Note: Descriptions are shown in the official language in which they were submitted.
I
DESCRIPTION
HARD SURFACE ACID COREY
There are many example of hard surface cleaners in
the art, containing some sort ox anionic ~uractant, solvent,
perhaps a dye and a fragrance to impart a pleasing color and
odor, and mostly water. Most of these prior art cleaners
suffer from one or more di~advan~ages~ For example, Rome
cleaners are effective only on hard water Tony. An example
of this clays of cleaner is a highly acidic toilet bowl cleaner
containing hydrochloric acid. Hard water stains axe mineral
stains caused by the deposition of calcium or magnesium salts
present in hard water. Certain other cleaners may be effective
only against soap scum stains, caused when a Patty acid soap,
such as a sodium laurel fatty acid soap precipitates in hard
water containing alkaline earth metal salts, such a calcium,
magnesium, or barium, causing the familiar soap SCUM stain.
Still other cleaners may be effective only on grossly
stains. Generally speaking, these are cleaner which have
either at least some water miscible solvent, and/or sure higher
amount of non ionic and/or anionic suxfactants.
one of the prior art cleaner have addressed all
three of these problematic areas together. As mentioned, a
particular cleaner may be effective against a particular stain
or cleaning problem, but not against the others. Thus,
ineffective cleaning results may occur against certain stains
using some of these cleaners, requiring purchase of other
cleaners which will effectively remove the target Tony This
will result in added expense as a particular cleaver mutt be
purchased for a particular stain.
--1--
Furthermore, many ox the prior art cleaner are very
slow acting That it after being applied to target stain
for long periods of time, they may show some cleaning effect,
but this slow action is considered a great disadvantage and
inconvenience.
Thus, heretofore no single cleaner has been formulated
which will satisfactorily clean all three types of stains.
There is also a need for an effective all purpose hard surface
cleaner which it faster than the prior art cleaners. There is
thus a long felt need for a multipurpose household cleaner
capable of quickly and effectively cleaning all three types of
stain.
Linear alkyd Bunsen sulfonic acid has been well
known in the detergent and cleaner field as a storage compound
which, upon neutralization with generally, an alkali metal
salt, is available for use an anionic surfactant. This was
recognized in Coupler, et at, USE 3,969,282 which utilized
alkyd Bunsen sulfonic acid in combination with a non ionic
sur~actant as a storage compound to be neutralized with alkali
I metal salts prior to using them to launder fabrics. Further,
Reid, US. 3,463,736 showed that linear alkyd Bunsen sul~onic
acids could be neutralized with triethanola~ine to act as a
cleaner. However, it was not realized in the art that linear
alkyd Bunsen sulfonic acids can be utilized as hard surface
cleaners themselves.
I
DISCLOSURE OF THE INVENTION
.
This invention relates Jo an improved hard surface
acid cleaner having a pi of no more ken approximately 6.5
comprising:
(a) alkyd aureole sulonic acid; and
(b) at least 50.0% by weight water.
The preferred alkyd aureole ~ulfonic acid it a linear
alkyd Bunsen sulfonic acid surfactant of the general structure
R - S03H
wherein R is an alkyd averaging 5 to 20 carbons.
In a further embodiment, this hard uric acid
cleaner further comprises I a solvent selected from straight
chain alXanols averaging 1 to 10 carbon, alicyclic alkanols
averaging 5 to 10 carbons, dialkyl ethers averaging 2 to 8
carbons, and glycol ethers averaging 3 to 20 carbon, and
mixtures thereof.
J
I
In yet another embodiment the hard Sergei acid
cleaner further comprises (d) an antimicrobial compound
selected from:
(i) a substituted phenol of thy general
structure;
lR6
I Al
wherein Al, R2~ R3, R4, and R5 can
separately be a phenol group, Of or H, and R6 can be
H or pa;
(ii) a qua ternary ammonium compound; and
(iii) mixtures thereof.
In yet another embodiment, the hard surface cleaner
further comprises (e) a thickener selected from gum,
polysaccharides and resins.
