Note: Descriptions are shown in the official language in which they were submitted.
CA 02219619 1997-10-29
1 960048
IMPROVED AQUEOUS COATING COMPOSITIONS
BACKGROUND OF THE INVENTION
This invention relates to improvements in aqueous coating compositions,
where an active is dissolved, suspended, or emulsified in water. In particular, this
invention relates to the use of the combination of a rheology modifying polymer
and a super wetting agent to provide improved coating compositions.
As environmental and government regulations continue to require more
environmentally-friendly products, consumer and industrial companies are
reformulating their products to reduced or zero-solvent based systems.
Unfortunately, the substitution of water-based compositions for solvent-based
~0 systems is not straight forward and often results in decreased applicationperformance, increased chemical cost to co~ ls~le for lower performance, and
higher complexity processing equipment. This is especially relevant to
applications where the drying characteristics affect the end product performanceas water-based systems dry differently than organic solvent-based systems.
For example~ in the polish and coatings markets, various types of oils,
polymers, and/or waxes are commonly employed to preserve, protect, renew, and
enhance the appearance of concrete, wood, rubber, leather, metals, and various
polymeric surfaces. These products are typically offered as oil-in-water
emulsions and are usually accomplished by employing a combination of various
emulsifying surfactants. However, the pelroll.,ance of these products may be less
durable, as compared to solvent-based systems, due to the presence of residual
surfactants in the coating and their tendency to re-emulsify when exposed to
water or moisture. Selection of the surfactant system is also highly dependent on
the oil type, loading level, and a variety of other factors. The durability of these
. CA 02219619 1997-10-29
surfactant b~ed emulsions can be increased via the addition of various types of
additives, such as amino-functional silicones. However, the addition of these
materials greatly increases the chemical cost of these products.
Combinations of acrylic acid polymers, which are employed as thickeners,
and surfactants are known, but their perfollllallce results are not always
predictable. For exarnple, U.S. Patent No. 4,686,254 notes that homopolymers of
acrylic acid and anionic surfactants are not compatible and do not effectively
suspend certain ingredients in the m~nuf~tllre of personal care products.
Crosslinked hydrophobically modified polyacrylic acid polymers are
often employed as the primary emulsifying agent instead of surfactants to
improve the performance and stability of oil-in-water emulsions. The use of
these polymers as primary emulsifiers for oil-in-water emulsion products is wellknown and used in the personal care, household, and industrial markets. U.S.
Patent No. 5,004.598 teaches a process for making emulsions for topical cosmeticskin compositions. Patent Application WO 94/05731 to Chandarana et al.,
teaches the use of polymers as primary emulsifiers for automobile polishes and
requires the application of the emulsion to the surface via heavy mechanical
action, e.g.~ rubbing and buffing. U.S. Patent No. 5,338,345 to Scarborough et
al.. teaches the use of polymeric emulsifiers in low viscosity oil-in-water
~0 emulsions, but requires the use of high shear homogenization to form the
emulsion viscosity belo~ 100 cP and an oil having a droplet size of less than 50
mlcrons.
In other household cleaning and industrial specialty applications, the use
of polymeric additives tO provide suspension or emulsification of insolubles,
" rheology modification. and vertical cling are well known, such as for example the
starting formulations published in the BFGoodrich Detergents and Industrial
Specialties Applications Product Binders. However, even though the addition of
the polymeric additive improves some of the performance deficiencies of these
products, there is room for further improvement. The addition of the polymeric
CA 02219619 1997-10-29
additive can result in poor or incomplete surface wetting and surface residue upon
drying. This is described in the literature as spotting and filming.
The use of wetting agents, also known as surfactants or surface active
agents, in coating compositions is known, as noted above, since they are used toemulsify deliverables in the coating compositions. Wetting agents have been
employed, for example, to improve the m~nllf~chlre of polyacrylic polymers,
such as U.S. Patent Nos. 4,345,949; 4,375,533; and 4,419,502. They have been
employed to improve the wettability characteristics of polyacrylic acid polymers,
which relates to getting the polymers into solution, as in U.S. Patent Nos.
5,373,044 and 5,468,797. This latter application involves the use of surfactantshaving a surface tension of less than 40 dynes/cm. However, these surfactants are
also limited to use with sterically stabilized carboxylic acid polymers, and does
not elimin~te or improve spotting and/or filming in the final coating composition.
The so called ~'superwetting" agents are a sub-class of wetting agents known forI S their ability to reduce surface tension subst~nti~lly.
