Note: Descriptions are shown in the official language in which they were submitted.
~zo~
098OL
CLEANING COMPOSITION FOR GLASS
AND SIMILAR HARD SURFACES
I. Description:
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates to an improved glass or similar
hard surface cleaning composition. More particularly, this
invention relates to an aqueous hard surface cleaning
composition, especially glass surfaces, or the general type
disclosed in the Stonebraker, et al U.S. Patent 3,463,735
in which a low molecular weight polyacrylic acid composition
replaces the alkali metal polyphosphate builder component to
provide improved cleaning capacity.
Discussion of the Prior Art
U.S~ Patent 3,463,735 to Stonebraker, et al discloses
a glass cleaning composition of the type containing a solvent
system consisting of a mixture of low boiling solvent and
moderately higher boiling solvent and a surfactant, and pre-
ferably ammonia, in which the effectiveness of the glass
cleaning compositions is improved by incorporating therein
an alkali metal polyphosphate, especially tetrasodium py-
rophosphate. In fact, since the Stonebraker patent issued
in 1969, the polyphosphate built compositions have consistently
provided the most superior performance of all commercially
available hard surface aqueous cleaning compositions with
regard to such properties as fat and grease removal, wipe-
off characteristics~ and the like. Attempts to replace the
alkali metal polyphosphate builders with alternative builders
have met with only marginal success in view of the superior
overall performance of the polyphosphate built compositions,
as well as the cost benefits of the polyphosphates as compared
to alternative builders.
~.~
~ `
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In general, the practitioner in this field does not expect
to find alternative buildexs for the alkali metal polyphosphates
which can give equivalent enhancement of the cleaning capa-
bilities of detergent compositions when used at the same
weights, much less at lower weights, of the alternative
builder.
For instance, in U.~. Patent 3,706,672 - Martin, et al
an essentially phosphate-free detergent washing composition
in which an organic alkaline builder-sequestrant selected
from relatively high molecular weight alkali metal, ammonium
or substituted ammonium polyacrylates having an inherent
viscosity, in 2 normal sodium hydroxide in the range of about
0.05 to about 1.25, is provided. The reader is also referred
to the prior art patents and literature referred to in columns
1 and 2 of the patent for other disclosures relating to acrylic
acid polymers, copolymers and salts thereof as detergent
builders.
U.S. Patent 3,922,230 - Lamberti et al discloses oligo-
meric polyacrylate biodegradable detergent builders useful
in detergent compositions comprising said polyacrylate, which
has a mol.ecular weight between about 500 and 10,000, and a
surfactant, the polyacrylate having biodegradable terminal
groups selected from the group consisting of sulfur and
hydroxy containing moieties. The ratio of builder to
surfactant is in the weight ratio of 1:20 to 20:1.
Other U.~. patents broadly relating to acrylic acid
polymers and copolymers or derivatives thereof for use in
detergent compositions include the following: 3,719,647 -
Hardy, et al; 3,825,498 - Altenschopfer, et al; 3,950,260 -
Eldib; 3,969,500 - Kennerley; and 4,021,376 - Lamberti, et
al. U.~. Patent 3,965,024 to Schmadel, et al discloses
washing agent compositions and washing assistant composi-
tions which contain from 0O5% to 70~ by weight of a phosphon-
opolycarboxylate monomerO
1204361
However, none of these prior art compositions suggest
the use of a low molecuIar weightpolyacrylic acid, a salt
thereof, and/or an acrylic acid polymeric resin complex
containing inorganic phosphate or sulfur moieties for in-
corporation in glass cleaning compositions or similar hard
surface cleaning compositions of the type disclosed by
Stonebraker in the aforementioned U,S. Patent 3,463,735.
A cleaning composition for glass and similar hard sur-
faces similar to that of Stonebraker is disclosed by Labarge,
et al in U.S. Patent 3,696,043. This patent is based upon
the incorporation of a water soluble polymeric salt which is
a copolymer of one to two moles of a monovinyl aromatic
monomer per mole of an unsaturated dicarboxylic acid or an
anhydride thereof wherein the acid is neutralized with a
sufficient amount of an amine, ammonia or an alkali metal
base to foxm a solubilizing salt group or wherein the an-
hydride is neutralized by a sufficient amount of ammonia or
a monoamine having no other groups reactive with the anhydride
group to form a solubilizing salt group. The glass cleaning
compositions of Stonebraker, et al and Labarge, et al are
characterized by, and can be distinguished from, the light
duty and heavy duty detergent compositions of the aforementioned
patents such as the Hardy, et al patent, by the presence of
an organic solvent system, especially an alcohol-glycol
solvent system, among others. Moreover, the glass cleaning
compositions to which the present invention is primarily
concerned, can be functionally distinguished from the light
duty dishwashing compositions and heavy duty laundry compositions
as having a much lower level of active constituents and by
the higher operating temperatures and foaming characteristics
of the latter. In particular, the glass cleaning compositions
and similar hard surface cleaning compositions to which the
present invention is concerned, are applied directly to the
surface to be cleaned at ambient room temperature, usually
by pump or aerosol type spray applicators.
