Note: Descriptions are shown in the official language in which they were submitted.
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w0 98/38143 PCT/US97102773
CREAM CRYSTALLIZER STONE FLOOR MAINTENANCE COMPOSITION AND
METHOD
_ Technical Field
This invention relates to a composition and method for maintaining the
appearance
of stone floor surfaces such as marble that avoids the need for use of oxalic
acid.
Background Art
Marble is a natural stone that is frequently used as a floor surface. Due to
its
characteristics, it is considered on of the best stone materials in terms of
durability and
appearance, but it requires some degree of maintenance as a floor surface.
In spite of its durability and hardness, marble is very sensitive to acids and
abrasive
oils. These materials can both easily and irreversibly damage marble. The
marble floor
that is exposed to floor traffic must receive certain considerations and care
when dirt is
removed to maintain the attractive characteristics of the floor such as shine.
Similar
considerations apply to other types of stone floors such as terrazzo,
magnesite, limestone,
concrete and granite. A great variety of stone maintenance products have been
developed
and tried.
2 0 Resins and wax pastes of the type used on wood or vinyl flooring are not
adequate
for marble floors. Some waxes exist that are modified with acrylic monomers or
polymers
and are periodically used on marble floors. However, they have the
disadvantage of a
short-lasting life that can be due to adhesion problems, require continuous
maintenance,
and provide the marble with an artificial appearance.
2 5 A more commonly used type of marble floor maintenance product is a paste
composition based on oxalic acid that forms calcium oxalate crystals in the
marble surface
("a crystallizer" or sometimes called an "acid conditioning agent"). It is
applied directly
on the floor with motor-driven rotary abrasive pads and has the advantage of
providing a
great amount of gloss to the floor surface at a very low cost. This type of
product is very
3 0 good at restoring marble floor surfaces that have been damaged in
appearance due to low
maintenance or high floor traffic. One example of an oxalic acid-containing
aqueous
emulsion marble floor maintenance product is Pasta Liquido Blanca sold by S.
C. Johnson
& Son, Inc. in Mexico and Asia that contains about 66% oxalic acid and an
aluminum
oxide abrasive that is suspended in an aqueous emulsion using stearic acid.
35 U.S. Pat. No. 4,738,876 to George et al. teaches a two step method for
treating
stone surfaces such as marble using an oxalic acid-containing composition
followed by
rotary buffing with a composition containing a crystallizing agent such as
magnesium
hexafluorosilicate or zinc hexafluorosilicate as a floor surface crystallizes.
George et al.
further teaches that other types of acid conditioning agents can be used in
the first step such
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_ _. _ -2-
as citric acid, tartaric acid, hydrochloric acid and other mineral acids.
Other examples of acid-containing compositions used to clean or treat stone
are
found in U.S. Pat. Nos. 90,754 to Ivers, et al.; 133,095 to Haggett et al.;
145,971 to
Sawyer; 181,790 to Love; 370,551 to McCarthy; 542,524 to Hutchison; 1,574,406
to
Nelson; 3,481,879 to Salamone; 4,297,148 to Zervopoulos and 5,490,883 to
McLaren et al.
Oxalic acid has long been the compound of choice for use in marble floor
resurfacing, but has a number of disadvantages. A large amount of oxalic acid
is generally
needed to obtain good floor surface gloss and appearance. Oxalic acid is an
aggressive
material that produces significant levels of wear on the surface of the marble
and thus
reduces the lifetime of the floor surface upon repeated maintenance
operations. Oxalic
acid is an irntating powder. Dusting can be a problem as the composition dries
during
application by motor-driven abrasive or buffing pads. Oxalic acid-containing
products
must be removed from the floor as completely as possible. The residual powder,
especially
when the typical particulate abrasives are also included. tend to dull the
floor upon
repeated foot traffic and the glossy shine is reduced over time. Oxalic-acid-
containing
stone floor resurfacing products are labor intensive and typically require
from 15-30
minutes to cover one square meter of marble floor surface.
Another approach to maintaining marble floors that are in reasonably good
condition, but in need of higher gloss and appearance, involves the use of
other types of
2 0 crystallizer compounds such as those mentioned in the George et al. Patent
above: metal
silicofluoride compounds such as magnesium or zinc hexafluorosilicate. Such
compounds
react with the calcium and magnesium carbonate salts in the marble to generate
crystals of
calcium or magnesium fluoride that actually harden the surface of the marble
and enable
the development of a harder and higher gloss surface. These compositions are
normally
2 5 provided in the form of abrasive-free liquids that make their application
to the floor easier.
Stannic chloride and other metal chlorides, oxychlorides and oxides have also
been
used to enhance the color of the marble floor and its hardness in an acid
conditioning
system as noted in the George et al. Patent above.
Examples of the use of fluorosilicate compounds in marble floor maintenance
3 0 products are given in the George et al. and McLaren et al. Patents noted
above as well as in
U.S. Pat. No. 4,756,766 to Thrower. A commercial aqueous marble floor
maintenance
crystallizer product containing 18% magnesium silicofluoride {"magnesium
hexafluorosilicate") is TERRANOVA~ product sold by S. C. Johnson & Son, Inc.
in
Spain. While the TERRANOVA~ product contains minor amounts of organic and
3 5 inorganic acids other than oxalic acid, a nonionic polyethoxylated
surfactant and
magnesium hydroxide as a buffering agent, it does not contain any abrasive or
silicone
compounds.
