.l was su3~-ctedi to -the degreasing test
method of E~ample 1 with tne following results:
:~ .
1st attack on r,reased ~lide ar 1 sec.
70~75~ removal of grease at 10 sec.
100% removal of grease at 15 sec.
Esample 12
E~ample 2 was repeated in preparing an aqueous
; cleaner/degreaser emulsion having the following composition:
Componen~ Wt,%
l-Phenoxy-2-propanol 20.0
(Dowanol PPh)
I~;ostearamide diethanolamide (1:1) 8.0
(Monamid 150-IS)
Monoethanolamine 0.2
Soft H20 171.8
200.0
The resulting composition ~as a very intense
bluish/white emulsion having a pH of 9. 85~ a Brookfield
~ viscosity (LV-#2 spindle, 60 rpm) of 6.5 centipoise, a
:
: . .
.~, .
~ . .
. .
~ ~U~IU iir S~I~LE~
~ ~ .
.. . , ~, , .
,
.
~,
WO91/09104 PCT/US90/07215
207067~
31
total solids content (theory) of 4.0%, and a total actives
` content (theory) of 14.1%. The emulsion e~hibited
e~cellent stability over at least a four month period.
At a 1:5 dilution with water, a bluish to
bluish/white microemulsion was formed which had a 1.67%
concentration of l-phenoxy-2-propanol. The microemulsion
~ very easily and completely removed all of the markings sat
-; forth in E~amples 2-4 from alkyd enameled rnetal surfaces.
The microemulsion was subjected to the degraasing
~ 10 test method of E~ample 1 with the following results:
`~ 1st attac~s on greased slide at 1 sec.
40% removal of grease at 10 sec.
65-70% removal of grease at 15 sec.
100% removal of grease at 22 sec.
~xam~le 13
.~ ~
A hand cleaner in the form of a semipaste emulsion was
prepared having the following composition:
:
ComPonent ~t.%
Polypropylene glycol 30.0
(Dow P-2000)
Linoleamide diethanolamide (1:1)4.5
(Soyamide DEA-Clindrol
LT-15-73-1)
Acrylic acid/alkyl 0.2
methacrylate copoIymer
30% aqueous
;;~ (Acrysol ICS-l)
~ Triethanolamine 0.5
.
Soft H20 261.0
;30
,
S~ T~TE SH~E~
. ` . . .. ..
. . . . ` i~ .`
., . ` ..
.
.
:
WO9l/09104 PCT/US90/07215
32
The polypropylene glycol and linoleamide
diethanolamide were pre-emulsified in water with stirring
and the Acrysol ICS-l thickening agent was then added with
stirring. The triethanolamine was then added dropwise with
stirring to form a s~mioaste, intens21~7 whit? amulsion.
The emulsion had a pH or 8.22, a Brookfield viscosity
(LV-#4 spindle, 6 rpm) of 13,259 c~n-~ipoiss, and 3 -total
solids content (theory? of ïl, i~;,
The emulsion had a very smootn eel and e.~hibited
fair/good r~moval of oily, g-aasy _oils Irom hands.
Fc~a~o 1 ~ 1",1
A hand cleaner in the form or a semipaste emulsion was
prepared having the following composition:
Com~onent 'W~
15 1-Phenoxy~2-propanol 15.0
tDowanol PPh)
Polypropylene glycol 15.0
(Dow P-2000)
Nonylphenoxypoly(ethyleneoxy) . 0.3
(8.5) ethanol (nonionic
surfactant-T-Det N-9.5)
Polyacrylic acid crosslinked 265.5
: with polyalkenyl polyether
(0.12% aq. Carbopol 940)
25 Linoleamide diethanolamide (1:1) 4.2
(Soyamide DEA- Clindrol
LT-15-73-1)
300.0
The first four components listed were pre~emulsified
with stirring, and the linoleamide diethanolamide was added
with vigorous stirring to form-a semipaste, intensely white
: ` ~
.,
~ .
. .
TITUT~ SHEEI
.
,
WO91/09104 PCT/US90/07215
2~70679
33
.
emulsion. The emulsion had a pH of 6.72, a Brookfield
viscosity (LV-#4 spindle, 6 rpm) of 23,000 centipoise, a
total solids content (theory) of 6.61%, and a total actives
content (theory) of 11.61%.
The emulsion had a smooth feel, excellent rinsing
properties, and e~hibited e2cellent, fast removal of oily,
greasy soils from hands although somewhak irritating to tne
skin.
E~am le 15
~':
A hand cleaner in the form of a thic~, paste/lo~ion
emulsion was prepared having the following composition:
ComPonent ~,~
l-Phenoxy-2-propanol 1.0
(Dowanol PPh)
15 Polypropylene glycol g.o
(Dow P-2000)
Mineral Oil 9.0
(Viscosity, 165
centipoise)
20 Linoleamide diethanolamide (1:1) 2.0
(Soyamide D~A- Clindrol
LT-15-73-1)
Soft H20 78.0
Acrylic acid/alkyl 1.0
methacrylate copolymer,
30% aqueous (Acrysol
ICS-l) -
100.0
All of the components except the Acrysol ICS-l
thickening agent were pre-emulsified with stirring, and the
thickening agent was then added slowly with vigorous
' ' ' '
: .