~204361
~,
.
SUMMAR~ OF THE l:NVENTION
.
Suprisingly, it has now been found that low molecular
weight polyacrylic resins not only can replace the conventional
alkali metal polyphosphate builders incorporated în glass
cleaning compositions, but, in fact, can provide superior
cleaning effectiveness to even tetrasodium pyrophosphate
(TSPP) built compositions, TSPP being the preferred
material of Stonebraker, et al and the most common of the
commercially used polyphosphate builders in glass cleaning
compositions, when used at the same weight levels.
Accordingly, in its broadest aspect, the present invention
provides an aqueous liquid glass or similar hard surface
cleaner composition of the type which includes at least one
organic solvent, at least one compatible a~ionic and/or non-
ionic surface active agent, optionally, but preferably,
ammonia, optionally, but preferably, a fluorocarbon surfactant,
and a polyacrylic resin having a weight average molecular
weight from about 5Q0 to about 8000.
mhe present invention provides aqueous compositions for
cleaning glass and similar hard surfaces comprising an
aqueous solution of
(a) about 0.5-8% of a~ least one lower aliphatic mono-
hydric alcohol having about 2-4 carbon atoms and a
boiling point not in excess of about 100C;
(b) about 0.5-5% of at least one higher boiling polar
organic solvent selected from the group consisting of
glycols having from 2-6 carbon atoms and 1-4 carbon
alkyl ethers of a glycol containing a total of about
3-8 carbon atoms, said polar organic solvent having
a boiling point not in excess of about 250C;
(c) about 0.05%-5% of at least one surface active agent
compatible with components (a) and (b) and selected from
the group consisting of water soluble anionic and non-
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5 _
ionic surface active agents;
(d) about 0.005 to about 2.0% of a low molecular weightpolyacrylic resin, which can be a polyacrylic acid or
salt thereof, or which can be a mixture of said poly-
acrylic acid or acid salt and a polymeric acrv~ic acidcomplex, for example a complex containing a phosphinate
moiety, said complex ~eing characterized by the formula
(c3H4o2.H3o2p.M)
where the M's are independently a hydrogen atom or a
member selected from the group consisting of alkali
metal, ammonium ion, and amino group, and y is a number
of from about 5 to about 60;
(e) 0 to about 0.5 of a non-ionic or anionic fluorinated
hydrocarbon surfactant, particularly a perfluorooxybenzene
sulfonic acid or a linear perfluoroalkyloxybenzoic acid,
and
(f) 0 to about 2.5% of a fugitive alkaline compound,
especially ammonia.
In another aspect of the invention, the composition is
provided as a concentrate, the water concentration thereof
being at least about 50% by weight, said concentrate being
diluted prior to use to provide the glass cleaning composition
of the previous paragraph.
In addition to the above mentioned cons~ituents (a) to
(f?, the hard surface cleaning composition of the present
invention may optionally include a monoalkanolamide surfactant.
It has been found that the polyacrylic polymers used herein
are compatible with the alkali metal polyphosphates used
previously as detergent builders, and same may be incorporated
in the formulation of the present invention if desired.
Aerosols of the present composition can be made by the in-
clusion of a suitable propellant, for example, propane,
butane,or a fluorocarbon. When in the aerosol form, an
~04361
oxidizer such as sodium nitrite, sodium nitrate, and the
like is included as a corrosion inhibitor.
DETAILED DESCRIPTION OF THE INVENTI~N
As previously noted, the hard surface cleaning compositions
of the present invention are improvements of the glass cleaning
compositions of the aforementioned Stonebraker, et al and
Labarge, et al patents wherein the alkali metal polyphosphate
of Stonebraker, et al and the polymeric salt of Labarge, et
al are replaced by a specific class of a polyacrylic resin
builder-sequestrant agent for enhancing the cleaning efficienc~
of the compositions when used at equivalent active weights,
beyond the general expectations of the ordinary practitioner.
The basic components of the glass cleaning compositions
include in addition to water, which is the main ingredient,
an organic solvent system, compatible surfactant or surfactants,
and the polyacrylic resin. Preferably, an organic fluorocarbon
surfactant for lowering surface tension and a fugitive alkaline
substance, such as ammonia, for enhancing the cleaning capability
o f the composition are included in the compositions. Additionally,
such other conventional ingredients as perfumes, antifog
agents, foaming agents, chelating agents, other inorganic
builders, propellants, and the like, in amounts which do not
adversely affect the cleaning and other beneficial properties
of the invention compositions, can be used within the scope
of the invention.