Hoechst Celanese Corporation publication "Floor Formula Bulletin, Formula
1401"
(published 1985) provides a suggested formula for use as a one step procedure
for
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polishing marble, terrazzo and hydraulic mosaic stone floors to provide a
mirror-like
surface and increased hardness of stone floors. The composition is composed of
58.0 parts
water, 18.0 parts magnesium silicofluoride, 4.0 parts Hostapal~ N 100
(nonylphenol with
moles of ethylene oxide), and 20.0 parts of Formula 1400. Formula 1400 was
described
5 as being a 20% solids cationic dispersion for use as a component for stone
polishes
composed of 7.0 parts Hoechst Wax 371 FP, 7.0 parts Hoechst Wax KSL, 6.0 parts
Ethomeen~ O/12 (oleyl amine with two moles of ethylene oxide), 1.0 parts
glacial acetic
acid, and 79.0 parts of water). Formula 1401 was to be applied to the floor
surface by
spraying or pouring followed by machine buffing with a steel wool pad until
the floor
10 surface is dry and glossy.
Articles from Batiment Entretien entitled "Crystallization of Marble Stone"
(Jan./Feb., 1985) and "Brilliant Marble: is it easy to obtain?" (No. 147,
Jan./Feb., 1990)
teach the maintenance of marble floors using three stages involving scrubbing,
leveling/smoothing and crystallization using compounds such as magnesium
silicofluoride.
However, one disadvantage of using maintenance products containing
silicofluoride
compounds instead of those containing acids such as oxalic acid is that such
products do
not reach the gloss standards needed to replace the need to use oxalic acid-
containing floor
maintenance products. Additionally, the application of such products is more
time-
consuming and thus they exceed the labor costs associated with the use of
oxalic-acid
2 0 based products. Furthermore, a heavier duty oxalic acid-based composition
is often
ultimately needed after repeated treatments with these types of floor
maintenance products
to bring the gloss and appearance of the floor back to desired levels.
Therefore, there is a need for a marble and stone floor maintenance
composition
that avoids the disadvantages associated with oxalic acid-based compositions,
but that still
2 5 provides a reasonably fast means to maintain the desirable gloss and
appearance of such
floors.
One object of this invention is to provide a stone floor maintenance
composition,
3 0 especially for marble floors, that avoids the use of oxalic acid, can be
applied in one step, is
less labor intensive to use, and still provides such floor surfaces with
desirable levels of
gloss and appearance.
Another object of this invention is to provide such compositions in a form of
a
cream that can be easily applied and that tends to stay in a machine-driven,
rotary
3 5 application pad during application to thereby reduce the amount of cleanup
of composition
needed after the floor maintenance process is completed.
A particularly advantageous object of this invention is to provide a
composition
that provides a finished floor surface with high gloss, depth of shine and
more attractive
color that does not need to be restored with strong acid conditioning products
on a regular
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basis.
These and other objects of the present invention are provided by a stone floor
surface crystallizer composition comprising
A. from about 12% to 25%, more preferably from about 15% to 20%, and most
preferably, 18%_by weight based upon the total weight of the composition of a
silicofluoride crystallizing agent, most preferably magnesium silicofluoride;
B. from about 15% to 25%, more preferably from about 18% to 22%, and most
preferably, about 20% by weight based upon the total weight of the composition
of at least
one fatty acid selected from the group consisting of natural or synthetic
fatty acids
containing from about 16 to 22 carbon atoms, preferably from 16 to 18 carbon
atoms, such
as stearic acid or mixtures of palmitic, stearic and oleic acids;.
C. from about 25% to 40%, more preferably from about 25% to 35%, and most
preferably, from about 30% to 35% by weight based upon the total weight of the
composition of at least one particulate abrasive, more preferably, an aluminum
oxide
abrasive;
D. from about 80% to 120%, more preferably from about 90% to 110%, and
most preferably, from about 100% to 110%, based upon the stoichiometric amount
of
carboxyl groups present in the fatty acid of the composition, of at least one
alkaline
neutralizing agent for fatty acid (B), more preferably a volatile amine such
as
2 0 triethanolamine;
E. from about 0.1 % to 2%, more preferably from about 0.1 % to 1 %, even more
preferably from about 0.1 % to 0.5%, and most preferably, about 0.25% by
weight based
upon the total weight of the composition of a silicone fluid such as
polydimethylsiloxane
fluid having a viscosity of from about 100 to 2000 centistokes (0.01 to 0.2
square meters
2 5 per second -- m2/s) at 20°C, more preferably, from about 250 to
1000 centistokes (0.025 to
0.1 m2ls), and, most preferably, about 500 centistokes (0.05 m2/s); and
F. the balance of the composition comprises water.
More preferably, the abrasive, fatty acid and neutralizing agent are added to
the
composition as an aqueous dispersion.
3 0 More preferably, the composition has the appearance of a cream and further
contains minor amounts of less aggressive acid conditioning agents such as
phosphoric
acid and tartaric acid, buffering agents such as magnesium hydroxide,
surfactants, and,
optionally, aqueous wax dispersions.
This invention also relates to a method of improving the appearance of stone
floors
3 5 through the application of the above compositions to floor surfaces,
especially those of
marble and terrazzo.