~ ~iJ~Sli~,~TE SHEEl
,
.
.~ `
WO91/09104 PCT/US90/07215
~ ~ 34
stirring. The resulting composition ~as an intensely
; bluish/white emulsion in the form of a thick,
paste/lotion. The emulsion had a pH of 7.~2, a Brookfield
viscosity (LV-#4 spindle, 6 rpm) o~ 5~,000 centipoise, a
total solids content (theory) of ~0.3;, ~nd a otal acti~es
content (theory) of 21.3%.
The emulsion had a smooth f9el, good rins~ ng
characteristics, and exhibit~d ~ood/~er~f good rer,o~al OL
oily and greasy soils from hands.
ExamPle 16
Example 15 was repeat2d in prepa-~-ng a sem-pas~e
:; emulsion having the following composition:
Component
Phenoxy-2-propanol l.0
}5 (Dowanol PPh)
2-Phenoxyethanol l.0
(Dowanol EPh)
Tripropyleneglycol l.0
monomethyl ether
(Dowanol TPM)
Polypropylene glycol 9.o
~Dow P-2000)
Mineral oil 9.0
(Viscosity, 165 centipoise)
25 Linoleamide diethanolamide (l:l) 2.0
(Soyamide DEA-Clindrol
LT-15-73-l)
. . ~ .
Soft H20 75.6
Acrylic acid/alkyl l.4
methacrylate copolymer,
30% aqueous (Acrysol
` ICS-l)
: ,. .
~: 100.0
-,,
. ~
S1~B~TIIUTE SHET
:: ,-,.: . .
:. - .
WO91/09104 PCT/US~0/07215
2070~9
The resulting composition was an intensely
~luish/white emulsion in the form of a semipaste. The
emulsion had a pH of 7.02, a Brookfield viscosity (LV-#4
spindle, 6 rpm) of 28,000 centipoise, a total solids
content (theory) of 20.4%, and a total actives content
(theory) of 23.42%.
The emulsion had a very smooth feel, e~cellent
rinsability characteristics, and e~hibited very good
removal of oily and greasy soils from hands with a low
level of irritation to the skin.
E~ample 17
Example 15 was repeated in preparing a thick lotion
emulsion having the following composition:
Com~onent Wt.%
15 Polypropylene glycol 9.0
(Dow P-2000)
Mineral oil 9.0
(Viscosity, 165 centipoise)
Linoleamide diethanolamide (1:1) 5.0
(Soyamide DEA-Clindrol
LT-15-73-1)
Soft H20 76.1
Acrylic acid/alkyl 0.9
methacrylate copolymer,
30% aqueous (Acrysol
ICS-l)
100.. 0
The resulting composition was an intensely white
emulsion in the form of a thick lotion. The e~ulsion had a
pH of 9.33, a Brookfield viscosity (Lv-#4 spindle, 6 rpm)
of 24,400 centipoise, and a total solids content (theory)
~ of 23.27%.
:,~
~BS I ITUTE SHET
.. . . . ;
.
.::
... .- . . .
. .
WO 91tO9104 PCT/US90/07215
~C ~ 3 6
: The emulsion had a very smooth feel, e~cellent
rinsability characteristics, and e~hibited e~cellent
removal of oily and greasy soilants from hands.
Example 18
E~ample 15 was repeated in prepari:~g 2 5-~eam/loclon
emulsion having the following composit~on:
: Component
,. .~
l-Pheno~y-2-propanol l.0
(Dowanol PPh)
- lO Polypropylene glycol 15.0
~ (Dow P-2000)
:, .
Nonylphenoxypoly(ethyleneo~y)3 . O
(7) ethanol (nonionic
surfactant-T-Det N-8)
:~ 15 Linoleamide diethanolamide (l:l) 2.0
(Soyamide DEA-Clindrol
LT-15-73-l)
Soft H20 78.0
Acrylic acid/alkyl 1.0
methacrylate copolymer,
30~ aqueous (Acrysol
ICS-l)
:
10 0 . 0
.
The resulting composition was an intensely white
emulsion in the orm of a cream/lotion. The emulsion had a
. pH of 8.07, a Brookfield viscosity (LV-#3 spindle, 12 rpm)
of 4300 centipoise, a total solids content (theory) of
~`~ 20.3%, and a total actives content (theory) of 21.3%.
. - .
,.
.
:'~
~ .
`.
'',
BS~lTUTE SHEET
: . ~ .. .
~ ~ .
.. -
.. . ..
.,. :: ~
WO9l/09104 PCT/US90/~72~5
37 .20~Ø~79
The emulsion had a very smooth feel, excellent
rinsability characteristics, and exhibited excellent
removal of oily and greasy soilants from hands. In
addition, the emulsion is fully biodegradable.
ExamPle 19
An emulsion was prepared having the following
composition:
ComPonent Wt.%
::
I-Pheno~y-2-propanol 20.0
;~ 10(Dowanol P~h)
; Nonylphenosypoly(ethyleneo2y) 4.0
(8) ethanol (nonionic
surfactant-T-Det N-8)
Acrylic acid/alkyl 1.60
methacrylate copolymer,
30~ aqueous (Acrysol
ICS-l)
Triethanolamine 0.7
~ Soft H20 173.7
:;. .