The improved cleaning efficiencies of the compositions
of the present invention have ~een measured with several
criteria including cleaning ofgrease films, cleaning of
aged grease films and cleaning more difficult to remove than
grease soils such as pigmented test soils, Against all of
these criteria, the formulations according to the present
invention containing the polyacrylic resin proved equal to
or superior to other wise identical compositions but con-
taining an alkali metal polyphosphate in place of the poly-
1204~;~L
acrylic resin. These test procedures are similar to thosedescribed in the Stonebraker et al patent but also include
more discriminating tests as will be described in the examples
given below.
The polyacr~lic resin used in the present in~ention is
a low molecular weight polyacrylic acid having the following
formula:
1 1 1
~C -- ~
- H I x
n=c
1H
where x is a number of from about 10 to about 100, the weight
average molecular weight being between about 500 to about
8000. The end groups are not considered to be critical, and
vary according to manufacturer and the method of preparation;
Rl i5 hydrogen or methyl. ~ypically, the end groups are
hydrocarbon chains of from one to six carbons containing one
or more carboxylic acid groups, which groups may be neutralized
to an alkali, ammonium or amino salt.
It is not necessary that the polyacrylic resin used herein
be a homopolymer of the acrylic repeating unit. For example,
an acrylic acid polymeric complex of the type
I H Rl
_ r C~ I .
1H+ LY--P~H ~ Y
wherein Rl is as previously described, X is a phosphinate
group, y is a number from about 5 to 60, and the M's are
independently hydrogen or a member selected from the group
consisting of alkali metal, ammonium or amino cations,
12043~;i
admixed with the homopolmer has provided excellent results
as the polyacrylic resin detergent builder. A particular
polymeric complex of this type is identified as 2-propenoic
acid, complexed with sodium phosphinate by the Chemical
Abstract Servi~es Registxy, CAS No. 71050-62-9, which
indicates the chemical formula as being (C3H4O2~ H3O2P.Na)y.
Polyacrylic complexes of this type also may include moieties
containing sulfur and other moieties in lieu of the phosphin-
ate moiety. The polyacrylic resin is generally provided in
the composition at a weight ratio of the polyacrylic acid
to the complex of from about 1:1 to about 15:1, preferably
from about 3:1 to about 10:1.
After preparation of the acid form (M=H) of the poly-
acrylic resin, hydroxyl groups of the terminal acid groups
may be partly or essentially completely neutralized with
alkali metal, ammonium, or amino cations. The alkali metal may
be lithium, potassium or sodium, preferably sodium. In practice,
generally from about 20 to about 80% of these acid groups are in
the acid form, tl.e remaining acid grGups having one hydrogen atom
of one of the hydroxyl groups replaced by the alkali metal, am-
monium ion or amino group, preferably the ammonium ion or sodium
metal.
The preferred value for x is in the range of from about
15 to about 70, while the preferred value for y is in the
range of from about 20 to about 50. The polymerization re-
actants can be any of those which are normally used for
forming polyacrylic acid polymers such as shown, for example,
in any of the aforementioned patents disclosing such poly-
acrylic acid resin polymers, copolymers, complexes and
derivatives thereof.
