Note: Descriptions are shown in the official language in which they were submitted.
WO 95/07335 PCT/L1S94/09240
2110023
MILDLY ~~CIDIC HARD SURFACE CLEANING COMPOSITIONS
CONTA:1~TING AMINE OXIDE DETERGENT SURFACTANTS
FIELD OF THE INVENTION
This invention relates to no-rinse hard surface cleaners which are mildly
acidic
and contain an, amine oxide detergent surfactant. These compositions will
effectively clean hard surfaces without leaving a visible residue when they
dry and
1o they will cause minimal or no staining of vinyl surfaces. The invention
also relates
to a process for cleaning vinyl surfaces using the compositions.
BACKGROUND OF THE INVENTION
The use of amine oxide detergent surfactants in cleaning compositions is well
known. Amine oxides are most commonly used as cosurfactants to boost and
maintain suds formation in laundry, shampoo, and dishwashing detergent
compositions. Amine oxides have occasionally been used in hard surface
cleaners
such as acidic toilet bowl cleaners (pH of 2 or less), dishwashing liquids
containing
occlusive emollients (pH of 4 to 6.9), and selected non-acidic (neutral to
alkaline)
2o hard surface cleaners. In non-acidic hard surface cleaners, amine oxide
detergent
surfactants are essentially non-ionic (pKa between about 4 and about 6 ).
These
nonionic amine oxides provide good cleaning properties and leave little or no
visible
residue on hard surfaces when they dry.
It was discovered, however, that non-acidic hard surface cleaners containing
amine oxides will stain or discolor vinyl (polyvinyl chloride) surfaces. The
staining
amounts to a light yellow to dark brown discoloration of the vinyl. Staining
will
also occur on wauced vinyl surfaces where areas of wax are worn thin or are
chipped
away so that the amine oxide can come in direct contact with the vinyl.
It is therefore an object of the present invention to provide a hard surface
3o cleaning composition containing amine oxide detergent surfactants that will
cause
minimal or no vinyl staining. It is a further object of the invention to
provide such a
composition which will also have superior cleaning properties and will not
leave a
visible residue on cleaned surfaces. It is also an object of this invention to
provide a
process for cleaning vinyl surfaces using such a composition.
SUMMARY OF THE INVENTION
In its product aspect, the present 'invention relates to mildly acidic, liquid
hard
WO 95/07335 PCT/US94/09240
L1 ~ ~~23
-2-
surface cleaning compositions comprising from about 1 % to about 50% of an
amine
oxide detergent surfactant, an aqueous carrier liquid, and an acidifying agent
having
a pKa of below about 6Ø The compositions contain the acidifying agent in an
amount sufficient to establish a composition pH of between about 3 and 7 and
in an
amount sufficient to protonate at least about 10% of the amine oxide detergent
surfactant in the composition. The present invention also embodies a non-
liquid
formulation from which the liquid composition can be derived. The non-liquid
formulation is essentially the liquid composition wherein the amount of the
aqueous
carrier liquid is reduced (e.g., gel) or eliminated (e.g., granules).
1o In its method aspect, the present invention relates to a method for
cleaning
vinyl surfaces using the liquid compositions herein. In accordance with the
method,
the liquid compositions are applied in diluted or undiluted form to a vinyl
surface.
The diluted compositions have a pH of between about 3 and 7 and comprise from
about 0.02% to about 0.2% of the amine oxide detergent surfactant, at least
about
10% of which is protonated. The diluted or undiluted liquid compositions are
applied to a vinyl surface, wiped with a porous material, and allowed to dry.
The liquid compositions can be used as no-rinse hard surface cleaners on
floors, walls, etc. It was found that non-acidic liquid cleaning compositions
containing amine oxides will stain vinyl surfaces. The liquid compositions of
the
2o present invention, however, will cause minimal or no vinyl staining.
Moreover, the
liquid compositions have excellent cleaning properties and will leave little
or no
visible residue when they dry.
BRIEF DESCRIPTION OF THE DRAWING
Figure 1 is a graph which shows the cleaning and residue profiles of several
hard surface cleaners. The horizontal axis represents residue profiles based
on a 0.0
(extremely visible residue) to 5.0 (no visible residue) scale. The vertical
axis
represents cleaning profiles (particulate soil removal) based on the
percentage of
soil removed via testing methods described hereinafter. Points A-E on the
graph
3o represent these profiles for commercially available hard surface cleaners.