200.0
The water was added with stirring to the
l-pheno2y-2-propanol and nonionic surfactant components.
The Acrysol ICS-l thickening agent was then added with
continued stirring, followed by the dropwise addition of
25 the triethanolamine with stirring. The resulting
composition was a white, creamy emulsion having a pH of
; 7.82, a Brookfield viscosity (LV-#2 spindle, 30 rpm) of 120
centipoise, a total solids content (theory) of 2.59%, and a
total actives content (theory) of 12.59~o.
, ~ .
- ~:
S~EEI
.. .
. . . ..
- , - . . . .
. . . ~ . ,
.
, . .
WO91/09104 PCT/US90/07215
.. ..
~ 38
At both a 1:~ and a 1:5 dilution with water, diluted
emulsions were formed which easily removed black Magic
Marker markings from alkyd enameled metal surfaces.
At a 1:4 dilution with water, the resulting
emulsion was subjected to the degreasing test method of
- Example 1 with the following results:
1st attack on greased slide at 3 sec.
55-60~o removal of grease at 10 sec.
100% removal of grease at 15 sec.
.
At a 1:5 dilution ~ith ~ater, the resulting emulsi~n
was subjected to the deqreasing test method of E~.amplz 1
with the following results:
.
1st attack on greased slide at 3 sec.
55-60% removal of grea~e at 10 sec.
lS 100% removal of grease at 20 sec.
:,~ .
E~ample 20
:` :
E~xample 19 was repeated in preparing an emulsion
having the following composition:
Component Wt,%
20 1-Pheno~y-2-propanol 20.0
` (Dowanol PPh)
Nonylpheno~ypoly(ethyleneoxy) 3.0
(8.5) ethanol (nonionic
surfactant-T-Det N-9.5)
.
~; 25 Triethanolamlne 0.7
Soft H20 containing 0.06% 176.3
^ polyacrylic acid crosslinked
with polyalkenyl polyether
(Carbopol 940 thickener)
200.0
~'.
S~BST~TlilTE SHET
:
. .. .. . . . j . ,~ ..
.
. . . . -
.
..... ..... .
WO91/09104 PCT/US90/07215
39 207~679
The resulting composition was a white, creamy emulsion
having a pH of 8.42, a Brookfield viscosity (LV-#2 spindle,
30 rpm) of 217 centipoise, a total solids content (theory)
of 1.75%, and a total actives content (theory) of
11.75%.
At a 1:5 dilution with water, an emulsion resulted
which e3silY remoYed black Magic Marker markings ~rom an
alkyd ~nameled metal surface. The emulsion was subjected
to the degreasing test method of Example 1 with the
followi~g ~sults:
: ,
1st attas~ on greased slide at 1 sec.
(almost instantaneous)
100% removal of grease at 9 sec.
At a 1:10 dilution with water, a slightly hazy
~; .
emulsion-solution was formed which was rather ineffective
in removing black Magic Marker markings from an alkyd
enameled metal surface. The emulsion-solution was
subjected to the degreasing test method of Example 1 with
the following results:
: ' ~ .
1st attack on greased slide at 3 sec.
60% removal of grease at 15 sec.
100% removal of grease at 25 sec.
,' :
: ! At a 1:20 dilution with water, a clear solution was
.. ,: .
formed which was totally ineffecti~e in removing black
Magic Marker markings from an alkyd enameled metal
surface. The solution was subjected to the degreasing test
; method of E~ample 1 with the following results:
~ ~ 1st attack on greased slide at 15 sec.
;~ ~ 10-15% removal of grease at 1.0 min.
~; 30 25% removal af grease at 2.0 min.
SUBSTITU~E SRFET
:
.. ~......................... . .
.. . . . ..
. . .
.
WOgl~O9104 PCT/US90/07215
~,~19~- 40
45% removal of grease at 30 min.
60~ removal of grease at 4.0 min.
70% removal of grease at S.0 min.
75-80% removal of grease at 6.0 min.
85% removal of grease at 7.0 min.
90-95~ removal of grease at 9.0 min.
100% removal of grease at 10.0 min.
The marked change in degreasing erficac~ (rates)
between the 1:10 and 1:20 composition dilution ratios can,
in part, be attributable to the change from emulsion to
solution form of the cleaner/degreaser.
Example 21
j Example 19 was repeated in preparing an emulsion
having the following composition:
Com~Qnent Wt.
l-Phenoxy-2-propanol 20.0
(Dowanol PPh)
I Octylphenol ethoxylate (5E.O.) 3.0
~Triton X-45)
` 20 Triethanolamine 0.5
Soft H20 containing 0.06% 176.5
polyacrylic acid crosslinked
with polyalkenyl polyether
(Carbopol 940 thickener)
200.0
- The resulting composition was a white, creamy emulsion
having a pH of 8.39, a Brookfield viscosity (LV-#2 spindle,
30 rpm) of 162 centipoise, a total solids content (theory)
of 1.75%, and a total actives content (theory) of 11.75%.
.
., .
~UBSTITi3T~ SHEET
WO91/09104 PCT/US90/07215
2070679
41 ' ' ,
~t a 1:5 dilution with water, an emulsion resulted
which was sub~ected to the degreasing test method of
Example l with the following results:
'
1st attack on greased slide at 5 sec.
35-40% removal of grease at 10 sec.