The polyacrylic resin can conveniently be provided in
the form of its aqueous solution, generally at about 40 to
about 60% by weight solids level. When the polyacrylic
resin is provided in this form, it is generally characterized
by having a Brookfield viscosity in the range of from about
~043~;1
_ 9 _
100 to about 1500 cps at 25C, preferably from about 400 to
about 850 cps at 25C. The resin has a pH range of from
about 1.5 to about 9~0, depending upon the degree of
neutralization, wi~h an acid value of from about 2 to 30,
preferably from about 5 to about 20 milliequivalents per gram
of polyacrylic resin calculated on a 100% active basis~ The
polyacrylic resins used herein have a molecular weight
distribution wherein the weight average molecular weight Mw
is from about 500 to about 8000, preferably from about 1000
to about 5000, the number average molecular weight Mn is
about 600 to about 4000, preferably from about 1200 to about
3000. The ratio Mw/~n is from about 0.2 to about 2.7.
The polyacrylic resin is present in the compositions in
amounts from about 0.005 to about 2~0~ by weight, preferably
from about 0.01 to about 0.50~ by weight, on an active basis
Specific polyacrylic resins which have been found to
provide excellent results when incorporated into the cleaning
composition of the present invention are resins sold by
Rohm and Haas Company under the trademark Acrysol LMW, for
example Acrysol LMW-45X, a polyacrylic acid resin containing
no phosphates having a molecular weight Mw of about 4500,
a viscosity of about 600 cps, and a pH of about 1~5 Acrysol
LMW-20X, a partially neutralized sodium salt polyacrylic
resin having a molecular weight Mw of about 2000, a viscosity
of about 600 cps, and a pH of about 3.8, and Acrysol LMW-20NX, a
polyacrylic acid sodium salt having a molecular weight Mw of about
2000, a viscosity of about 300 cps, and a pH of about 9.1; a resin
sold by Colloids, Inc. under the tradename Colloid 119/SO, which
has a molecular weight of about 1200, a viscosity of about 125 cps,
and a pH of about 2.1, and Eesins sold under the trademark Calnox
by Aquaness Chemicals, Inc., for example Calnox 214, having a
viscosity of about ~6-24 cps (Hoeppler at 77F) and a pH of 4.7-5.3,
and which is at least 70% neutralized to the sodium salt, and phos-
phate free Calnox 236, having a molecular weight of about 5000, a
viscosity of about 320 cps (Hoeppler at 77F?, and a pH of
about 2.0 tlO~ solution).
:IZ043
-- lo ~
The organic solvent Which has proven to be particularly
useful for the glass cleaning compositions of this invention
is based on a mixture of at leas-t one lower alkylene or poly-
alkylene glycol or lower alkyl ether thereof, of moderately
higher boiling point than the aliphatic alcohol, The pre-
ferred lower aliphatic alcohols are those containing from
two to four carbon atoms and having a boiling point lower
than ahout lOO~C, preferably from about 75 to about 100C.
Examples of suitable alcohol components include, for example,
isopropyl alcohol, n-propyl alcohol, ethyl alcohol, sec-butyl
alcohol and tert~butyl alcohol. Isopropyl alcohol is preferred
A suitable amount of the lower alcohol is about 0.5-8% by
weight, preferably about 1 to about 5~ by weight, based on
the total composition. Two or more of the alcohol compounds
can be combined, if desired.
As the higher boiling polar organic solvent, glycols
having from 2-6 carbon atoms and the alkyl ethers thereof
are conveniently used. Preferably`the higher boiling solvent
is selected from alkylene and polyalkylene glycols containing
about 2-6 carbon atoms and the Cl 4 lower alkyl ethers thereof
containing a total of about 3-8 carbon atoms. The boiling
point of the polar organic solvent should be less than about
250C. Suitable higher boiling solvents include, for example,
ethylene glycoll propylene glycol, trimethylene glycol, 1,2-
butanediol, 1,3-butanediol, tetramethylene glycol, 1,2-pantane-
diol, 1,4-pentanediol, pentamethylene glycol, 2,3-hexanediol,
hexamethylene glycol, glycol monoethyl ether, glycol mono-
butyl ether, glycol monomethyl ether, propylene glycol mono-
ethyl ether, and diethylene glycol monoethyl ether. Part-
icularly good results, especially in combination with iso-
propyl alcohol, are provided by the glycol monobutyl ether
and propylene glycol monomethyl ether. The amount of the
higher boiling component is generally in the range of from
about 0.5 to about 5~ by weight, preferably about 1 to
about 3% by weight, based on the total compositionO Mixtures
of two or more of the higher boiling compounds may be employed
~æO4;~;~
11 --
within these weight ranges. The total amount of the organic
sol~ent system is not particularly critical but generally
it is pre~erred that the total amount of the alcohol (a)
and polar organic solvent (b) be within the range of from
about 2 to about 10% by weight, preferably from about 3 to
about 7.5% by weight, with a weight ratio of (a) to (b)
being in the range of from about 5:1 to 1:1, preferably 4:1
to 2:1.
Virtually any compatible surface active agent which
does not react with the organic solvent system or other
components of the aqueous compositions can be used in the
present inventibn. The preferred surface active agents are
the water soluble anionic and non-ionic surface active
agents which can be selected from among any of the known
materials in these categories, Typical anionic and non-
ionic surfactants are described, for example, in the afore-
mentioned patents to Stonebraker, et al and Labarge, et al,
as well as the other patents mentioned above . Typical
examples of the anionic surfactants include the sulfonated
fatty alcohols containing from about 8-18 carbon atoms or
more, sulfated fatty oils or esters, sulfated polyethylene
oxides ethers or fatty alcohols, and alkyl aryl sulfonates,
which are present in the form of the alkali metal salts
thereof, especially the sodium or potassium salts thereof,
most expecially the sodium salts. The preferred anionic
surfact~nts are the alkali metal fatty sulfates, especially
sodium lauryl sulfate.
Examples of the non-ionic surfactant include, for example,
the polyethylene oxide ethers of fatty alcohols and polyoxy-
ethylene ethers of alkyl phenols, the latter being especially
preferred.