In still another embodiment, the hard surface acid
cleaner further comprises (f) a defamer selected from the
dialkyl polysiloxane polymers.
he hard surface acid cleaner of this invention can
also include at least one other cleaning ad juvant selected from
20 dyes, pigments, fragrances, and builders.
Surprisingly, the hard surface acid cleaner of this
invention has proven to be both effective and fast acting
against all three major problem stain , namely, (1) soap scums;
(2) hard water stains; and I greasy oily stain.
DETAILED DESCRIPTION OF E IVY
The prune invention it a hard surface cold cleaner
which has surprisingly effective and fast cleaning results on
all threw problem area: I soap scums; (2) hard water stains;
and (3) greasy/oily stains The surprising revelation way that
alkyd aureole ~ulfonic acid compound, most ~peci~ically/ linear
alkyd Bunsen sulfonic acids, ("HAS") were responsible for the
improved cleaning in all three awry. These alkyd Bunsen
sulfonic acid surfactants are not neutralized with alkali
metal, alkaline earth metal, or ammonium alto as are the
typical detergents using substituted alkyd Bunsen sulfonate~.
The linear alkyd Bunsen sulfonic acids used in this
invention are, as previously mentioned, commonly neutralized
with sodium or other alkali metal salts to make common
15 cleaners. Linear alkyd ensign sulfonic acid itself is
produced by a two step synthesis, in which Bunsen it first
alkylated with some allele chloride in the presence of
catalyst. Next, the alkylated Bunsen it reacted with
~ulfonating reactant. A third step, which does not concern
I the present invention,c~occurwhen the thus produced linear
alkyd Bunsen sul~onic acid is neutralized with an alkali metal
hydroxide, such as Noah, to produce the sodium salt, which is
commonly called "WAS."
Linear alkyd Bunsen sulfonic acid- which way
25 introduced for heavy industrial use, aster it was discovered
that branched alkyd Bunsen sulfonate ("AS") way significantly
less biodegradables produced by many Companies including
Continental Oil Company under the brand name of Kink SUE;
and Pilot Chemical Company under the brand name Caliphate LAS-99,
30 Witch Chemical Corporation under the brand name of Witch 1298
Soft acid and Steepen Chemical Company under the brand name of
Boo Soft S-100.
- Pi
Linear alkyd Bunsen clonic acid hag the general
structure
A
R - S03
/
wherein R it alkyd averaging 5 to 20 carbon atoms,
Most preferable for use in the formula of this invention are
dodecylbenzene sulfonic acids, wherein R averages about 11.4
carbon atoms in length.
Other alkyd aureole sulfonic acids suitable for use in
this invention include alkylated diphenyl oxide disulfonates of
the general structure
\ __ / 2
I
H 03S ~03H
wherein Al is H and R2 is alkyd, averaging 5 to 20
carbon atoms in length. When Al is alkyd, R2 is H/
Preferably, a range of 0,001~ to 50.0% particularly,
1.0~ to 30.0% end most preferably 5.0~ to 15% by weight of acid
surfactant is present in composition ox this invention.
Further, the preferred surfactant of this invention will cause
the formulas of this invention to have pi of no more than
6.5, and preferably, below 3.
it 76~
An example of a suitable alXyl sulfonic acid it Dow fax TAO
manufactured by Dow Chemical Company corresponding to the
structure immediately above when Al it H and R2 average 12
carbons.
SOVIETS
In a further embodiment, solvents are added to the
acid surfactants of this invention. Solvent appropriate for
use in this invention include straight chain, primary,
secondary and tertiary Of 10 alkanolsl C5_10 alicyclic
10 alcohols, C2 8 dialkyl ethers, C3_20 azalea and aureole
glycol ethers and mixtures thereof.
1. Alkanols: appropriate alXanol solvents in this
invention have the general formula R-0~ wherein R can be a
straight, or substituted carbon chain ox 1-10 carbon atoms.
15 Solvents of this type include methanol, ethanol, n-propanol,
isopropanol, n-butanol, sea buttonhole, left buttonhole, hexanol,
heptanol, etc.
2. Aliphatic Cyclic Alcohols (Alicylics): Further
appropriate solvents herein are ring structures such a
I cyclohexanol, cyclooctanol, cyclodecanol, etc. These
alicyclics preferably average 5-10 carbon atom in their ring
structures.