Point F
represents these profiles for a composition of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The liquid compositions of the present invention comprise three key elements:
1) an amine oxide detergent surfactant, 2) an acidifying agent, and 3) an
aqueous
carrier liquid. The liquid compositions can be used in diluted or undiluted
form on
hard surfaces.
WO 95/07335 PCTIUS94/09240
_3_ 2 ~ ioo~
As used herein, "mildly acidic" means a pH of between about 3.0 and 7Ø All
pH values herein are measured in aqueous systems at 25°C (77°F).
As used herein, "vinyl" means material or surfaces containing polyvinyl
chloride. Such material or surfaces can be waxed or unwaxed.
As used herein, "non-liquid" means granular, powder or gel formulations
which can be diluted with the aqueous carrier liquid described hereinafter to
produce a mildlly acidic liquid hard surface cleaning composition of the
present
invention.
As used herein, "liquid compositions" mean the mildly acidic, liquid hard
1o surface cleaning compositions of the present invention, or aqueous
dilutions
thereof.
As used herein, all percentages and ratios are based on weight unless
otherwise specii:ied.
The presE;nt invention, in its product and process aspects, is described in
~5 detail as follows.
Amine Oxide Detergent Surfactant
The com positions comprise an amine oxide detergent surfactant which
typically has a pKa of from about 4 to about 6. As described hereinafter, at
least
2o about 10% of the amine oxide species within the composition must be in
cationic
(protonated) form.
Specificall',y, the compositions comprise from about 1% to about 50%,
preferably from about 2% to about 30%, more preferably from about 2.5% to
about
25%, of an amuse oxide detergent surfactant. The amine oxide preferably has
the
25 formula RRR"I~fO, where R is a substituted or unsubstituted alkyl or alkene
group
contauning from about 8 to about 30, preferably from about 8 to about 18,
carbon
atoms. Groups R' and R" are each substituted or unsubstituted alkyl or alkene
groups containing from about 1 to about 18, preferably from about 1 to about
4,
carbon atoms. More preferably, R' and R" are each methyl groups, examples of
3o which include dodecyldimethyl amine oxide, tetradecyldimethyl amine oxide,
hexadecyldimethyl amine oxide, octadecyldimethyl amine oxide, and
coconutalkyldim~ethyl amine oxides.
The amine oxide detergent surfactant can be prepared by known and
conventional methods. One such method involves the oxidation of tertiary
amines
35 in the manner sta forth in U. S. Patent No. 3,223,647 and British Patent
437,566.
In general terms, amine oxides are prepared by the controlled oxidation of the
corresponding tertiary amines.
WO 95/07335 PCT/US94/09240
21
Examples of suitable amine oxide detergent surfactants for use in the
compositions include dodecyldimethyl amine oxide, tridecyldimethyl amine
oxide,
tetradecyldimethyl amine oxide, pentadecyldimethyl amine oxide,
hexadecyldimethyl amine oxide, heptadecyldimethyl amine oxide,
octadecyldimethyl
amine oxide, docecyldi~thyl amine oxide, tetradecyldimethyl amine oxide,
hexadecyldiethyl amine oxide, octadecyldiethyl amine oxide, dodecyldipropyl
amine
oxide, tetradecyldipropyl amine oxide, hexadecyldipropyl amine oxide,
octadecyldipropyl amine oxide, dodecyldibutyl amine oxide, tetradecyldibutyl
amine
oxide, hexadecyldibutyl amine oxide, octadecyldibutyl amine oxide,
1o dodecylmethylethyl amine oxide, tetradecylethylpropyl amine oxide,
hexadecylpropylbutyl amine oxide, and octadecylmethylbutyl amine oxide.
Also useful are the amine oxide detergent surfactants which are prepared by
the oxidation of tertiary amines prepared from mixed alcohols obtainable from
coconut oil. Such coconutalkyl amine oxides are preferred from an economic
standpoint inasmuch as it is not necessary for the present purposes, to
separate the
mixed alcohol fractions into their pure components to secure the pure chain
length
fractions of the amine oxides.