Generally, the surface active agent is present in amounts
of from about 0.05 to about 5% by weight of the total
composition. The surface active agents can be used as mix-
tures, and, in fact, mixtures of the water soluble anionic
120436~
surface active agent with small amounts of the non-ionic
surface active agent have been found to be especially pre-
ferred. The preferred amount of the surface active agent
or mixtures thereof is in the range of from about 0.05 to
about 1% by weight, based on the total composition.
It is also preferred to incorporate small amounts of a
fugitive alkaline agent such as 26 Baume ammonia in the
aqueous cleaning compositions of the invention. The ammonia
is generally added as ammonium hydroxide. Other volatile
alkaline materials such as alkanol amines, morpholine, and
the like can also be used. Suitable amounts of the fugitive
alkaline agent are in the range of from about 0.005-2.5%
preferably about 0.015-0.8%, by weight based on the total
composition and calculated as ammonia (NH3). The ammonia
or other fugitive alkaline agent can be added in amounts
sufficient to provide aqueous compositions having a pH in
the range of from about 9.5-13, preferably about 10-12.5.
It has also been discovered in accordance with the
present invention that the effectiveness of the aqueous
glass cleaning compositions of this invention can be even
further enhanced by incorporating a small amount of an organo-
fluorocarbon surfactant in active amounts within the range
of from about 0.005-0.5% by weight, preferably from about
0.01-0.5% by weight, based on the total composition. The
preferred fluorocarbon surfactants include the perfluoroali-
phaticoxybenzene sulfonic acid anionic salts and the anionic
salts of linear perfluoroalkyl oxybenzoic acids. Examples
of the former class of fluorocarbon surfactants can be
represented by the following formula:
(Rf)-O- ~ -sO3-A
.,
3~i1
- 13 -
where Rf is a perfluoroaliphatic group of from about 5 to
about 15 carbon atoms, preferably from about 8 to 12 carbon
atoms in the aliphatic group which may be an alkyl group or
alkenyl group, and A is an cation such as an alkali metal
ammonium or amineO
Examples of the latter class of fluorocarbon surfactants
can be represented by the formula:
~=\
n m O ~ -COOH
wherein n is a number of from about 2 to about 16 and m is
a number from about 3 to about 34.
Especially preferred results have been obtained with 4-
[[4,4t5,5,5-pentafluoro-3-(pentafluoroethyl)-1,2-3-tris(tri-
fluoromethyl)-l-penteny l]oxy]-benzene-sulfonate, sodium
salt, sold under the trademark ~lonflor 31 by ICI Americas,
Inc. and with a particular linear perfluoroalkyloxybenzoic
acid sold under the trademark Surflon S-113, also manufactured
by ICI Americas, IncO UOS. Patent 4,302,348 to Requejo des-
cribes these and other fluorinated surfactants which are suitable
for the present composition.
The composition may~ of course, include other conventional
adjuvants commonly used in hard surface cleaning compositions,
for example, other inorganic builders in small amounts~ such
as borax, sodium polyphosphates, and the like; foaming or anti-
fog agents, such as the various organosiloxane-oxyalkylene
compounds and polysiloxanes; perfumes; dyes, and the like.
Generally, the amount of the additional inorganic builders,
if added, should be below about 005% by weight, preferably
less than about 0~05% by weightO Amounts of the anti-fog
agents are generally less than about 5% by weight, especially
less than about 2% by weight, especially preferably less
than about 005% by weightO Amounts of dyes and perfumes up
to about 002% by weight, preferably up to about 001% by
weight can also be included in the compositionsO
The glass cleaning composition described above may also
~1
:IZ0~3~;1
be obtai~ed by dilution of a concentrate prior to use, the
concentrate containing no moXe than 50% actives by weight,
In a particular formulatio~, the concentrate contains up
to about 30%, preferably 15 to 2S% by weight of the lower
aliphatic alcohol solvent, up to about 12%, preferably between
6 to 10%, by weight of the higher boiling solvent, less than
about 2% by weight of the polyacrylic resin, and between
about 0.5 to about 5% by weight of the surfactant. Optional
constituents, for example, the fluorosurfactant and the
fugitlve alkaline agent can be incorporated at suitable
levels. The ability to formulate a concentrate is a part-
icular advantage over Stonebraker et al, inasmuch as there
is no incompatibility between the builder and the higher
solvent concentration.
In aerosol formulas, in addition to the propellant, for
example propane, butane, or a fluorocarbon, it is preferred
to include a corrosion inhibitor, for example sodium nitrite
or sodium nitrate, and a foaming agent identified abovèO The
corrosion inhibitor is typically incorporated at a level of
about less then la 0% by weight, preferably less than about
0.5% by weight.
The formulations may be applied simply as a solution by
wiping it on the surface to be cleaned or the container may
also havean atomizer attachment for spraying on the surface.
In addition to the ingredients named above, it is of
course apparent that the main ingredient of the compositions
of the invention is water and preferably soft water containing
not substantially more than about l grain hardness per
gallon.