The aqueous stone floor surface crystallizer compositions of the present
invention
. , .-_ ... _~
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require five ingredients plus water to achieve the objects of this invention.
The first required ingredient is a conventional metal salt silicofluoride
crystallizing
compound such as magnesium silicofluoride (MgSiF6 or magnesium
hexafluorosilicate).
Such compounds react with the calcium and magnesium compounds in the stone
floor
surface to form crystals that harden the surface and enable the development of
a high gloss
and attractive appearance. Examples of other such crystallizing compounds
include zinc
hexafluorosilicate although any other silicofluoride crystallizing compound
may find use in
the compositions of the present invention. The most preferred crystallizing
compound is
magnesium silicofluoride. The crystallizing compound comprises from about 12%
to
about 25% by weight of the total composition, more preferably from about 15%
to 20%
and, most preferably, 18%. Floor surface gloss levels were reduced as compared
with
oxalic acid treatments at the lower limit while more than about 21 % of the
magnesium
silicofluoride resulted in compositions that were more increasingly difficult
to apply with
motor-driven machinery and gave less uniform. floor surface gloss levels.
The second required ingredient is at least one fatty acid selected from the
group
consisting of natural or synthetic fatty acids containing from about 16 to 22
carbon atoms.
more preferably from 16 to 18 carbon atoms, such as stearic acid or mixtures
of palmitic.
stearic and oleic acids. As is well known in the art, fatty acids are
typically~mixtures of
one or more fatty acids of varying chain lengths, especially for naturally-
derived fatty
2 0 acids.
The fatty acid serves several purposes in the composition of this invention.
One is
to act as a suspending agent for the abrasive used in the compositions of the
present
invention. The carboxyl groups present in the fatty acid are neutralized to
from about 80%
to about 120% of the stoichiometric amount with a neutralizing agent to form a
suspending
2 5 soap or surfactant.
Another purpose for the fatty acid is to provide a waxy, solid material that
can fill
in some of the minor scratches in the stone or marble surface being maintained
to provide a
more attractive, smooth looking appearance. This enables the composition to
repair
scratches in the marble surface and extend the time before any harsher
treatment such as
3 0 with oxalic acid-based compositions becomes a necessity to restore the
floor surface to its
original condition.
A particularly preferred fatty acid mixture for use in the present invention
is a
double pressed fatty acid composed of about 3% oleic acid, and the balance a
ratio of about
55:45 parts by weight of palmitic acid and stearic acid. These are
commercially available
35 materials.
The fatty acid, particularly free fatty acid, can also act as a lubricating
agent to
assist in the polishing process. The amount of free fatty acid present can be
adjusted by the
neutralization level selected. However, very little free fatty acid is
desirable in the aqueous
emulsion of abrasive.
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The third required ingredient is from about 25% to 45%, more preferably from
about 25% to 35%, and most preferably, from about 30% to 35% by weight based
upon the
total weight of the composition of at least one particulate abrasive, more
preferably, an
aluminum oxide abrasive. Conventional abrasives of the type commonly used in
stone
floor finishing and polishing compositions can be used such as boron carbide,
silica,
quartz, and talc as well as aluminum oxide.
Aluminum oxide is presently preferred as a particulate abrasive material. One
such
material that was found to be useful had an analysis of 95% A1203, 1.5% Si02,
0.5%
Fe203, and 3.0% Ti02; a mohs hardness of 9.0; and an average particle size of
+325 mesh
(at least 98% of the aluminum oxide abrasive had an average particle size of
less than
44 microns).
The abrasive is used to simultaneously scratch the floor surface to enable
better
treatment of the underlying stone as well as to grind and polish the surface
to provide the
desirable appearance (e.g., more clarity and depth of gloss) observed on floor
surfaces
treated with the compositions of the present invention. Abrasives are not
typically used in
combination with a silicofluoride compound as a one step floor maintenance
product.
This invention thus enables several operations to be accomplished at once. It
also
reduces the need for an extensive grinding and treating operation such as is
commonly
done when abrasive-containing oxalic acid-based compositions are used to
restore more
2 0 heavily damaged marble floor surfaces.
The fourth required ingredient is from about 80% to 140%, more preferably from
about 90% to 130%, and most preferably, from about 100% to 130%, based upon
the
stoichiometric amount of carboxyl groups present in the fatty acid of the
composition, of at
Ieast one alkaline neutralizing agent for the fatty acid. A variety of
alkaline neutralizing
2 5 agents can be employed such as organic and inorganic bases such as lower
alkyl amines
such as ethylamine, dimethylamine, triethylamine, isopropylamine,
diethanolamine,
triethanolamine, dimethylethanolamine, diethylaminoethanol, 2-amino-2-methyl-
1,3-
propanediol, 2-amino-2-methyl-1-propanol, morpholine, ammonium hydroxide,
alkali
metal hydroxides such as sodium or potassium hydroxide, with volatile bases
being more
30 preferred and triethanolamine being presently preferred. Mixtures of one or
more such
neutralizing agents can also be used.
The fifth required ingredient is from about 0.1 % to 2%, more preferably from
about
0.1 % to 1 %, even more preferably from about 0.1 % to 0.5%, and most
preferably, about
0.25% by weight based upon the total weight of the composition of a silicone
fluid such as
3 5 polydimethylsiloxane fluid having a viscosity of from about 100 to 2,000
centistokes (0.01
to 0.2 m2/s) at 20°C, more preferably, from about 250 to 1000
centistokes (0.025 to 0.1
m2/s), and most preferably, about 500 centistokes (0.05 m2/s).