3. Dialkyl ethers: the dialkyl ethers suitable for
use as solvents in this invention have a general structure
R~0-Rl, wherein R and Al are equal, and each comprise a
carbon chain of at least 1. Preferably the dialkyl ether
herein comprise two to eight carbon atoms in average chain
length. Examples of this particular group of solvents include
dim ethyl ether, deathly ether, and dipropyl ether.
-7
4. Glycol ether: particularly preferred a solvents
in this invention aye the glycol ethers having thy general
structure Rural, wherein R it an alkoxy of 1 to 20 carbon
atoms, or airlocks of at least 6 carbon atoms, and Al is an
ether condensate of propylene glycol and/or ethylene glycol
having from one to ten glycol monomer units. Preferred are
glycol ethers having one to five glycol monomer units. These
are C3_20 glycol ethers-
Examples of particularly preferred solvent include
10 propylene glycol methyl ether, dipropylene glycol methyl ether,tripropylene glycol methyl ether, propylene glycol isobutyl
ether, ethylene glycol methyl ether, ethylene glycol ethyl
ether, ethylene glycol bottle ether, diethylene glycol methyl
ether, diethylene gly~ol ethyl ether, diethylene glycol bottle
lo ether, ethylene glycol phenol ether, and propylene glycol
phenol ether.
These glycol ethers are especially preferred because
whey are colorless liquids with mild, pleasant odors. They are
very miscible with water, and have been found to be a3pecially
I stclble with the acid surfactants noted above.
Addition of 0.001-25.0~ by weight of any of top
solvents disclosed to this hard surface acid cleaner appears
desirable, and especially preferred it .1 to 15% by weight of
added solvent. As will be further discussed in greater detail,
25 addition of solvents to the hard surface acid cleaner herein
provides surprisingly even greater cleaning benefits.
ANTIMICROBIAL COMPOUND
In yet another embodiment of this invention,
antimicrobial compounds are added to the novel hard surface cleaners
of this invention which are selected from substituted phenols and
qua ternary ammonium compounds.
1. Substituted phenols: suitable antimicrobial
compounds can be selected from the substituted phenols having
the general structure
~R6
I
1' R2~ R3, R4, and R5 can be separately
phenol group, Of, H, and the alkali metal salts thereof, and
10 R6 can be H or Nay Phenols suitable for use in -this invention
include those sold by Dow Chemical Company under the brand name
Dodd, such as sodium o-phenyl phenol tetrahydrate (Dodd
I), o-phenyl phenol (Dodd I), 2,4,5 triehloro-phenol
(Dodd II), 2,4,5 triehloro-phenol, sodium Walt, l/2
lo hydrate (Dodd B), and pentaehlorophenol (Dodd ESSAY.
urethra phenols include ortho-benzyl-para-ehlorophenol told
under the brand name Santophen I by Monsanto Chemical
Corporation.
2. Qua ternary Ammonium Compounds: particular,
surprisingly effective antimicrobial compound suitable for use
20 in this invention are qua ternary ammonium compounds.
One would normally expect that ~uaternary ammonium
compounds, some of which are eationie aurfaetants, having
essentially positively charged species in aqueous solution, would
react with the anionic surfaetant~ in equilibrium with the acid
25 surfactants disclosed above and eye a precipitate to form.
go
,.~
However, the quatexnary ammonium compound used a
antimicrobial compounds in this invention are miscible with the
mixture of acid reactant and solvent in thy formula and do
not precipitate. Instead, a thickening it seen to occur with a
preferred percentage of up to 5.0% ox qua ternary ammonium
compound. Surpassing 5.0% has a thixotropic effect on the
cleaner, and this latter application may be suitable for use as
very substantive cleaners, i.e., bathroom leaners.
Suitable qua ternary ammonium compounds include the
10 dialkyldimethyl Amman salts of the general structure
To l
R N - SHEA A
SHEA
wherein R and Al are alkyds of C5 to C~0, and A it an acid stable
anion. Preferred anion include Of , By , I , SUE,
C104-, C103-, and NO-. Other anions stable in the acid
15 surfactants of this invention are possible. Al can also be
an alkyd Bunnell group (in which R it a methyl grout).