Acidifying Agent
2o It was found that amine oxide staining of vinyl surfaces can be reduced or
eliminated by using certain acidifying agents in the liquid composition. These
acidifying agents are used to protonate a minimum percentage of amine oxide
species in the liquid composition. It was also found that these protonated or
cationic amine oxides species reduce (i.e., at 10% protonation) or eliminate
(i.e., at
90-100% protonation) staining thus increasing the lifetime of the vinyl
surface.
The composition herein comprises an acidifying agent having a pKa of below
about 6.0, preferably below about 5.0, more preferably below about 4Ø When
selecting an acidifying agent, its pKa should be less than that of the
selected amine
oxide, preferably from about 2 to about 3 units less, to provide for maximum
3o protonation of the amine oxide species in the compositions.
The acidifying agent can contain organic acids, inorganic acids, or mixtures
thereof. Preferred inorganic acids are H2S04, HCI, HN03, H3P04 , HC103 and
mixtures thereof. Preferred organic acids are methane sulfonic acid, oxalic
acid,
glycerolphosphoric acid, ethylenediamine tetracetic acid (EDTA), diethy-
lenetriamine pentaacetic acid (DTPA), malefic acid, mellitic acid, brucine
tretrahydrate, benzenepentacarboxylic acid, pyromellitic acid, malonic acid,
salicylic
acid, hemimellitic acid, 1,4-piperazinebis-(ethanesulfonic) acid, tartaric
acid,
y WO 95/07335
PCT/US94/09240
-5-
fumaric acid, citric acid, o-phthalic acid, trimesic acid, dimethymalonic
acid,
mandelic acid, malic acid, 1,1-cyclohexanediacetic acid, 2-methylpropane-1,2,3-
triscarboxylic acid, hippuric acid, tricarballylic acid, formic acid, 3,3-
dimethylglutaric acid, 1,1-cyclopentanediacetic acid, itaconic acid, lactic
acid,
barbituric acid, ascorbic acid, 2,2-dimethylsuccinic acid, succinin acid,
benzoic acid,
2,2-dimethylglutaric acid, acetic acid, n-butyric acid and propionic acid. The
acidifying agent is more preferably selected from the group of phosphoric
acid,
nitric acid, hydrochloric acid, oxalic acid, malefic acid, o-phthalic acid,
and mixtures
thereof. Most preferred are phosphoric acid, hydrochloric acid, nitric acid
and
1o mixtures thereof.
The liquid compositions contain enough of the acidifying agent to establish a
composition pH of between about 3.0 and 7.0, preferably between about 4.0 and
about 6.0, more preferably between about 4.0 and about 5.5. Liquid amine oxide
compositions employed on hard surfaces at a pH of less than 3.0 tend to harm
surface waxes, and when employed at a pH of 7.0 or above will cause excessive
staining of vinyl surfaces.
The liquid compositions must also contain enough of the acidifying agent to
protonate at le;~st about 10% of the amine oxide species within the
composition,
preferably betv~~een about 50% and about 100%, more preferably between about
90% and 100°/i. As used herein, the term "protonated" refers to
cationic amine
oxide species containing a quaternary ammonium group. The protonation or
conversion of nonionic to cationic amine oxides is represented generally by
the
reaction fonmul;a
RRR"N~O + H+ --~ RRR"N~'(OH)
To achie~re the requisite composition pH and amine oxide protonation, the
concentration of the selected acid in the liquid compositions will typically
be
between about 0.005% and about 5%, more typically between about 0.005% and
about 3% by weight of the liquid composition. Acid concentrations will vary
depending on the pKa of the amine oxide, the pKa of the selected acidifying
agent,
3o the desired target pH of the composition, and the chemical characteristics
of other
materials in the. composition. Since the inorganic acids tend to have lower
pKa
values than the organic acids, target pH values are more easily reached with
the
inorganic acids. Organuc acids are less preferred in the composition because
target
pH values are snore difficult to reach with higher pKa acids and because they
tend
to increase composition viscosity making them less desirable for handling and
processing reasons. Inorganic acids can be combined with the weaker organic
acids
to more easily reach the target pH and to better control composition
viscosity.
WO 95/07335 PCT/US94109240
_
L
The liquid compositions can be used in diluted or undiluted form on hard
surfaces. The compositions will typically be diluted with an aqueous liquid,
usually
tap water, prior to use. When diluted, the compositions comprise from about
0.02% to about 0.2%, preferably from about 0.04% to about 0.1%, of the amine
oxide detergent surfactant. Whether diluted or undiluted, the liquid
composition
employed on hard surfaces must have the requisite composition pH and amine
oxide
protonation described herein.