The silicone fluid is used in an amount that is effective to provide a higher
depth of
gloss to the floor surface than is obtained without such an additive, but not
to the extent
_ ~._ _ .. ... _ .. ~ . , ~,_
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that the floor surface is left unacceptably slippery or greasy. For
polydimethylsiloxane
fluid, the depth of gloss on marble floor surfaces was not much improved at a
fluid
viscosity of about 100 centistokes (0.01 m2ls). The marble floor surface had
good depth of
gloss, but was too slippery or fast when the viscosity of the fluid was about
1000
centistokes (O.l .m2/s). This contributes to the overall unique and attractive
appearance of
stone floors finished with the compositions of the present invention. The
nature of the
fluid used will determine the actual viscosity of useful silicone fluids in
this invention
since, as is well-known, hydroxy-endblocked silicone fluids tend to have
higher general
viscosities for a given molecular weight than do trimethylsilyl-endblocked
polydimethylsiloxane fluids. The improvement in depth of gloss and also with
the color of
the stone with the use of such silicone compounds was particularly noticeable
on marble of
green color.
The balance of the required composition comprises water. Sufficient water is
used
to produce a composition having the consistency of a cream that is readily
spread across a
floor surface and that is retained within a machine-driven rotary pad without
excessive
splashing. The composition is generally a non-newtonian fluid or pseudoplastic
fluid
whose properties are dependent upon the shear exerted on the composition. One
such
composition was found to have a viscosity of 2,200 centipoise (2.2
pascal~seconds) at
room temperature (about 25°C) as measured using a Brookfield~
Instruments Company
Viscosimeter at 30 r.p.m. with a #3 spindle.
In its most preferred embodiment, the particulate abrasive is included within
the
compositions of the present invention in the form of an aqueous emulsion of
the abrasive,
fatty acid and neutralizing agent. In that emulsion, the fatty acid soap
formed by the
neutralization of the fatty acid with the alkaline neutralizing agent serves
as a suspending
2 5 agent for the abrasive particles. If needed for purposes of stability,
minor amounts of other
surfactants such as conventional synthetic nonionic or anionic surfactants may
be included
in the formulation of such an emulsion. In such an emulsion, it is preferred
that the weight
ratio of fatty acid to particulate abrasive in the emulsion be in the ratio of
from about I :2.5
to 1:3. Use of too low of a ratio of fatty acid can cause a reduction in gloss
and an
3 0 undesirable increase in the buffing time needed for the cream composition
of the present
invention. Use of too much fatty acid can produce a poor or unstable emulsion.
Generally,
it was found that neutralization to a pH of from about 7.5 to 8.5 gave useful
emulsions.
Formulation of such emulsions is well within the skill of a person of ordinary
skill in the
art of making emulsions containing suspended abrasives.
3 5 Likewise, the production of a cream composition of the present invention
can be
assisted by the addition of minor amounts (up to about 5% by weight) of other
conventional surfactants such as synthetic nonionic, anionic, or amphoteric
surfactants or
combinations thereof to form suitable cream emulsions having the desired
consistency for
easy application to a floor surface. Surfactants also serve to help wet the
surface of the
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_ _. _ -2-
as
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stone floor being treated to improve the ability of the stone to be treated
with the
crystallizing and other compounds being applied. Examples of nonionic
surfactants
include polyethoxylated alkanols, phenols, and fatty. acids, and alkyl amine
oxides; anionic
surfactants such as fatty acid salts other than those already noted above,
alkyl sulfates and
sulfonates; and amphoteric surfactants such as alkyl betaines. More preferred
are the
nonionic surfactants such as the polyethoxylated alkyl ethers. Amines such as
triethanolamine can also help in the wetting of the stone surfaces.
Additional minor amounts of ingredients can also be included to improve the
performance of the compositions of the present invention.
Up to about 10%, more preferably up to about 5%, by weight of the total
composition can be inorganic or organic acids other than oxalic acid for the
purpose of
modifying the surface of the stone to make it more receptive to the
crystallizing action of
the silicofluoride compounds. Examples of such acids include phosphoric acid
and tartaric
acid.
Conventional hardness and/or color enhancing additives such as calcium
chloride.
stannic chloride, and zinc chloride can be included in minor amounts of up to
about 5°~0.
more preferably up to about 1 %, by weight of the total composition to improve
the surface
hardness of the stone surface being treated.
Buffering compounds such as magnesium hydroxide can be added in amounts of up
2 0 to about 5%, more preferably up to about 1 %, in combination with other
compounds such
as weak acids and bases to maintain the pH of the compositions in the acidic
range of from
about 2 to 3, more preferably from 2.0 to 2.5 (the pH of a solution of 10% of
the
composition in water was about 2.6): This also assists in absorbing carbon
dioxide
released from the floor surface during the process of cleaning the floor.
Compounds such
2 5 as magnesium hydroxide are preferred because can additionally assist in
the desirable
formation of magnesium difluoride crystals in the marble during the
crystallization reaction
of the magnesium silicofluoride and the calcium carbonate in the marble.