80~ removal o graas2 at 20 sec.
lO0~ ~2moval of grease at 25 sec.
.t ~ l:10 ~lluti~n with water, an emulsion resulted
which was subjected to t'ne degreasing test method of
E~ample 1 with the following results:
~. ,
1st attack on greased slide at lO sec.
` 40% removal of grease at 20 sec.
75% removal of grease at 30 sec.
lO0~ removal of grease at 45 sec.
At a 1:20 dilution with water, a hazy
emulsion-solution resulted which was subjected to the
degreasing test method of E~ample 1 with the following
results-
~`~' '
1st attack on greased slide at 20 sec.
106 removal of grease at l min.
20-25% removal of grease at 2 min.
i 40% removal of grease at 3 min.
~ 65% removal of grease at 4.25 min.
,
85-90% removal of grease at 6 min.
~ 100% removal of grease at 7.5 min.
~ ~ ,
~ .
. ~
-
:: :
.
:~ S'JB~TITUTE S'~EEI
,~
. . ~ ; . . .
. . .
. ~ ~,; . .
, ~ .
;:
WO91/09104 PCT/US90/07215
~9
42
Exam~le 22
E2ample 19 was repeated in preparing an emulsion
having the following composition:
ComPonent Wt.%
5 1-Pheno~y-2-propanol 30.0
(Dowanol PPh)
Dodecylbenzenesulfonic acid 0.6
Acrylic acld/alkyl 2.2
methacrylate copolymer,
30% aqueous (Acrysol
ICS-l)
Triethanolamine 1.4
., .
Soft H20 165.8
200.0
The resulting composition was an intense white, creamy
emulsion having a pH of 7.67, a Brookfield viscosity ~LV-#2
spindle, 30 rpm) of 230 centipoise, a total solids content
(theory) of 1.33% and a total actives content (theory~ of
16.33~.
At a 1:5 dilution with water, an emulsion resulted
which very easily removed black Magic Marker markings from
an alkyd enameled metal surface. The emulsion was
subjected to the degreasing test method of E~ample 1 with
the following results:
' '
` 1st attack on greased slide at 1 sec.
(almost instantaneous)
100% removal of grease at 7 sec.
At a dilution of 1:10 with water, a very slight
, 30 emulsion or almost hazy solution resulted which was only
i moderately effective in removing black Magic Marker
.
~ , . .
~æSl'l~U~E S~EEI
- -
.
~: :
WO91/09104 , PCT/US90/~7215
2~7067~ ~
43
markings from an alkyd enameled metal surface. The
emulsion or solution was subjected to the degreasing test
method of'E~ample 1 with the following results:
1st attack on greased slide at 1+ sec.
100'~ relnoral os grease at 12 sec.
~, At a dilu~ion OL 1:20 -~ith water, a clear solution was
formed which was wholly ineffective in removing black Magic
~arl{er mark~ngs ~-rom an alkyd enameled metal surface. The
solution was subjected to the degreasing test method of
~ 10 E.sample 1 ~7ith the following results:
'~ 1st attack on greased slide at 5 sec.
40% remo,val of grease at 15 sec.
75% removal of grease at 30 sec.
100% removal of grease at 45 sec.
.- . . . .
' 15 , Example 23
;!
E~ample 19 was repeated in preparing an emulsion
having ths following composition:
Component Wt.%
l-Phenoxy-~-propanol 20.0
(Dowanol PPh)
Octylphenol etho~ylate - - 4.0
(7-8 E.O.) tTriton X-114)
Triethanolamine' ~ 1.0
Soft H20 172.0
25 Acrylic acid/alkyl 3.0
methacrylate copolymer,
30% aqueous (Acrysol
~ ICS-l)
'~ 200.0
,; .
~ .
SUBSTITUTE SHEET
.. . ... '. i ,. . ~ -
- ,
. .
~ ~ ,
~ `.. . .
. ..
. . . .
.~ . . . .
. , .
, . . .
` ~. . ..
WO91/09104 PCT/US90/07215
44
All of the components except the Acrysol ICS-l
thickening agent were pre-emulsified with a high-speed,
motor driven, 3-bladed propeller for 3 minutes, and the
Acrysol ICS-1 was then added very slowly with vigorous
stirring to provide immediate thickening. The resulting
composition was an intensely bluish/white emulsion in the
form of a thick lotion or semipaste having a pH of 7.88, a
Brookfield viscosity (~V-~4 spindle, 12 rpm) of 8600
centipoise, a total solids content (theory) of 2.8%, and a
; 10 total actives content (theory) of 12.8%.
At a I:5 dilution with water, a bluish/white
microemulsion formed which very easily and fully removed
the following markings from alkyd enameled metal surfaces:
black ~agic Marker felt pen, blue and black indelible
ballpoint pen, #1 hardness pencil and red (waxy) crayon.
`~ The microemulsion was subjected to the degreasing test
method of Example 1 with the following results:
;~ 1st attack on greased slide at 1 sec.
60~ removal of grease at 10 sec.
~ 20 100% removal of grease at 20 sec.
`::
ExampIe 24
Example 23 was repeated in preparing an emulsion
having the following composition:
wt.%
; 25 1-Pheno~y-2-propanol 20.0
tDowanol PPh)
Cg-Cll alkanol/2.5 E.O. 4.0
condensate (Neodol 91-2.5)
Triethanolamine 1.0
.