Example 1
The following compositions are prepared:
`?~
~Z0~3~;~
- 15 _
Pexcent By Weight (Active_
This
in~ention Comparisons
.. .. . . . - --. .. .. ..
Ingredients A~ B C D E F
.
Isopropyl Alcohol 4~0 4.0 4.0 400 4.0 400
n-Butyl monether ethy-
lene glycol 2.5 2.5 205 2.5 205 205
Sodium lauryl sulfate 0.1 Ool Ool 0.1 Ool
Polyacrylic Resin* 0.01 OoOl
Fluorocarbon Surfactant** 0002 0.02 0002
Tetrasodium Pyrophos- .
phate OoOl
Ammonium Hydroxide 0.6 O. 6 0~6 0~6 0~6 006
Deionized Water qs 100 qs 100 I qs 100 qs 100 qs 100 qs 100
* an aqueous solution, approximately 50% by weight actives,
of a polyacrylic resin comprising a mixture of polyacrylic
acid hauing the formula ~ C - Cl ~ where x averages about 70
O=C
OH
and an acrylic acid complex of the formula
r
H ¦ t
O=C
x
wherein H02P , y is about 5C-55, and M is either hydrogen or
sodium, about 80~ of the total resin being in the acid formO
This product is further characterized by a ratio of polyacrylic
acid to the polymeric acrylic acid complex of about 4:1, a
specific gravity of about 1018 g/ml, and a pH of about 2~5~
The weight average molecular weight by gel permeation chrom-
atography is about 6000. Brookfield viscosity is between about
150 to 350 cps at 22C~ The polymeric complex is of the type
defined by CAS No. 71050-62-9o
;
i~O4;~
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** Monflor 31, a product of ICI Americas, Inc. --30% by
weight solution in a mixed isoprop~l alcohol/water solvent
of 4-~4,4,5,5,5-pentafluoro-3-(pentafluoroethyl)-1,2,3-
tris(trifluoromethyl)-l-pentenyl~oxy~-benzene sulfonate,
sodium salt.
.
Exam~le_2
This example shows the results which are obtained when
the compositions A, C, D and F from example 1 are used in a
static fat-grease film removal test. The fat-grease film is
prepared as described in U.S. Patent 3,463,735 -- a 1%
solution of beef fat in hexane is sprayed on a microscope
slide and allowed to dry for 90 minutes, after which the
slide is wiped gently several times with paper toweling
to remove excess fat and leave a thin uniform grease film
on the surface of the slide. A drop of the cleaning solution
is then placed on the surface of the slide bearing the film
and allowed to remain in contact with the film for five (5)
secondsO The results are shown in the following table:
Fresh Grease Plate - Grease Removal Test
Contact Time: 5 seconds
. .
Composition% Grease Removal
A 100
C 55
D 18
F 100
The percent grease removal is measured qualitatively by
visual inspection, each composition being tested a number
of times to ensure reproducibility of the test. Compo-
sitions A and F both removed approximately all grease from
the slide. The data indicates that the formulation of the
present invention is at least as effective as the formulation
F containing the heretofore preferred builder,TSPP. Accuracy
of about 5% is achieved with the procedure.
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- 17 -
E~ample 3
This example shows the results which are obtained with
the compositions of example l in remoYing a fat~grease film
prepared as in example 1 except that the film is allowed to
age overnight (about 24 hours), the compositions are allowed
to remain in contact with the aged film for 15 seconds. The
results are shown in the following table:
Aged Grease Plate - Grease Removal Test
Contact Time: 15 seconds
Composition% Grease Removal
A 99
B lOO
C 51
D 39
E 14
F lOO
These results show that the fluorochemical surfactant
by itself (Composition E~ offers very little detersive properties
on grease. When sodium lauryl sulfate is combined with the
fluorosurfactant (Composition C?, the attack on the grease
film improves. However, the results using sodium lauryl sul-
fate without a builder and without the fluorosurfactant
(Composition D) and with the fluorosurfactant (Composition C)
are about the same.
The polyacrylic resin built compositions of this invention --
Compositions A and B -- have comparable cleaning ability in
the grease film removal test for removing the relatively
fresh grease film as well as the more difficult to remove
aged grease film as compared to the phosphate built glass
cleaning composition (Composition F).
The fresh grease film and aged grease film plate cleaning
tests of examples 1 and 2 are adequate to distinguish the
lesser cleaning capacity formulas (Compositions C, D and E)
~;~04~;~
- 18 -
from those having greater capacity (A! B and F). Moreover,
these tests show that merely wetting a surface, or soil is
not enough to achieve effecti~e cleaning, but the presence
of at-least one ingredient haYing detersive properties, e.g.
sodium lauryl sulfate, is also necessary (compare Compositions
C and E).