The requisite pH of the composition is maintained by the amine oxide
component. Amine oxide detergent surfactants normally have an adequate
1o buffering capacity in the pH range described herein. Even when diluted with
tap
water, the amine oxide component can normally maintain the composition pH
below 7Ø Additional buffers can be added if necessary to help maintain
acidity.
Such buffers are not usually necessary.
The vinyl staining described herein comes from the dehydrochlorination of
polyvinyl chloride surfaces. It is believed that this dehydrochlorination
reaction is
accelerated by nonacidic amine oxide compositions. This accelerated
dehydrochlorination is represented by the reaction formula
-(CH2-CHCI)-n + RR'R"NCO -i -(CH=CH)x-(CH2-CHCI)-~-x +((RR'R'N~O)2-HCL)x
Polyvinyl chloride Amine oxide Dehydrochlorinated
(colorless) polyvinyl chloride
(yellow-brown color)
Dehydrochlorinated polyvinyl chloride has a yellow to brown appearance,
depending on the degree of dehydrochlorination. This dehydrochlorination is
believed to be accelerated by nonionic amine oxide species occasionally found
in
nonacidic liquid hard surface cleaners. By protonating the amine oxide to the
extent described herein, and by maintaining an acidic environment, the rate of
dehydrochlorination is greatly reduced and vinyl staining is reduced or
eliminated.
3o In the liquid compositions herein, the protonated amine oxides form ion
pairs with
the deprotonated acidifying agents. These ion pairs are much less reactive in
dehydrochlorination reactions and do not penetrate vinyl surfaces as readily
as
nonionic amine oxide species.
The data summarized in Table 1 shows that mildly acidic, liquid amine oxide
compositions of the present invention cause little or no staining when used on
vinyl
tiles.
WO 95/07335 PCT/US94/09240
.._ _7_ 217~~23
Table 1
Dilute Product Vinyl Tile Staining From the Use
of Liquid Amine Oxide Compositions
Com- CoconutAcidifyingpKa of ConcentrationCompositionDegree
positiondimet6;ylagent acidifyingof acidifyingpH of vinyl
amine: agent agent (gm/cc) staining
oxide
cc
K 0.07 none none none 8.0 severe
L 0.07 H PO 2.12 0.02 5.4 none
M 0.07 HCI - 0.017 5.5 none
N 0.07 HNO - 0.017 5.4 none
O 0.07 H SO - 0.014 5.4 none
P 0.07 Malefic 2.00, 6.260.015 5.4 none
acid
0.07 Oxalic 1.19, 4.210.015 5.5 none
acid
R 0.07 Ethylene1.7, 2.6, 0.015 5.4 none
diamine 6.3,
10.6
tetraacetic
acid
S 0.07 0-Phthalic3.10, 5.270.015 5.4 light
acid
T 0.07 Succinic4.19, 5.570.015 5.4 light
acid
U 0.07 Tartaric3.02, 4.540.015 5.5 light
acid
V 0.07 Citric 3.06, 4.74,0.015 5.5 light
acid 5.40
W 0.07 Malic 3.40, 5.050.013 / 5.4 light
acid 0.051 /
moderate
X 0.07 Acetic 4.76 j 0.039 5 5 mode
l acid
~
To generate the data summarized in Table l, the following vinyl staining
method was employed. This method accelerates staining but it correlates well
with
long term vinyl staining under normal conditions in the field. In accordance
with
this method, white vinyl floor tiles were rinsed with warm tap water, rinsed
twice
to with isopropanol, and then allowed to air dry. About 1 cc of each
composition K-X
was separately ~~pplied to discreet regions of the tiles. The tiles were kept
at room
temperature for 1 hour and then placed in an oven at 60°C
(140°F) for 1 hour, 45
minutes. The tiles were removed from the oven and allowed to cool to about
room
temperature. The cooled tiles were rinsed with tap water. The treated regions
on
each tile were then visually inspected for vinyl staining. The degree of
staining was
rated as "none" (no color change), "light" (very slight but noticeable
discoloration),
"moderate" (yellow color change) or "severe" (brown color change). Each
_g_
2~ X0023
composition K-X was a I :128 dilution of a liquid concentrate with a pH of
between
about 4.0 and about 5Ø After dilution, each composition as applied to the
tiles had
a pH of between about 5.4 and 5.5. Each diluted composition therefore
consisted
of water, coconut dimethyl amine oxide, and a specific acidifying agent.