Further particularly preferred are C7 to C12
Delilah dim ethyl ammonium salts. Other cat ionic surfactants,
notably other qua ternary ammonium salts and tertiary amine
20 surfactants may be suitable for use as disinfectant compounds.
As previously discussed, it is generally unknown why
the cat ionic sur~actants used as antimicrobial compounds in
this invention are compatible with the acid sur~actants. One
would normally suspect that the qua ternary ammonium compounds
25 would co-precipitate with the anionic form of the acid
surfactants. However, a proposed theory, which it not meant
herein to be binding, is that these
--10--
acid surfactants, not being neutralized by any alkali metal
salts as the more common anionic sur~actant~ are, may exhibit
non ionic moieties in solution which act to syllables the
cat ionic surfactants (qua ternary ammonium compounds) and keep
the from precipitating loath thy anion form of the ac~alc
surfactants herein.
Additionally, the antimicrobial compounds can
apparently be used in combination. Jo loss in stability it
seen by combining these two antimicrobial compound Further,
either or both of these antimicrobial compound may be present
in the invention from approximately 0.001 to 15.0% by wright.
Particularly preferred percentages ox these antimicrobial
compounds are from 0.1 to 10~ by weight.
CLEANING ADJUTANTS
Further, approximately 0.0001-25% by weight of further
cleaning adjutants may be added to the present invention,
These cleaning adjutants include thickeners selected from gums,
resins and other polysaccharides, such as xanthan gums, starch,
and mixtures.
Further cleaning adjutants include defamers, such as
dialXyl polysiloxane polymers. Particularly preferred as the
defamers are those sold by Dow-Corning under the trade name
Do 100 for 100% dimet~yl polysiloxane~ Further defamer may
be applicable for use in this invention, including various
cat ionic and non ionic surfactants.
1 7
Still further cleaning Advents include dye,
pigments, fragrances and builders. The dyes and pigments in
this invention are merely limited to those which will not
substantially deposit and stain the surface to be cleaned.
Fragrances selected must generally by those which will not be
degraded by the low pi of the hard Ursa acid cleaner.
Builders can include many inorganic and organic builders, such
as sodium ethylenediaminetetraacetate or HIDEOUT (hydroxyethyl
ethylenediaminetriacetic acid). Further builders include many
organic acids and their alkali metal salts, erg., citric acid,
sodium citrate, sodium lactate, sodium Malta, etc.
Various formulations of the hard surface acid cleaners of this
invention were assayed in the three soiling problem area
soap scums; (2) hard water stain and (3) oily/greasy stains,
as described in the following section, under "EXPERIMENTAL."
Test methodologies and results of aye are set forth in
greater detail below.
EXPERIMENT _
A. Synthetic Soap Scum Test Preparation and Method:
A standard soap scum suspend ion was prepared using the
following ingredients:
White
Ethyl Alcohol 85.0%
Calcium Stewart 5.0%
Distilled ~2 10.0%
100 . 0%
This suspension was applied and boxed onto tilts which
were then cleaned with various formulations of the hard surface
acid cleaner (1) using a Gardner Wear Tester (i.e., "Scrubbing
Test") and (2) by simple application according to the "Soak
Test." Impartial panelists were asked to grade the cleaning of
the synthetic soap scum stains by the formulations of this
invention as well as the performance of competitive cleaners
on a 0 to 5 scale, wherein 0 = no cleaning, 5 = total
cleaning. The grading was averaged for a number of trials.
These results are reported below in TABLES I,II and III.
Competitive products were also tested. Grading was conducted
over various time periods to show that the hard surface acid
cleaners of this invention clean effectively much more rapidly
than competitive products.
B. Hard Water Stain Test Methods:
Two "premixes" were prepared from the following
ingredients:
Premix A % wt. Premix B wit
*Nay Sue X 5H205.0% Distilled H20 73.0%
Distilled H2095.0% Ethanol 24.0
Calcium Chloride 2.0
Magnesium Chloride 1.0
100.~% 100.0%
US *Metro 20 (Trademark,
PI Corporation)
Each premix was sprayed on preheated brown tiles, then
baked and allowed to cool.