In order to further compare the effectiveness of the
polyacrylic resin built compositions to the phosphate built
compositions, the procedure of the aged grease film removal
test is repeated except that the contact time between the
cleaning compositions and the aged grease film is reduced
to only 5 seconds. The results are shown in the following
table:
Aged Grease Plate - Grease ~emoval Test
Contact Time: 5 seconds
.__
Composition % Grease Removal
.
A 78
B 72
C 30
D 20
E 20
F 63
G 80
Composition G has the same formula as Composition B
except that the amount of the polyacrylic resin is increased
from 0.01 active weight % to 0.1 active weight ~.
From these results, it can be appreciated that the
compositions containing the polyacrylic resin builder alone
(Composition A) or both the polyacrylic resin and fluorocarbon
surfactant tComposition A, B and G) provide greater cleaning
capacity than a similar composition containing an equivalent
amount of a phosphate builder (Composition F). Moreover, it
is again observed that compositions which do not include any
builder, but do include sodium lauryl sulfate (Composition D)
'X
i~O4361
-- 19 --
or which contain only the fluorosurfactant, without the
sodium lauryl sulfate (Composition E) are least efficient
and only a moderate improvement in the grease removal
capacity is provided by combining the fluorosurfactant and
sodium lauryl sulfate (Composition C),
Example 4
In this example Compositions A, B, C, and D from example
1 are evaluated in their ability to clean a different
type of soil from a glass substrate. In this test procedure
a film of a waxy China marker is applied to a glass plate
and the plate immersed in the test cleaning composition for
30 seconds. The treated film is then scrubbed using 25
scrub cycles on a Gardner Washability and Abrasion machine
using a cellulose sponge as the scrubbing medium. An array
of nine test plates for each composition is cleaned in accord-
ance with this procedure. The arrays of cleaned plates are
then evaluated by a panel of evaluators (at least 10 in number)
who select the cleanest plates in a side-by-side blind com-
parison. Side bias is minimized by rotation of the plates.
The results are shown in the following table:
Run No. Compositions Cleanest Panel, % Preference*
1 C 60
vs
D 19
2 ~ 14
vs
A 74
3 A 26
vs
B 58
4 A 77
vs
C 15
* The difference between 100% and the combined indicated
percentages represents % ties.
.~
~Z04~
Example 5
In this example, the polyacrylic resin built com-
position A from example 1 is compared to similar compo-
sitions except that an equivalent amount (0.01% by weight)
of other typical builders is used in place of the poly-
acrylic resin in the waxy China marker soil removal test.
The results are shown below:
% Preference
Cleanest Panel*
Run No. Builder Variable vs. Control
1 Polyacrylic resin Control
(Composition A) (this invention)
2 Sodium Carbonate 23% vs 74%
3 Sodium Metasilicate 8% vs 90%
4 Sodium Borate 10% vs 87X
Ammonium Carbonate 37% vs 60%
6 Ammonium Bicarbonate 23% vs 69%
7 Sodium Citrate 42% vs 51%
8 Builder M** 31% vs 62%
* ~he difference between i00% and the combined indicated
percentages represent % ties.
** Builder M is a mixture of carboxymethyltartronate,
ditartronate and diglycolate, and is sold under that
tradename by Monsanto Chemical Company.
The above procedure is repeated with Composition B
of example 1 and the sodium carbonate (Run No. 2 of this
example) and sodium metasilicate (Run No. 3 of this
example) built compositions with the following results:
. ~
~20~361
% Preference
Builder Cleanest Panel
Composition B 59
vs
Sodium Carbonate 27
(Run No. 2)
Composition B 87
vs
Sodium Metasilicate 13
(Run No. 3)
Example 6
.
To test the ability of the polyacrylic resin built
composition to clean a more difficult to remove test soil,
a synthetic soil described in UO~. Government Federal
Specification PD-1747C, and which is generally used to
evaluate heavy-duty spray-on wipe-off cleaners, is applied
to white linoleum substrates, This soil, which is oily in
nature and which contains a high level of finely ground
brown pigment, provides a severe staining characteristic that
is not easily removed.
Each linoleum test panel is smeared with a small quantity
of the synthetic soil, rolling it out with a printer's rubber
ink roller until a uniform and smooth coating is obtained.
Each linoleum strip was dryed for about a half hour at 90C
and cooled slowly to room temperature. Five strips were
soaked in each of the test compositions H to J tabulated
below for 60 seconds, followed by 10 to 20 scrub cycles using
a sponge saturated with the respective compositions.