Composition K was the control product. It had a pH of about 8Ø
Essentially I00% of the amine oxide surfactant was therefore in nonionic form.
This composition caused severe staining.
Compositions L-R were mildly acidic amine oxide compositions where 90
100% of the amine oxide species were protonated with acidifying agents having
1o pKa values below about 3Ø Compositions L-R caused little or no vinyl
staining.
Compositions S-X contained weaker acids (pKa values above about 3.0)
which caused only light to moderate staining. Note however, that all of the
mildly
acidic compositions (L-X) caused significantly less staining than composition
K
which had a much higher pH (8.0) and therefore had less than 10% of its amine
oxide specie;. in cationic form.
Aqueous Carrier Liquid
The compositions herein are employed on hard surfaces in liquid form.
Accordingly, the foregoing components are admixed with an aqueous carrier
liquid.
2o The choice of aqueous carrier liquid is not critical. It must be safe and
it must be
chemically compatible with the components of the compositions. It should be
either
neutral or acidic to minimize the amount of acidifying agent needed.
The aqueous carrier liquid can comprise solvents commonly used in hard
surface cleaning compositions. Such solvents must be compatible with the
componrnts of the compositions and must be chemically stable at the mildly
acidic
pH of the compositions. They should also have good filming/residue properties.
Solv~aits for case in hard surface cleaners are described, for example, in
U.S. Patent
5,108,660.
Preferalbly, the aqueous carrier liquid is water or a miscible mixture of
alcohol
3o and water. V«ater-alcohol mixtures are preferred inasmuch as the alcohol
can aid in
the dispersion and dissolution of the amine oxide and other materials in the
compositions. Moreover, the alcohol can be used to adjust the viscosity of the
compositions. The alcohols are preferably C2-C4 alcohols. Ethanol is most
preferred.
Most preferably, the aqueous carrier liquid is water or a water-ethanol
mixture containing from about 0% to about 50% ethanol.
~B
l j
WO 95/07335 ~ L ,~ PCT/US94/09240
_g_
Non-liquid Formulation
The presE;nt invention also embodies a non-liquid composition from which the
mildly acidic, liquid hard surface cleaning compositions can easily be
obtained by
adding an aqueous carrier liquid. The non-liquid compositions can be in
granular,
s powder or gel forms, preferably in granular forms.
The non-liquid compositions comprise from about 1% to about 50%,
preferably from about 2% to about 30%, more preferably from about 2.5% to
about
25%, of the amiine oxide detergent surfactant described herein.
The non-:liquid compositions also comprise an acidifying agent as described
to herein, preferably an organic acidifying agent. The non-liquid compositions
contain
enough of the acid to provide, upon dilution with the aqueous carrier liquid,
a pH
and percent arrune oxide protonation within the ranges described herein for
the
mildly acidic, liquid compositions.
The non-liquid gel compositions contain reduced amounts of the non-aqueous
15 carrier liquid. The non-liquid granular compositions contain substantially
no
aqueous carrier liquid. In either form, an aqueous carrier liquid is added to
the non
liquid composition prior to use to form the mildly acidic, liquid hard surface
cleaning compositions of the present invention.
2o Auiiliary Materials
Optionally, the compositions herein can contain auxiliary materials which
augment cleaning and aesthetics.
The compositions can optionally comprise a non-interfering auxiliary
surfactant in addition to the amine oxide detergent surfactant. Additional
auxiliary
25 surfactants can effect cleaning activity. A wide variety of organic, water
soluble
surfactants can optionally be employed. The choice of auxiliary surfactant
depends
on the desires of the user with regard to the intended purpose of the
compositions
and the commercial availability of the surfactant.
The compositions can contain any of the anionic, nonionic and zwitterionic /
3o amphoteric surfactants commonly employed in liquid hard surface cleaning
compositions.
Examples of compatible auxiliary surfactants useful in the compositions are
set forth below. The term "alkyl" used to describe these various surfactants
encompasses the; hydrocarbyl alkyl groups having a chain length of from about
Cg
35 to C22, i.e., materials of the type generally recognized for use as
detergents.