SUBSTITUTE SH~ET
,
.~. ... .
-. - .
. . .
.. . .
WO91/09104 P~T/US90/07215
` 2~7D~79
Soft H20 172.0 :
Acrylic acid/alkyl 3.0
- methacrylate copolymer,
30% aqueous (Acrysol
ICS-l)
200 . 0
The rosulting composition was an intensely
~luish-T~7hit~ omulsion ha~ing a pH of 8.27, a Brookfield
iscosi!cv ~LV-~3 spindle, 12 rpm) of 3650 centipoise, a
~: 10 total solids ~ontant (thaory) of 2.8~, and a total actives
content ~theory) of 12 . 8%.
~ a ':5 dilutlon wl~h .water, a bluish/white
- microemul~ion Eormed which very quickly, easily and totally
. removed the following markings from alkyd enameled metal
~ 15 surfaces: black Magic Marker felt pen, blue and black
; indelible ballpoint pen, #l hardness pencil, red (waxy)
crayon, and automotive grease smearings.
~`` The microemulsion was subjected to the degreasing test
method of Example 1 with the following results: ~
,' ,
1st attack on greased slide at less than 1 sec.
. 10~0o rcmGYal Of gLaase at 15 sec.
.
Example 25
; An aquesus cleaner/desreaser emulsion in the form of
`~ an aerosol formulation was prepared having the following
composition:
~` Component Wt.%
Phenoxy-2-propanol 3.0
. (Dowanol PPh)
: Octylphenol etho~ylate 0.2
(Triton X-45)
~ ,
,
~U8SlIIU~E SH~EI
"~ . . ~ - .
. ~ .
,.. , , ~ ~. .
~ , . . .
.
., ` , ~.. .
~ . . ..
WO91/09l04 PCT/US90/072~5
,:
.
~ 46
Deionized H20 95.2
Acrylic acid/alkyl 1.2
methacrylate copolymer,
30% aqueous (Acrysol
ICS-l)
Ammonium hydroxide (23%) 0.2
Sodium Nitrite 0.2
.
~' 100 . O
The fiLsL ~our compon2nts listed above were
pre-emulsified undsr hi~h speed stirring for three minutes
with a ~7ater d iven impeller, the ammonium hydroxide was
then very slowly added with vigorous stirring to give
immediate thickening, and the sodium nitrite was added last
with vigorous stirring until it was dissolved. The
resulting composition was a white emulsion/fluid with a pH
of 8.78, a Brookfield viscosity (LV-#2 spindle, 30 rpm) of
68 centipoise, a total solids content (theory) of 0.79%,
a~d a total actives content (theory) of 3.79%.
` The above composition was aerosolized in a 6 oz.
aerosol can using 8.32 g (15.0 ml~ of a propane-isobutane
blend sropellant (sold under the trade designation A-55).
The can was equipped with an AR-75 valve and Mark-18-1525
actuator. The fill ratio was 87/13.
It was found that the resulting aerosol formulation
very easily, quickly and totally removed the following
markings from alkyd enameled metal surfaces (spray on/wipe
off): black, indelible Magic Marker felt pen, blue and
black indelible ballpoint pen, #1 hardness pencil, red
(waxy) crayon and automotive grease smearings. The aerosol
formulation also readily removed fingerprints, smudges, and
similar markings from walls and woodwork.
.
` S~TITUTE SUEET
~:
..
WO9l/09104 PCT/US9~/0721
:
47 ~ ~ 7 ~ 6 ~ 9
E~ample 26
An aqueous cleaner/degreaser emulsion was prepared
; having the following com~osition:
. Component 1~1t.%
5 Phosphate ester coupler/ 0.30
emulsifier (MonaI3~ 1293~
`Isostearamide diethanolamide 0.40
:. (l:l) (~onamid 150-IS~
Monoethanolamine 0.40
lO Deionized H20 192.9
2-Ethylhe~o~yQthanol 2.0
~:~ (Ektasolv E~H~Eastman)
,
l-Pheno~y-2-propanol - 4.0
(Dowanol PPh)
200.0
The first four components were stirred at room
temperature until fully dispersed. The two organic
. solvents were then added with vigorous stirring for 0.5
hr. The resulting composition was an intensely
b:luish/white emulsion having a pH of 10.20, a Brookfield
viscos:ity (LV-#2 spindle, 60 rpm) of 4.5 centipoise, a
total solids content (theory) of 0.35% and a total actives
:: content (theory) of 3.55%. The emulsion exhibited
::~ e~cellent stability characteristics.
l'he emulsion possessed excellent, rapid, and efficient
cleaning/degreasing action against the following soilants:
;~ : black Magic Marker markings, ballpoint pen markings, #l
: hardness pencil markings, red (wa~y) crayon markings,
. automotive greases, Vaseline, lard, shortening, and
: 30 lipophilic oils.
.
.
~ SUBSTITUT~ Sl!~ET
., . ~
.; . .. . . .
,.,; . ,. . , . , .. .-
.. . , . ~ ~,
, . ,. . . , . . ;.. ~ . ~ . . . ... . .. ... .
, . , . `. . . . .
, . . . `
. . . . .~ ~. , ;.