Natural and synthetic wax aqueous emulsions can also be included in the
compositions of the present invention in minor amounts of up to about 5%, more
30 preferably less than about 1%, by weight of the total composition for the
purpose of
improving the application properties of the composition. Such emulsions can
also help to
speed up the buffing process of the rotary pad by acting as a slip lubricant.
Such aqueous
wax emulsions comprise waxes such as polyethylene waxes, a suspending aid such
as oleic
acid neutralized with dimethylethanolamine to form a suspending soap, water,
and
3 5 optionaily, a preservative such as formaldehyde.
The compositions of the present invention can be prepared using standard
mixing
and blending techniques that are well known to those of ordinary skill in the
art. The
Examples give specific details on methods for preparing the compositions of
the present
invention.
,. . , , . ~w .
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Industrial A~licabilitv
This invention provides, in its more preferred embodiment, an aqueous cream
composition for application to stone floors, especially those composed of
marble or
' 5 containing marble such as terrazzo, that returns the floor surface to the
natural beauty and
gloss of the original stone. These compositions are applied with conventional
motor-
" driven rotary application pads of steel wool or plastic to both refinish and
polish the stone
floor surfaces to a high degree of gloss and depth of shine. They require less
labor and less
cleanup time than has been the case when either conventional acid-treating
compositions
based on oxalic acid or conventional maintenance compositions based on
magnesium
silicofluorides have been used.
The following Examples are provided to show various aspects of the present
invention without departing from the scope and spirit of the invention. Unless
otherwise
indicated, all parts and percentages used in the following Examples are by
weight. In the
Examples, times are described where 3' means 3 minutes and 20" means 20
seconds;
measurements are described where 5 in means 5 inches, 2 m means 2 meters and 6
mm
means 6 millimeters; weights are described where 10 kg means 10 kilograms and
volumes
are described where 7 ml means 7 milliliters and 16 oz means I6 fluid ounces.
"Room
temperature" is about 20°C.
The following ingredients were used in the Examples:
Abrasive Emulsion A: Aqueous emulsion of 48% aluminum oxide, 12% Fatty
Acid Mixture A; 1% oleic acid, 37% water and 2% Triethanolamine (85%); the
emulsion
had a viscosity in excess of 50,000 centipoise (50.0 pascal~seconds) at room
temperature.
Aluminum Oxide: This abrasive contained 95% A1~0~, 1.5% SiO~, 0.5% Fe203,
2 5 and 3.0% Ti02; had a mohs hardness of 9.0; and had an average particle
size of +325 mesh
(at least 98% of the aluminum oxide abrasive had an average particle size of
less than
44 microns).
Calcium Chloride: calcium chloride containing at least 94% active material.
Fatty ~,id Mixture A: A blend of 55% palmitic acid and 45% stearic acid that
is
3 0 prepared by crystallization in a solvent. It is made from the
hydrogenation of stearic acid
that is then vacuum distilled to obtain a product that contains about 40-45%
oleic acid and
about 10% linoleic acid in addition to the stearic acid. The vacuum-distilled
product is
stored in pails and cooled to 4°C in a refrigerated chamber. The
resulting chunks of solid
product are wrapped in cloth and subject to moderate pressure in a hydraulic
press. The
3 5 liquid that is pressed out from this process is "red oil" and the
resulting solid obtained is
"stearic acid from a single press". In a similar way, three different grades
of stearic acid
are produced: one of a single pressure, one of double pressure and one of a
triple pressure,
which is of the best quality. For the purposes of this invention, the product
of double
pressure is preferred and was used; it contained more than about 3% of oleic
acid.
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-10-
Magnesium Hydroxide: magnesium hydroxide containing at least 97% active
material.
Magnesium Silicofluoride: magnesium hexafluorosilicate hexahydrate.
Phosphoric Acid: concentrated phosphoric acid containing at least 75%
phosphoric
acid content and-the balance water.
Polv_eth"~ene Wax: Oxidized polyethylene wax, Chemical Abstracts Service No.
68441-17-8, specific gravity of from 0.92-0.99 g/cm3 and drop point (Mettler)
of 219°F
(104°C), obtained as AC-680 polyethylene wax from AlliedSignal of
Morristown, NJ.
Silicone Fluid. 100 Cstks: Trimethylsiloxy-endblocked polydimethylsiloxane
fluid
of 100 centistoke (0.01 m2/s) viscosity identified as corresponding to
Chemical Abstracts
Registry No. CAS#63148-62-9 (CTFA Name: dimethicone).
Silicone Fluid, 500 Cstks: Trimethylsiioxy-endblocked polydimethylsiloxane
fluid
of 500 centistoke (0.05 m2/s) viscosity identified as corresponding to
Chemical Abstracts
Registry No. CAS#63148-62-9 (CTFA Name: dimethicone).
Silicone Fluid. 1000 Cstks: Trimethylsiloxy-endblocked polydimethylsiloxane
fluid of 1000 centistoke (0.1 m2/s) viscosity identified as corresponding to
Chemical
Abstracts Registry No. CAS#63148-62-9 (CTFA Name: dimethicone).
Tartaric Acid: tartaric acid containing 99.5% active material.
Tergitol~ 15-S-12: nonionic surfactant of CTFA name: Pareth 15-12 - a
polyethylene glycol ether of a mixture of synthetic C"-Ct5 fatty alcohols with
an average
of 12 moles of ethylene oxide from Union Carbide Corporation of Danbury, CT.