-13-
The tiles were cleaned by applying approximately 4 grams of
various formulations of the hard surface acid cleaner, scrubbed
and rinsed ("Scrubbing Test"). Impartial panelists then graded
the cleaning results on a 0 to 5 scale, as previously discussed.
Competitive products were also compared. Further, in a second
test, "Soak Test," formulations were allowed to soak the target
stain for time intervals of 30, 20, 10, 5, 3, and 1 minutes, or
lo, 5, 3, 2 , 1 minutes and 45 second to demonstrate rapid
cleaning efficiency. The results are reported in TABLES I,II and
III below. Participants noted also how quickly elective
cleaning occurred at the various time intervals.
C. Oily/Greasy Soil Test Methods
The following oily/greasy soil mixture was prepared:
Wilson's Lard 60.0 grams
Weston Oil 38.0 grams
Grumbacher Cobalt Drier 2.0 trams
(Cobalt Linoleate) 100.0 grams
'this mixture was applied in a thin layer to precleaned white
enameled metal sheets which material is the same a used for
manufacturing porcelain kitchen sinks and allowed to dry (age)
for approximately 24 hours.
Thereafter, each panel was cleaned via the Oil Grease Stain
"Soak Method," wherein approximately 5 grams of various
formulations of the hard surface acid cleaner we e applied and
25 allowed to soak for time interval of 30, 20, 10, 5, 3 and 1
minutes. Competitive products were similarly compared. Speed in
cleaning, as previously noted, was scrutinized carefully. The
results are reported below in TABLES I,II and III below.
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TABLE III - Perfoxmance9 of Hard Surface Acid Cleaner
Versus Competitive Product
("SCRUBBING TEST")
Soap Scum Hard Water
Exile Formula% wettest Stain Test
(Visual Grading) (Visual Grading)
13. 2-Butoxyethanol 5.0%
HLASL 5.0% 4.8 3.7
H20 90.0~
14 . Ethanol . 0%
HAS 5.0% 408 3.5
H20 90 . 0%
15. DOW DBC 1.9 1.3
16. Lucille 1.1 0 9
17. Borax 206 1.3
18. Soft Scrub 2.1 4.0
19. Comet Lydia 3.8 2.3
1) HAS is alkyd Bunsen sulfonic acid, wherein R
averages lo to 14 carbon atoms.
2) "DOW DUB a trademark of Dow Chemical Company.
3) "Lucille" is a trademark of ennui and Fink Company.
4) "Borax" is a trademark ox US, Borax and Chemical
Corporation.
5) "Soft Scrub" is a trademark ox The Clucks Company.
6) "Comet Liquid" is a trademark of Procter and Gamble
Company.
7) Soap Scum Test was outlined above in "EXPERIMENTAL,"
"A".
8) Hard Water Stain Test was outlined above in
"EXPERIMENTAL," "B."
9) Performance was graded by visual assays performed by
impartial panelists on a O to 5 scale, wherein O = no
cleaning, and 5 = total cleaning. The grading was
averaged for a number of trials. Test administrators
did not disclose or identify what products the
panelists were using.
.
In TABLES IV-V, below, the effect ox adding a solvent,
selected from the preferred solvents discussed previously, to
the hard surface acid cleaners of this invention was tested.
Surprisingly, it was found that even stronger cleaning
performances were obtained without any loss in formula
stability.
_20_
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O I O O t O
it it O It fed
it O ID 5fD o
I t O I 5 3' ED O
O no
4 4
I on 1- n n 1- n 1- n
I n n n 1- ox: OKAY O
O O on I 1- n 1- n
n o 1- 0 0
on n n O aye o
I 0 O I rut n
O a
O O I:: 3 5 0
on n I em ^ us Owe O X
n
n O m em I
em to I o wow
us m O O W -- m
D m t
O o Jo
O o O Pi O
I: w
P
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o 1-- _,
Us
(D
o I-
n Jo
4
TABLE VI, below, illustrates the effect of adding a
germicidal compound to the hard surface acid cleaners of this
invention. As previously discussed the preferred germicidal
or antimicrobial compounds are chosen from substituted phenols,
qua ternary ammonium compounds, or mixtures thereof.