, . , ` .
.. .. , ~ .~ . . ~ . . . ...
. . ,
-
WO9t/09104 PCT/US90/07215
.~9
7~9 ~8
Example 27
Example 26 was repeated in preparing an aqueous
cleaner/degreaser emulsion having the following composition:
ComPoner.~ Wt.%
5 Diethanolamino lauryl sulrata 0.20
(S-te~arol DEA, 35%)
Isostearamide diethanolamide0.40
xlonamid 150-1-S)
: Monoethanolamine 0.60
So~t ~2 192.3
l-Phenoxy-2-~ropanol 5.0
: (Dowanol ~Ph)
. Acrylic acid/alkyl methacrylate1.5
copolymer, 30% aqueous
: 15 ~Acrysol ICS-l)
; 200.0
The resulting composition was a bluish emulsion
(iridescent cast) having a pH of 10.21, a Brookfield
viscosity (L~-~2 spindle, 60 rpm) of 72 centipoise, a total
; 20 solids content (theory) of 0.46% and a total actives
content ttheory) of 3.26%. The emulsion exhibited
eæcellent stability characteristics.
The emulsion possessed excellent, rapid, and efficient
cleaning/degreasing action against all the soilants
listed in Example 26.
.
.
'^ .
~IBS~IIU~E SHEEI
: ~. . . . .
.: - ,. ,
. .
... . .
, .
WO91/09104 PC~/US~0/07215
:
2 ~ 7 9
49
ExamPle 28.
Example 26 was repeated in preparing an aqueous
:. cleaner/degreaser emulsion having the Eollowing composition:
:
Com~onent ~7t.%
~: . 5 Isostearamide diethanolamide 0.5
onamid 150-IS)
Sodium dodecyldiphenyletner O.l
disul:Eonate-coupler
~Dowfa~ 2Al, 45%)
. lO Monoethanolamine O.S
:; Soft H20 190.3
2-Pheno~yethanol 7.0
- (Dowanol EPh)
Acrylic acid/alkyl methacrylate l.5
copolymer, 30% aqueous
(Acrysol ICS-l)
,~ .
200.0
~ The resulting composition was a light, slightly
:~. bluish/white emulsion having a p~ of lO:08, a ~rookfield
~ 20 viscosity ~LV-#2 spindle, 60 rpm) of 57 centipoise, a total
:~ st~lids content (theory) of 0.50% and a total actives
content (theory~ of 4.30~. The emulsion e~hibited
e~cellent stability characteristics.
The emulsion possessed excellent, rapid, and
complete cleaning/degreasing action against all the
soila~ts listed in E~ample 26.
E~ample 29
..
Example 26 was repeated in preparing an aqueous
cleaner/degreaser emulsion having the following composition:
:`.' .:
.
. ~
~ SIIIUI~ SHEEI
.,
.
~`, - .. ~ . . . ;.
., ~ .-. , " :
. .. .
~ .. ` ~. . ; . .
,
-,. . ~ ,
, .
.
~; , ` ` ~ . .
WO91/09104 PCT/US90/07215
~ 50
Com~onent Wt.%
Isostearamide diethanolamide 0.3
(1:1) (Monamid 150-IS)
Mi~ed caprylamide DEA/ 0.2
capramide DEA coupler
(Clintwood CP-Z-61-2)
Monoethanolamlne 0.3
~;
; Soft ~2 19~.2
l-Pheno.. ~y-.-p-o~anol . 5.0
~Dowanol PPhj
~:~ 200.0
The resulting sompos~tion was an intensely
.
.~, bluish/white emulsion having a pH of 10.43, a Brookfield
: viscosity (L~-#2 spindle, 60 rpm) of 4.3 centipoise, a
total solids content (theory) of 0.25% and a total actives
content (theory) of 2.90%. The emulsion e~hibited
: . e~cellent stability characteristics.
The emulsion possessed excellent, rapid, and complete
cleaning/degreasing action against all the soilants
listed in E~ample 26.
,
E3ample 30
.
An aqueous cleaner/degreaser emulsion was prepared
~ havlng the following composition:
`~ Component Wt.%
- 25 Isostearamide diethanolamide 0.30
(1:1) (Monamid 150-IS)
:~ ~ Soft H20 194.2
: Butoxyethyl acetate 3.0
(EB acetate)
~-,'' ~ ~ . .
.
,'~ .
. .~ -
`~ S~'IPl~ITU~E SI~E~
..; ..
~. . .
... . . .. .
~ , ..... ~,
. - ..... . . . .
,. .
.
.- ,~. ` . .
. . . . . . .
. . . .
WO91/09104 PCT/US90/~7215
Sl 2i~ 7~
Acrylic acid/alkyl methacrylate 1.0
copolymer, 30% aqueous
(Acrysol ICS-l)
Aqueous ammonium hydro~ide 0.0
(28% NH3)
100.0
The first two components were stir.ed at room
temperature for 15 minutes to complately di~perse 'che
; isostearamide diethanolamide in water. The buto~yetnyl
acetate was then added with vigorous stirring at room
temperature for 30 minutes. The Acrysol ICS-l was ne~t
` added with stirring followed by dro2wise addition of ~he
; ammonium hydro~ide with ~igorous stirri~.g at room
temperature for 15 minutes.