% actives by weight
H I J
Isopropyl alcohol 4.0 4.0 4.0
n-Butyl ether ethylene glycol 2.5 2.5 2.5
Sodium lauryl sulfate Ool 0.1 0.1
Polyacrylic resin 0.2 0.2 0.2
(same as example 1)
Fluorocarbon Surfactant 0.02 0.06
(same as example 1)
"~1
i:204;3¢~
% actives by weight
H I J
Ammonium Hydroxide 0.6 0,6 0.6
Water (deionized) qs to 100% qs to 100% qs to 100%
The cleaning efficiency is measured in terms of percent
soil removed by averaging the results of the five test
strips for each composition. The results are based on average
reflectancereadings taken from the strips before soiling,
after soiling, and after cleaning, three readings being
taken for each strip. The following results are obtained:
Formulation % Cleaning Efficiency
-
H 57;59%*
I 60~
J 67%
*Values based on two different trials.
Example 7
This example tests the "misuse wipe-off characteristics
of the compositions of this invention. "Misuse" means that
the cleaning composition is allowed to remain on the glass
or other substrate for a longer than normal time, for example,
about 5 minutes, to leave a dry residue of the cleaning
composition on the substrate. The easier it is to remove the
dry residue, the better the wipe-off characteristics.
It is found that the compositions based on the alkali
metal salts, especially the sodium salt, of the polyacrylic
resin, have better misuse wipe-off characteristics than the
ammonium salt form. In the composition A used in example 1
some of the ammonia is found to react with the polyacrylic
acid to form the ammonium salt thereof, the composition A
being difficult to remove in the misuse test. The following
composition K containing the composition A resin as the sub-
stantially neutralized sodium salt thereof is prepared by
first diluting 0.26 gm of the polyacrylic resin used in
120436~
- 23 -
example 1 (as its 50% aqueous solution) in 999~7 gm distil~ed
water, and then adding 8.3 ml of 0~2 N NaOH to raise the pH
to 9~5O This solution is then used to prepare the following
composition K:
actives by weight
K
Isopropyl alcohol 4.0
n-Butyl ether ethylene glycol 2.5
Sodium lauryl sulfate 0.1
NH40H (26 Baum~ NH3) . 0.6
Polyacrylic resin, Na Salt,
deionized water solution qs to 100%
Dye 0.00088
This composition has a final pH of 11.2.
When this composition is applied (spraye.d-on) to a glass
panel and allowed to dry, the residue could be removed by
washing with water, or with additional compositoin K, and
gentle rubbing. The dried composition A from example 1
required vigorous rubbing for complete removal.
Example 8
The following compositions are prepared:
Ingredient L M N 0 P Q 2
Isopropyl alcohol 2.76 2.76 2.76 12.0 1.012.0 5.23
n-Butyl ether
ethylene glycol 1.73 1.73 1.73 2.5 8.0 8.0 3.27
Polyacrylic resin 0.04 0.03 0.05 0.005 2.0 0.2 0.02
tfrom example 1)
Fluorocarbon surfac- 0.02 0.02 0.02 0.02 O.B0.06 0.02
tant (from example 1)
Nonyl phenoxy-poly- 0.0050.06 0.05
ethoxyethanol
(lgepal C0-630)
Ammonium hydroxide 0.6 0.6 0.6 0.005 0.6 2.0 1.0
Fragrance(s) 0.04 0.04 0.04
~;1
12043~;
- 24 -
Ingredient LM N 0 P Q 2
Dye(s) 0.0027
Water (dei~nized) qs 100qs 100 qs 100 qs 100 qs 100 qs 100 qs lOG
. _ _
The values above are on an active basis.
.
Example 9
The following composition S illustrates the incorporation
of tetrasodium pyrophosphate:
% actives by weight
Isopropyl alcohol 4O0
n-Butyl ethylene glycol 20 5
Sodium lauryl sulfate 0.1
Polyacrylic resin 0O005
(from example 1)
Tetrasodium pyrophosphate 0.005
Ammonium hydroxide 0.60
Deionized water qs 100%
Example 10
Composition T is prepared with Colloid 119/50 polyacrylic
acid, a product of Colloids, Inc. provided as a 50% aqueous
solution, this particular resin having a molecular weight of
about 1200, a specific gravity of about 1.18 gtml at 25C, and
a viscosity of about 125 cps at 25C t50% aqueous solution).
The pH is 2.1.
% actives by weight
Isopropyl alcohol 4.00
N-Butyl ethylene glycol 2.50
Sodium lauryl sulfate 0.10
Polyacrylic resin (Colloid 119/50) 0.01
Ammonium hydroxide 0.60
Pye OoO01
Fragrance 0.02
Water qs 100%
~,,
1204361~
- 25 -
This composition, when included in the static grease
remQ~al test, pxovided the following xesults in comparison
to an equiva~ent composition having 0.01% TSPP actives
(Composition U):
Aged Grease Plate (1~2 day) - Grease Removal Test
.
% Grease Removal
-
.
Contact Time Composition TCom~osition U
30 seconds 90 95
93
43 25