Surprisingly, not only were the phenols stably miscible with
the hard surface acid cleaners, but thy qua ternary ammonium
compounds as well. Since the qua ternary ammonium compounds are
cat ionic species, it positively charged species in aqueous
solutions, it was presumed that precipitation would occur upon
combination with the acid surfactants of the present
invention. Surprisingly, no precipitation occurred, and the
qua ternary ammonium compounds also caused a thickening of the
formulas when used in percentages of 5.0% or more. Adding more
than 5.0% may cause a thixotrope to form, which helps the
cleaning formula stay in place when applied to a vertical
surface. This is a substantial benefit over other cleaners
which are not as substantive and which tend to drain off.
Furthermore, as disclosed in TABLE VI below, the antimicrobial
activity of the antimicrobial compounds was very efficacious.
TABLE VI-Effect of Adding an Antimicrobial Compound
to the lard Surface Acid Cleaners
Formula
Gram tram Fungus
Positive Negative
Bacteria Bacteria
56. (Control) Jo effect Jo Effect No effect
57. HAS 500% Both fresh Both fresh Fresh samples
Ethanol Andy 60 day and 60 day effective
Xanthan Gum 0.1~ aged samples aged samples
Burdock 2~30.25% effective effective
58. HAS 5.0~ south fresh Both fresh Fresh samples
Ethanol 5.0~ and 60 day and 60 day effective
Xanthan Gum 0.1% aged samples aged samples
Santophen 130.25~ effective effective
59. HAS 5.0% Both fresh Both fresh Fresh samples
Ethanol 5.0% and 60 day and 60 day effective
Xanthan Gum 0.1% aged samples aged samples
Burdock 222 ~.125% effective effective
Santophen 1 0.125~
60. HAS 5.0% Both fresh Both fresh Fresh samples
2-Butoxyethanol 5.0~ and 60 day and 60 day effective
Xanthan Gum 0.1% aged samples aged samples
Santophen 13 0.25% effective elective
1) (Control) = 5.0% HAS, 5~0% ethanol, and 0.1% xanthan gum. Xanthan
gum is a thickener compatible with the acid surfactants of this
invention
I) Burdock 22, a trademark of Lyons Chemical Company, is a qua ternary
ammonium compound with the following structure:
_
C~3
R 1 Al Of
SHEA .
wherein R = Al and R averages 10
carbon atoms in length.
-26-
3) Santophen 1, a trademark of Monsanto Chemical Company, is a finlike
compound with the following structure:
OH
[SUE
Of
4) Gram Positive Bacteria: Representative examples include Bacillus
sup., Lactobacillus sup., Streptococcus sup., Staphylococcus sup., etc.
5) Gram negative Bacteria: Representative examples include Escherichia
golf, Salmonella sup., Proteus sup., etc.
6) Fungus: Representative examples include Trichophyton mentagrophytes,
Tine penis (mostly Athlete' 5 Foot fungi), etc.
-27-
Review of TABLES VOW grows that the hard surface acid
cleaners of the present invention show surprising efficacy and
fast action.
In direct comparison tests with other commercially
available cleaners in TABLES I,II and III, the hard surface
acid cleaners showed that total cleaning was consistently
achieved, whether a "Scrubbing Test" or "Soak Test" was
considered, and cleaning results were achieved faster than when
using any of the competitive products TABLES IV-V disclosed
the even greater cleaning efficiency when using a variety of
different solvents of varying structure. Further, using move than
one type of solvent as in Example 48 is possible, but in the
interest of cost effectiveness may not be as de treble,
although such increases still constitute a part of this
invention. Lastly, TABLE VI shows that effective antimicrobial
action is obtained by adding either a substituted phenol, a
qua ternary ammonium compound, or both, with surprisingly no loss
in stability prom addition of the qua ternary ammonium compound.
The present invention therefore provides a multipurpose,
fist acting and effective hard surface acid cleaner which is
effective over the three major problem cleaning area.
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