The resulting composition was a slightly ~luish/white,
milky emulsion having a pH of 7.17, a Brookfield viscosity
(LV-#2 spindle, 60 rpm) of 134 centipoise, a total solids
content (theory) of 0.62% and a total actives content
- (theory) of 3.62%. The emulsion e~hibited excellent
stability characteristics.
The emulsion possessed e~cellent, rapid, and complete
cleaning/degreasing action against all the soilants listed
in Example 26.
Egample 31
A hand cleaner emulsion was prepared having the
following composition:
ComPOnent Wt.~
Polypropylene glycol monobutyl 10.0
ether (Dow PolyglycoI
L-1150)
~''
.
: , ~
` S~BSTl~UT~ SHEET
i . . ..
,.~. .
., , " . . .
WO91/09104 PCT/US90/07215
52
Mineral oil (Penreco, 30.0
Drakeol 5 L~O)
Octylphenol/7-8 E.O. 10.0
~Triton ~
5 Isostearamide diethanolamide 6.0
( 1 : 1 )
Soft H20 1~1.0
Acrylic acid/alXyl methacrylata 3.0
copolymer, 30?~ acu~ous
(Acrysol IC~
100 . O
- The firs'~ e ,o:;n~onsn~ sre emul~ d and tne
Acrysol ICS-l was c~en added ~ith ~tigorous stirring. The
resulting composition was an intensely bluish/white
emulsion which had a creamy, smoo~h feel. The emulsion had
a pH of 6.98,-a Brookfield viscosity (LV-#4 spindle, 6 rpm)
of 9500 centipoise and a total actives content (theory) of
28.45%.
The emulsion exhibited superior removal of oily/greasy
soilants from hands. When reformulated to contain no
Polyglycol L-1150, the cleaning/degreasing action was
~; drastically reduced.
E~ample 32
An aqueous cleaner/degreaser emulsion in the form of
an aerosol formulation was prepared having the following
composition:
,
! ~ Component ~t %
Liquid lauramide 0.30
diethanolamide (1:1 Superamide)
~ 30 (Mackamide LLM)
:,.
~; Monethanolamine 0.60
.~.
.:
.
~BSTITUTE SI~EET
. ~
WO91/09104 PCT/US90/~7215
2070~79 `
53
Sodium nitrite 0.30
Perfluoroalkylphosphate 0.40
ester antifoaming agent
(Atsurf F-12, 15%)
Deionized H20 191.80
l-Phenoxy-2-propanol 5.00
(Dowanol PPh)
Acrylic acid/alkyl 1.~0
methacrylate copolymer,
30% aqueous (Acrysol ICS-1)
~' 200.00
The first fiYe components lis~ed aDov2 wer2 s~i red at
high speed for 15 minutes to fully disperse the lauramide
diethanolamide and to form a microemulsion. The
1-pheno~y-2-propanol was then added with vigorous stirring
for 30 minutes at room temperature after which the Acrysol
ICS-l was added dropwise with good stirring. The resulting
composition was a bluishiwhite emulsion with a pH of 9.86,
a Brookfield viscosity (LV-#2 spindle, ~0 rpm) of 28
centipoise, a total solids content (theory) of 0.57~, and a
total actives content (theory) of 3.37~. Ths emulsion
,:
exhibited excellent stability.
The above composition was aerosolized as described in
Example 25 using a fill ratio of 100/15.
It was'found that the resulting aerosol formulation
produced a moderately wet, fast-br~aking foam-with
~` e~cellent vertical cling. The formulation exhibited
excellent cleaner/degreaser action against the markings
listed in Example 25 and had good/excellent wet-out
properties.
., .
.' `
::,
`~:
.,
SUBSTlTUTr SHEET
... ~. ... . . -.~ ~ ,
,
.
.
.
WO~I/09104 PCT/US90/07215
54
Ex2mple 33
An aqueous cleaner/degreaser emulsion was prepared
having the rollowing composition: -
Component r~7t.~
5 Isostearamida diet'nanolamide8.0
; (l:l)(Monamid 150-IS)
Monethanolamine 0.95
Tap Water ~pH 9.55, '55p~170.05
hardness)
10 1-Phenoxy-2-propanol 20.0
(Dowanol P h)
Perfluoroalkylphosphate~ 1.0
ester antifoaming agant
; (Atsurf F-12, 15%)
200.00
The first three components listed above were stirred
until the mixture was fully homogeneous and formed a
microemulsion. The l-phenoxy-2-propanol was then stirred
into the microamulsion with stirring continued for one hour
at room temperature after which the antifoaming agent was
added with stirring. The rasulting composition was a very
intense bluish whita emulsion having a pH of 10.53, a
~rookfield viscosity ~LV-~2 spindlP, S0 'pm) of 7.5
centipoise, a total solids content (theory)-of 9.08%, and a
total actives content (theory) ~of 14.55%. The emulsion
e~hibited excellen~ stability.
At a 1:5 dilution with water, a bluish to bluish/white
microemulsion formed which very ~asily, quickly, and
completely removed all of the markings set forth in
Examples 2-4 from alkyd enameled metal surfaces.
, . .
S~IB~,TITU~ SH~LET
.,.
., j
,
.