Suitzble surfactants which can be employed in the compositions herein include
anionic surfactants such as the alkyl sulfates, alkyl benzene sulfonates,
olefin
WO 95/07335 PCT/US94109240
02~ -io_
21
sulfonates, fatty acyl isethionates and taurides, alkyl sulfoccinates, alkyl
ether
sulfates (AE2S04) and many others.
Examples of suitable nonionic surfactants include the polyethoxysorbitan
esters, fatty acyl mono- and di-ethanol amides, Cg-C22 ethoxylates and mixed
coconut ethoxylates containing 1 to 30 ethoxylate groups.
Examples of suitable zwitterionic surfactants include the fatty alkyl betaines
and sulfobetaines and similar compounds such as Cg to C 1 g ammonio propane
sulfonate and Cg to C 1 g hydroxy ammonio propane sulfonates.
The anionic surfactants can be in the form of their water soluble salts, for
1o instance the amine, ammonium, alkanolammonium or alkali metal salts. For
most
purposes it is preferred to use the anionic materials in their acid form to
reduce the
amount of auxiliary acid needed to acidify the composition. Especially
preferred
anionic surfactants herein the alkyl ether sulfates of the general formula
AEXS04
wherein A=C 10-C'22 alkyl, E is ethylene oxide, and wherein x is an integer
from 0
to 30; the C 1 p-C 14 olefin sulfonates, and mixtures thereof.
Optionally, and preferably, the compositions contain water miscible
substances having disinfectants properties. Preferred disinfectants are
quaternary
ammonium compounds, which are well known in the detergency art. Examples of
suitable quaternary ammonium disinfectants include didecyl dimethyl ammonium
2o chloride, N-alkyl (C 12 to C 1 g) dimethyl ammonium chloride, and N-alkyl
(C 12 to
C 1 g) dimethyl ethyl benzyl ammonium chloride.
Other optional additives such as perfumes, brighteners, enzymes, colorants,
and the like can be employed in the compositions to enhance aesthetics and/or
cleaning performance. These additives must be acidic or neutral, they must be
compatible with the active components in the composition, and they should not
interfere with the inhibition of vinyl staining provided by the compositions.
Detergent builders can also be employed in the compositions. These builders
are especially useful when auxiliary surfactants or cosurfactants are
employed, and
are even more useful when the compositions are diluted prior to use with
3o exceptionally hard tap water., e.g., above about 12 grains. Detergent
builders
sequester calcium and magnesium hardness ions that might otherwise bind with
and
render less effective the auxiliary surfactants or cosurfactants. The
detergent
builders can be employed in the compositions at concentrations of between
about
0% and about 10%.
Alkaline builder materials are not useful herein since they will interfere
with
the acidulation of the composition. Instead, the optional builder materials
should
comprise acidic or neutral sequestrants which do not interfere with the
inhibition of
WO 95/07335 PCT/US94/09240
-11- ~ 110U23
vinyl staining provided by the instant composition. Acidic or neutral builder
materials include, for example, water soluble polycarboxylic acids (e.g.,
acrylic and
malefic acid polymers and copolymers), polysulfonic acids, aminopolyacetic
acids,
and the like.
Suds suppressors are especially useful in the composition. In the hard surface
cleaning composition herein, suds formation and maintenance are undesirably
promoted by the amine oxide component. The compositions therefore preferably
comprise a suf,6cient amount of a suds suppressor to prevent excessive sudsing
during employnnent of the compositions on hard surfaces. Suds suppressors are
1o especially useful to allow for no-rinse application of the composition.
The suds suppressor can be provided by known and conventional means.
Selection of the suds suppressor depends on its ability to formulate in the
compositions, and the residue and cleaning profile of the compositions. The
suds
suppressor must be chemically compatible with the components in the
compositions, it must be functional at the pH range described herein, and it
should
not leave a visible residue on cleaned surfaces.
Low-foanung cosurfactants can be used as suds suppressor to mediate the
suds profile in the compositions. Cosurfactant concentrations between about 1
and about 3% ~~re nonmally sufficient. Examples of suitable cosurfactants for
use
2o herein include hlock copolymers (e.g., Pluronic~ and Tetronic~, both
available
from BASF Company) and alkoxylated (e.g., ethoxylated/propoxylated) primary
and secondary alcohols (e.g., Tergitol~, available from Union Carbide; Poly-
Tergent~, available from Olin Corporation).