Trie~hanolamine (85%7: Mixture of 85% triethanolamine and 15% diethanolamine.
Wax OA: Oxidized polyethylene wax with a specific gravity of 0.96 g/cm3
obtained
as Wax "OA" from BASF Corporation of Parsippany, New Jersey.
2 5 In the Examples, the 60° Gloss value was measured using a Model# JG-
100
Glossmeter from Power DC, of Japan using 15 reading per square meter of floor
surface
measured and averaging the readings obtained to obtain the reported value.
3 0 Table I presents an overall formula for a presently preferred cream
crystallizer
composition of the present invention.
CA 02282634 1999-08-25
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Table I
Ingredients Percent by Weight
Tergitol~ 15-S-12 0.20
Magnesium Hydroxide 0.30
Phosphoric Acid 2.12
Calcium Chloride 1.33
Tartaric Acid 3.00
Magnesium Silicofluoride 18.00
Silicone Fluid, 500 Cstks 0.25
Triethanolamine (85%) 1.224
Aluminum Oxide 33.624
Fatty Acid Mixture A 8.94
Oleic Acid 1.44
Water 29.572
This composition is prepared by preparing an aqueous emulsion of the abrasive,
which is then used to prepare the final composition having a pH of from about
2.0-2.5. 1n
the following, the amounts of each ingredient used are given in parts by
weight according
to percentages given in Table 1.
The aqueous emulsion of the abrasive is prepared by placing the solid Fatty
Acid
Mixture A in a container and heating the container with steam for about 15-20
minutes
until the Fatty Acid Mixture A is completely melted (final temperature is
about 75-81 °C).
A portion of the water (27.072 parts) is placed in a second mixing container
equipped with
a spiral mixer and is heated to 80-85°C over a period of about 10-15
minutes. The
Aluminum Oxide is then added to the water in the second container with mixing
(mixer set
at 29 r.p.m.) over about a 5 minute period (temperature of contents on
completion is about
75-80°C). The Oleic Acid is then added to the mixing contents of the
second container
over about a 3 minute period while the temperature of the contents is
maintained at about
75-80°C. The heated, melted stearic acid is poured from the first
container into the mixing
contents of the second container over a period of about 3 minutes while the
temperature of
the contents is maintained at about 75-80°C. The Triethanolamine is
added to the
contents of the second container with mixing and the contents are allowed to
mix for 5 to
2 0 10 minutes maximum to form the aqueous emulsion of the abrasive having a
pH of from
about 7.5 to about 8.5.
The cream crystallizer composition is prepared by placing the remainder of the
water (2.5 parts) in a mixing container equipped with a spiral mixer at
20°-25°C and the
mixer is started (40 r.p.m.). The Tergitol~ 15-S-12 is added to the mixing
water in the
2 5 mixing container over 2-3 minutes at 20°-25°C. The Magnesium
Hydroxide is then added
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to the mixing contents and allowed to mix for 10 minutes. The Phosphoric Acid
is then
added to the mixing contents of the container and allowed to mix for 10
minutes during
which time the temperature rises to 50°-60°C. No heat is added,
so the contents of the
mixing container begins to decrease with time. The Silicone Fluid, 500 Cstks
is then
added to the mixing contents of the container and allowed to mix in over a
five minute
period at 40-50°C. The Calcium Chloride is then added to the mixing
contents of the
container and allowed to mix in over 15-20 minutes (an increase in viscosity
occurs as the
mixing continues) at 25-30°. The mixer speed is increased from 40
r.p.m. to between 40-
60 r.p.m. to insure good mixing as a result of the increase in viscosity of
the contents. The
Tartaric Acid is then added to mixing contents of the container and allowed to
mix in over
a 10 minute period at 25°-30°C. The Magnesium Silicofluoride is
then added to the
mixing contents of the mixing container and allowed to mix for 10 minutes at
25-30°C.
The aqueous emulsion of the abrasive is then added to the mixing contents and
allowed to
stir over a period of 10 minutes at a temperature of 25-30°C. The
resulting emulsion
composition is then recirculated through a homogenizer for a period of 20
minutes to
insure that the contents of the mixing container are completely mixed and a
good emulsion
is formed.
Example 2
This comparative Example illustrates a conventional prior art oxalic-acid
containing composition for resurfacing marble floors and the improvement in
60° Gloss
angle on the floor surface after the composition is applied to the marble
floor using
machine-driven rotary floor polishing pads.
Example 2 contained 66% oxalic acid, 0.7% tin oxide polishing compound, 0.3%
sodium bicarbonate and 33% of an aqueous emulsion polishing product. The
aqueous
emulsion polishing product contained 40% aluminum oxide abrasive, 7.8% stearic
acid,
0.8% polyethylene wax, 1.3% petrolatum, 1.5% Pareth 15-12, 9.1% brightening
(polishing)
dust and 39.4% water.
Example 2 was applied to a test piece of black marble tile using the following
3 0 procedure (which was also the same procedure used in the other Examples
where a
laboratory evaluation of gloss value is reported).
1. The surface of the tile is sanded under cold running water using No. 320-A
wet sanding paper until the surface appears uniform.
2. The sanded tile surface is gently wiped with a soft sponge to remove any
3 5 remaining grit.
3. Gloss readings on the sanded are taken (10 readings are taken and the
average is reported as the initial gloss value). The target gloss reading for
sanded tile
surfaces is a 60° gloss value of no more than 5%.