WO91/~9104 PCT/US90/07215
2070~79
The microemulsion was subjected to the degreasing test
method of E~ample 1 with the following results:
1st attack on greased slide at l sec.
45% removal of grease at 10 sec.
75% removal of grease at 15 sec.
100% removal of grease at 20 sec.
- .
This emulsion composition is especially suitable rsr
use in mechanized high pressure/spray equipment T,qhere Soam
~' generation cannot be tolerated.
~: ,
E~amPle 34
An aqueous cleaner/degreaser emulsion was prepared
~-~, having the following composition:
~ Component Wt.
.,.j .
Phosphate ester coupler/ 0.10
emulsifier (Monafa~ 1293)
., .
Isostearamide diethanolamide 0.40
(l:l)(Monamid 150-IS)
Monethanolamine 0.60
:.~
Soft H20 192.40
20 1-Pheno~y-2-propanol 5.00
~` (Dowano1 PPh)
Acrylic acid/alkyl 1.50
;~ Methacrylate copolymer
30% aqueous (Acrysol ICS-l)
200.00
~ .
The first four components listed above were stirred at
room temperature until fully dispersed (ca 15 minutes).
The l-phenoxy-2-propanol was added with vigorous stirring
'
.~ .
~ ,
~ .
~U~STI~UTE SHEET
,: . - . , .
. .
. .
~ , . . . ..
.~ , . .
: . .
.
WO91/091~4 PCr/US90/07215
6q9 56
for 0.5 hour at room temperature and ths Acrysol ICS-1 was
added dropwise with vigorous stirring to viscosify the
composition. The resulting composition was an intensely
bluish/white emulsion having a pH of 10.38, a Brookfield
viscosity (LV-~2 spindle, 60 rpm) of 49 csnkipo1se, a total
solids content (theory~ OL 0 . ~a~, and a cocal accives
content (theory) of 3.28~. The emlilsion e~r.hi-3ited
excellent stability.
The emulsion e~hi`oited exceïl2nt cleaneridegreaser
action agai.nst all OL the ma, lSings a't Eor'c'1 tn Examples
2-4 and against Vaseline, iard, short~ning and iipophilic
oils.
; This emulsion is suitabls rfor US~ as a r~ady-to-l~2
formulation applied by pump spray or trigger spray action.
Exam~le 35
An aqueous cleaner/degreaser emulsion was prepared
having the following composition:
` ComPonent Wt.
Polyglycol copolymer ~ 3.0
containing ethylene oxide
and propylene oxide (Dow
Polyglycol 112-2)
Octylphenol ethoxylate 0.3
(5 E.O.)~Triton X-45)
Soft H20 96.7
100.00
The water was added very slowly to the stirred mixture
of the other two components llsted above. The formulation
goes through a water/oil to oil/water transformation to
form a bluish/white emulsion without the addition of a
viscosifying thickener.
~ .
S'~B~TlTll~ SH~ET
.
..
.. . .
WO91/09104 PCT/US90/07215
57 2~067g
The emulsion had a pH of 7.67, a Brookfield viscosity
(LV-#2 spindle, 30 rpm) of 53 centipoise and a total
solids/total actives content (theory) of 3.3%.
This emulsion readily removed tar, grease, asphalt,
black (rubber) heel and red (waxy? crayon marks from floor
tile coated with polymeric floor finish using a wetted
paper towel or cloth. The tile buffs to a clear,
colorless, high shine on air drying with no damage/solvent
~- action on the floor finish.
Example 36
An aqueous cleaner/degreaser emulsion was prepared
having the following composition:
Gom~onent Wt.
Polypropylene glycol 6.0
(Dow P-2000)
Soft H20 190.8
. Octylphenol ethoxylate (5 E.O.)0.6
(Triton X-45)
Triethanolamine 0.6
: .
;~ 20 Acrylic acid/alkyl 2.0
~, Methacrylate copolymer
30% aqueous (Acrysol ICS-l)
:~ .
200.00
The first four components listed above were pre-emulsified
with high speed stirring and the Acrysol ICS-l was added
dropwise under vigorous high speed/hiah shear stirring
conditions. The resulting composition was a white, creamy
:; :
~: .
~ .
'leSll~U~E SHEET
- : -
WO91/09104 PCT/US90/07215
~ ` 58
emuls~ion having a pH of 7.81, a Brookfield viscosi~y (LV-~3
spindle, 12 rpm) of 870 centipoise and a to~al solids/total
actives content (theory) of 3.9%.
This emulsion readily removed tar, grease, asphalt,
black (rubber) heel and red (wa7y) crayon mar~s from vinyl
tile coated with polymeric floor finish usin~ a w2ttea
paper towel or cloth. The tile ouf rS to 3 cl~ar,
colorless, high shine on ai r dryiny Wi tn no damaging
solvent action occurring on the floor finis'n.
I0 In view of the above, it will be s22n t.1a~ ~'n._ several
objects of the invention are achieved and othsr
advantageous results attained.
As various changes could b2 mad2 in t'n_ abov2
:
~` compositions without departing from the scope of the
;~ 15 invention, it is intended that all matter contained in the
above description shall be interpreted as illustrative and
not ln a limiting sense.
~ `
:~
:: '
`'~'i
.,~
:-
:: , , .
.
: .
- SU~SIITUTE SHET
~. . .
-
.