The optional suds suppressor preferably comprises a silicone-based material.
These materials are effective as suds suppressors at very low concentrations.
The
compositions preferably comprise from about 0.01% to about 0.50%, more
preferably from about 0.01% to about 0.3%, of the silicone-based suds
suppressor.
At these low concentrations, the silicone-based suds suppressor is less likely
to
interfere with the cleaning performance of the compositions. Examples of
suitable
3o silicone-based suds suppressors for use in the compositions include Dow
Corning
AF-2210 and Dow Corning~ AF-GPC, both available from Dow Corning
Corporation.
These optional but preferred silicone-based suds suppressors can be
incorporated unto the composition by known and conventional means. Such
materials are t~~pically water insoluble and require suspension in the aqueous
environment of l:he compositions. The silicone-based suds suppressors are
typically
suspended by eeither increasing the viscosity of the liquid compositions or by
WO 95/07335 PCT/US94/09240
~ ~ ~2~
21
matching the specific gravity of the compositions with that of the silicone-
based
suds suppressor. The specific gravity of the compositions can be increased to
that
of the silicone-based suds suppressor, for example, by adding a low level of a
cosurfactant. A preferred cosurfactant for this purpose are betaine
zwitterionic
surfactants, preferably at concentrations of from about 0.5% to about 3%.
Benefits
In addition to their effect on vinyl staining described hereinbefore, the
compositions also have excellent cleaning properties and leave little or no
visible
residue on hard surfaces when they dry.
to It was found that these compositions leave surprisingly little or no
visible
residue on hard surfaces whether used in a rinse or no-rinse application. As
described hereinbefore, at least about 10% of the amine oxide species in the
composition are cationic. Cationic surfactants, however, tend to form
crystalline
salts upon drying thus resulting in cloudy residues. This does not occur,
however,
with the application (rinse or no-rinse application) of the instant
compositions to
hard surfaces.
It was also found that the compositions exhibit excellent particulate and
greasy soil removal properties. This was surprising since acidic liquid hard
surface
cleaners do not typically clean particulate or greasy soil from hard surfaces
as well
2o as non-acidic hard surface cleaners do. Acidic hard surface cleaners are
used
mostly in bathrooms to remove hard water stains.
The compositions provide excellent soil removal properties while also leaving
little or no visible residue on cleaned surfaces. Hard surface cleaners
typically have
either good soil removal properties or good residue properties (e.g., they do
not
leave a visible residue on cleaned surfaces), but not both. The compositions
herein
provide both of these desirable properties in a single product. It is therefor
uniquely suited to clean, for example, heavily soiled shiny surfaces, e.g.,
waxed
vinyl floors.
Figure 1 is a graph showing the relationship between particulate soil removal
3o properties (vertical axis) and residue forming properties (horizontal axis)
for the
several hard surface cleaning samples A-F listed below. These properties for
samples A-F correspond to points A-F on the graph.
WO 95/07335 PCT/US94/09240
.... -~~ 17UU~3
Sample ~~: Ecolab Oasis 266 All Purpose Cleaner 266
Labeled ingredients
nonyphenol ethoxylate
n-alkyl (C12-16) dimethyl benryl ammonium chloride
sodium ethylene diamine tetracetic acid
water
am 1 H.: Scott #8 Neutral Floor Cleaner
Labeled ingredients
1o butoxyethanol
alkylnaphthalene sodium sulfonate
sodium citrate
nonylphenol ethoxylate
water
am le C: S. C. Johnson G.P-Forward
Labeled ingredients
sodium hydroxide
sodium silicate
2o nonylphenol ethoxylate
potassium hydroxide
water
Sample D: S. C. Johnson Stride
Labeled ingredients
C12-18 ethoxylatedlpropoxylated alcohol
citric acid
sodium citrate
water
am 1 E' Butcher #4 Neutral Floor Cleaner
Labeled Ingredients
isopropanol
nonylphenol ethoxylate
WO 95/07335 PCT/US94/09240
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2
Sample F: Example 1 composition
Ingredients
coconut dimethyl amine oxide
Betaine
Dow Corning ~ AF-2210
Phosphoric acid
Hydrochloric acid
DyelPerfume
Deionized water (q.s. to 100%)
io pH=4.0
Samples A-F are tested for residue formation on hard surfaces using the
following method. Each sample is diluted to recommended usage with tap water
(about 8 grain hardness) at between about 30° and about 38°C
(between about 86°
and about 100°F). About 5 grams of each diluted sample is applied to a
folded lint-
free towel wrapped around a small block, which is then used to apply the
sample in
one swipe lengthwise alone a clean 3x12 inch chrome panel. After the applied
sample dries, the residue remaining on the chrome panel is graded on an
absolute
scale of 0.0 (extremely visible residue) to 5.0 (no visible residue). The
residue
2o grade for each sample is then plotted along the horizontal axis of the
graph in
Figure 1.