4. A portion of the product to be tested is applied to the tile with a small
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portion of water and the surface is polished with an electric motor driven
hand buffing
machine for 3 minutes.
5. The surface of the tile is cleaned with water and absorbent paper to remove
any residue.
6. Tl~e dry tile is inspected and gloss readings are taken (10 readings are
taken
and the average is reported as the final gloss value).
The initial 60° gloss value of the tile before treatment in the manner
above was
13% and the final 60° gloss value after treatment with Example 2 was
69%.
Example 3
The stone floor surface crystallizer composition described in Table II was a
stable
emulsion in the form of a white cream that was easy to apply and provided
marble flooring
with good 60° gloss and a rich marble color.
Table II
Ingredients Percent by Weight
Water 2,5
Tergitol I S-S-12 0.20
Magnesium Hydroxide 0.3
Phosphoric Acid 2.12
Wax Emulsion A 0.3
Silicone Fluid, 500 Cstks 0.25
Calcium Chloride I.33
Tartaric Acid 3.00
Magnesium Silicofluoride 18.00
Abrasive Emulsion A 72.00
Example 3 was applied to a test piece of black marble tile using a procedure
of the
same type as described in Example 1. However, the Wax Emulsion A (not present
in
Example I ) was added after the addition of Phosphoric Acid and before
addition of the
Silicone Fluid, 500 Cstks. Another difference was that the last step described
in Example 1
2 0 involving recirculation of the final product was not done for Example 3
because the
equipment used to prepare this composition was not equipped to carry out
recirculation
through a homogenizer.
The initial 60° gloss value of the tile before treatment was 6% and the
final 60°
gloss value after treatment with Example 3 was 60%.
E~cample 4
In these Examples, a comparison between the application of prior art Example 2
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and inventive Example 3 was made on installed stone flooring surfaces that
were in need of
maintenance and were situated at various locations that were subject to
commercial foot
traffic. The compositions were applied using a commercial swing machine, motor
driven
rotary floor polishing machine running at 175 r.p.m. that weighed
approximately 60-70
pounds (27.2 - 32.8 kg). The flooring surface was buffed using 3M Company Tan
Polishing Pads for the evaluations reported in Tables III - V and 3M Company
Red
Polishing Pads for Tables VI - IX. The flooring surface was then rinsed to
remove any dry
composition residue left behind to reduce subsequent dulling of the floor
surface by any
such residue. The initial temperature of the flooring was about 70°F
(21. I °C) and the final
temperature immediately after application was about 85°F
(29.4°C) due to the heat of the
buffering operation. In the above evaluations, the application of Example 3 to
the flooring
surfaces was found to be easier and faster than that of Example 2. In all
cases involving
marble surfaces, the color of the flooring after treatment with Example 3 had
a richer-
looking color to the eye than was observed after the application of Example 2.
In the evaluations conducted in Tables III - V, 60° gloss values of the
sections of
flooring evaluated were measured before treatment and then after treatment of
the area
being tested after a specific amount of polishing time to evaluate the effect
of polishing
time on the gloss developed.
In the evaluations conducted in Tables VI - IX, an area of flooring was
artificially
2 0 damaged with three grades of sandpaper--fine - 150 grit; medium - 100
grit, and coarse -
60 grit--to simulate Low, Medium and High, respectively, levels of damage to
the flooring
surface. In these evaluations, the floor surface was buffed for 9 minutes
(until dry)
followed by an additional 3 minutes of buffing.
Table
III
- Gray
Marble
Flooring
Run No. Example Initial 60 Final 60 GlossFloor Area Buffing
No. Gloss (m2> Time
1 2 19 48 1.5 15
2 2 20 56 1.0 12
3 3 22 80 1.0 6
4 3 17 82 1.0 9
S 3 10 74 1.0 6
6 3 11 80 1.0 6
7 3 14 SS 1.0 6
8 3 11 81 1.0 9
9 3 12 85 1.0 9
10 3 10 85 1.0 9
As shown in Table III, inventive Example 3 produced higher levels of gloss in
a
r . , . . _ ..~... ,
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shorter period of time than did prior art Example 2 containing oxalic acid and
abrasive.
Run 7 was the lowest gloss reading for Example 3, but that was comparable to
the best
gloss reading obtained for Example 2 although Run 2 was polished twice as
long.
- Table
IV
- White
Terrazzo
Flooring
Run Example Initial 60 Final 60 GlossFloor Area Buffing
No. No. Gloss (rnzl Time
1 3 52 84 10 6
2 3 52 90 1.0 8
3 3 45 65 1.0 9
Table
V -
Gray
Granite
Flooring
Run No. ExampleInitial 60 Final 60 GlossFloor Area Buffing
No. Gloss (mz~ Time
1 3 9 31 1.0 9
Good results were obtained on White Terrazzo that does contain marble pieces
which granite showed the least improvement in gloss due to its nature.