Samples A-F are also tested for the ability to remove particulate soil from
hard surfaces using the following method. White vinyl floor tiles are rinsed
with
warm tap water, rinsed twice with isopropanol, and allowed to dry. Particulate
soil
suspended in isopropanol (4.0 gram soil / 6.0 grams isopropanol / tile) is
rubbed
onto each tile with a lint-free paper towel. Once the isopropanol evaporates
and
the excess soil is brushed away, the tiles are washed with samples A-F using a
Gardner Straight Line Washability Machine. Percentage of particulate soil
removed
by each sample is determined by reflectance measurements using Hunter Lab
3o Tristimulus Colorimeter (DP-9000) before and after washing. Values
representing
the percentage of soil removed by each sample is then plotted along the
vertical axis
of the graph in Figure 1.
It can be seen in Figure 1 that Sample F, which is a composition of the
present invention, is superior to samples A-E both in cleaning performance and
in
residue formation. This represents a significant departure from the trend seen
in
no-rinse hard surface cleaners that cleaning performance should decrease as
residue
formation tendencies decrease. Unlike most no-rinse hard surface cleaners,
Sample
WO 95/07335
21 ~ ~ U ~ ~ P~~S94/09240
-15-
F exhibits excellent cleaning properties and residue/filming (i.e., leaves
little or no
visible film on cleaned surfaces) properties.
Method of Use
The present invention has been firlly set forth in its composition aspects.
The
invention also encompasses a method for cleaning vinyl surfaces (waxed or
unwaxed). The benefit of using this composition on vinyl surfaces is described
hereinbefore.
The method comprises applying to a vinyl surface the mildly acidic liquid
compositions herein or, preferably, applying an aqueous dilution thereof. The
vinyl
1o surface is then wiped with a porous material,. e.g., cloth or mop, and
allowed to
dry.
In a preferred method, the mildly acidic liquid composition is first diluted
with
an aqueous liquid, preferably tap water. The diluted composition has a pH of
between about 3.0 and 7.0, preferably between about 4.0 and about 6.0, and
comprises from about 0.02% to about 0.2%, preferably from about 0.04% to about
0.1 %, of the arrune oxide detergent surfactant described herein. At least
about 10%
of the amine oxide species in the diluted composition are protonated,
preferably
from about 50°~o to about 100%, more preferably from about 90% to about
100%.
The diluted composition is then applied to and wiped over (with a porous
material)
2o the vinyl surface and allowed to dry.
BI. Ezamplat
The following examples illustrate the compositions of the present invention,
but are not intended to be limiting thereof.
Example 1
Coconut dimethyl amine oxide 9.0%
Betaine 1.0%
Dow Corning~AF-2210 0.3%
3o Phosphoric acid 1.5%
Hydrochloric acid 1.4%
DyelPerfume 0.8%
Deionized water (q.s. to 100%) pH =
4.0
Amine oxide protonation 95-100%
WO 95/07335 PCT/US94/09240
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21
Example 2
Coconut dimethyl amine oxide 9.0%
Dow Corning ~AF-2210 0.3%
Phosphoric acid 1.0%
Malefic acid 1.5%
Dye/PerFume 0.8%
Deionized water (q.s. to 100%) pH =
4.0
Amine oxide protonation 95-100%
l0 Example 3
Coconut dimethyl amine oxide 9.0%
Dow Corning ~AF-GPC 0.06%
Nitric Acid 1.5%
Dye/PerFume 0.8%
15 Deionized water (q.s. to 100%) pH = 5.0
Amine oxide protonation 75-85%