Table
VI -
Brown
Marble
Flooring
Run No. ExampleSandpaper Initial 60 Final 60
No. Damage Gloss Gloss
1 3 Fine 36 82
2 3 Medium 26 93
3 3 High 20 90
4 2 Fine 46 69
5 2 Medium ~33 70
6 3 High 32 74
l0
Table arble Flooring
VII
- White
M
Run No. Example Sandpaper Initial 60 Final 60
No. Damage Gloss Gloss
1 3 Fine 43 85
2 3 Medium 33 83
3 3 High 25 61
4 2 Fine 34 74
5 2 Medium 31 78
6 3 High 18 73
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-16-
Table arble Flooring
VIII
- Black
M
Run No. Example Sandpaper Initial 60 Final 60
No. Damage Gloss Gloss
1 3 - Fine 51 91
2 3 Medium 34 88
3 3 High 20 88
4 2 Fine 42 61
2 Medium 42 65
6 3 High 13 64
Table
IX -
Green
Marble
Flooring
Run No. Example Sandpaper Initial 60 Final 60
No. Damage Gloss Gloss
1 3 Fine 36 68
2 3 Medium 34 66
3 3 High 14 56
4 2 Fine 22 27
After simulated damage using sandpaper, the brown, white and black marble
5 flooring all showed better gloss values for Example than did prior art
Example 2 except for
Run 3 in Table VII on white marble that received high sandpaper damage.
The stone floor surface crystallizer composition described in Table X was
prepared
to have 12% magnesium silicofluoride.
Table X
Ingredients Percent by Weight
Water 4.5
Tergitol 15-S-12 0.20
Magnesium Hydroxide 0.3
Phosphoric Acid 2.12
Wax Emulsion A 0.3
Silicone Fluid, 500 Cstks 0.25
Calcium Chloride 1.33
Tartaric Acid 3.00
Magnesium Silicofluoride 12.00
Abrasive Emulsion A 76.00 _
_ r_. , , , .. . .... -_
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_ _ -17-
The composition of Example 5 was evaluated on a marble tile floor. The initial
60°
gloss value of the tile before treatment (no sanding of the tile was done) was
28% and the
final 60° gloss value after treatment with Example 3 was 47%. Thus,
treatment with this
composition did improve the gloss value of the tile, but not as much as was
typically seen
for compositions containing 18% magnesium silicofluoride as in Example 3.
Exam lei s 6-7
The stone floor surface crystallizer compositions described in Table XI were
prepared with different types and amounts of silicone fluids.
Table X1
Ingredients Example 6 Example 7
Percent by Weight Percent by Weight
Water 2,p 2,0
Tergitol 1 S-S-12 0.20 0.20
Magnesium Hydroxide 0.3 0.3
Phosphoric Acid 2.0 2.0
Wax Emulsion A 0.3 0.3
Silicone Fluid, 100 Cstks 0.87
Silicone Fluid, 1000 Cstks 0.75
Calcium Chloride 1.33 1.33
Tartaric Acid 3.00 3.00
Magnesium Silicofluoride 18.00 18.00
Abrasive Emulsion A 72.00 72.00
The compositions of Examples 6 and 7 were evaluated on marble tiles according
to
the test procedure of Example 2.
For Example 6, the initial 60° gloss value of the tile before treatment
was 2% and
the final 60° gloss value after treatment with Example 3 was 61 %. The
appearance of the
tile after treatment was judged to be much less desirable than when the more
preferred
Silicone Fluid, 500 Cstks was used.
For Example 7, the initial 60° gloss value of the tile before treatment
was 3% and
2 0 the final 60° gloss value after treatment with Example 3 was 85%.
The tile after treatment
had a high gloss value, but was judged to be much slipperier than when the
more preferred
Silicone Fluid, 500 Cstks was used.
2 5 Stone floor surface crystallizer compositions of the type described in
Example 3
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were compared to commercial products for treating marble tile floors in this
Example using
the test procedure described in Example 2. The results obtained are reported
in Table XII.
PASTA BLANCATM marble floor restorer product was an abrasive- and oxalic
acid-containing commercial product of the type described in Example 2 sold by
S. C.
Johnson & Son; Inc. in Mexico.
TERR.ASHINETM marble floor crystallizer was an aqueous emulsion commercial
product sold by S. C. Johnson & Son, Inc. in Mexico. TERRASHINE used 18%
magnesium silicofluoride as the crystallizing agent along with 1 % calcium
chloride. It
contained 3% tartaric acid and 2% phosphoric acid along with 0.3% magnesium
hydroxide
and a polyethoxylated surfactant and small amounts of wax emulsions, but did
not contain
any abrasive or oxalic acid. It was intended for use from time to time to
maintain the finish
of marble floors between treatments with oxalic acid-containing products.
Table XII
Products Used Initial 60 Gloss Final 60 Gloss
Value Value
PASTA BLANCA Product 3% 63%
TERRASHINE Product 2% 24%
PASTA BLANCA followed by 3% 71 ro
treatment with TERRASHINE
Product
Example 3 2% 74%
Example 3 followed by TERRASHINE2% 85%
Product
Table XII shows that the compositions of Example 3 perform better than the
oxalic
acid-containing products without the disadvantages of having to use such
products.
Even better gloss was obtained when Example 3 was followed by a TERRASHINE
product treatment. Thus a more preferred way of using the composition of the
present
invention is to use it in combination with a product such as TERR.ASHINE which
can be
2 0 used to maintain the appearance of the stone, especially marble or
terrazzo, floor.
Example 3 contains both an abrasive and a silicone fluid not found in prior
art
silicofluoride-containing compositions and shows advantages over such
compositions as
well as over compositions containing oxalic acid that did contain abrasives.
.. r. . , __