Although the use of polymers has greatly aided in the formulation of
reduced solvent-based systems, there is still a need to improve the wetting and the
ultimate drying characteristics of water-based coating formulations. A
composition which wets or coats the surface being treated in a manner which
'0 leaves a uniform coating~ does not leave spots or bead-up, and/or elimin~tec or
minimi7~s the rubbing step would be desirable. Such a coating also may require
a relatively low viscosity in order for it to be applied by spraying.
SUMMARY OF THE INVENTION
'5 The present invention is the result of a discovery that the use of a
combination of a small percentage of a super wetting agent with a surface tension
of less than 35 dynes/cm and a rheology modifying polymer in aqueous
compositions results in significantly improved surface wetting and uniform
surface coating. The rheology modifying polymer can be a natural, modified
natural or synthetic polymer, although crosclinked polycarboxylic polymers and
CA 02219619 1997-10-29
copolymers are l,le~lled. The aqueous coating composition contains an active
m~teri~l(s) which is dissolved, suspended, or ~m~ ified in the water phase. The
composition is dilution stable and can have a low viscosity, which is desirable for
certain applications.
For example in one embodiment of the present invention, the active
material is a solvent which is dissolved in the water. The combination of the
superwetting agent and a rheology modifying polymeric additive allows the
composition to be sprayed on to a vertical surface, such as glass, and exhibit
vertical cling (i.e., it will not run or drip) resulting in increased surface contact
time. The addition of the superwetting agent allows a ullifollll film to form
which decreases the potential for spotting and filming to occur upon drying.
In another embodiment of the invention, the active material is silicone oil
which is emulsified via the use of a rheology modifying agent. The addition of
the superwetting agent allows this composition to be sprayed or rubbed, with
uniform surface coverage, onto, e.g., automotive surfaces, such as rubber tires
and vinyl interior components,
Coating compositions employing the combination of the present invention
can be applied by spraying, wiping, or pouring and leave a uniform coating
having improved wetting characteristics which can be subjected to further wiping~0 or buffing, if necessary, or left as a coating. They can be applied to a wide
variety of surfaces, including, but not limited to, glass, porcelain, fiberglass,
concrete, leather, plastic, metal, ceramic, wood, and other industrial and
household surfaces, as well as a variety of personal care surfaces or applications,
such as skin or hair care. and the like.
~S
DETAILED DESCRIPTION
In the present invention, the combination of a surface tension modifying
agent, a rheology modifying polymer, and an active material, which can be
dissolved, suspended, or emulsified in water are employed in aqueous coating
compositions with improved wetting and/or uniform coating characteristics.
CA 02219619 1997-10-29
The surface tension modifying agent or superwetting agent is a highly
efficient, low surface energy s..rf~rt~nt The term dynarnic surface tension
modifying agent or superwetting agent is intçnded to mean any wetting agent or
surfactant having an equilibrium surface tension of 35 or less dynes per
centimeter at 0.1% concentration in water and as measured by the DuNouy
method, preferably less than 31 dynes per centimeter, with less than 30 dynes
per centimeter also being plcr~ d. Examples of superwetting agents are as
follows:
Equilibrium
Surface Tension
at 0.1%
Concentration
Superwettin~ (dynes/cm) Chemical
Agent Supplier Description
I 5 Zonyl~ FSO 19.0 E. I. duPont Fluoro chemical
with ethylene
glycol
Fluorad~FC- 20.0 3M Company Fluorinated
171 alkyl alkoxalate
DC Q2 521 1 21. I Dow Corning Polyoxy
ethylene
modified
polydimethyl
siloxane
TergitolX 15-S-7 27.3 UnionCarbide Mixtureof
linear secondarv
alcohols reacted
with
ethyleneoxide
'0 Surfynol~ TG 30.4 Air Products & 2,4,7,9-
Chemicals tetramethvl - 5 -
decyne-4,7-diol
Makon~ OP-9 30.g Stepan ~th
ChemlCal Wl 9 moles of
ethylene oxide
Fluowet OTN 19.2 Hoechst Fluoroaliph~tic
Celanese oxyethylate
Forafac 1157N 18.9 Atochem Polyfluoroalkyl
betaine
Fluorad FS- 21.2 3M Company Fluorinated
'5 170C alkyl polyoxy
ethylene ethanol
CA 02219619 1997-10-29
Silwet L-77 21.3 Union Carbide Pol~alkylene
oxi e modified
heptamethyl
trisiloxane
Fluorad FC-120 22.4 3M Company Ammonium
perfluoroalkyl
sulfonate
Zonyl FSP 24.4 E. I. duPont Ammoniated
phosphate
luorochemical
Zonyl FSN 24.4 E. I. duPont Hydroxy
tennln~ted
fluorochemical
Silwet L-7600 25.2 Union Carbide Pol~alkylene
oxi e modified
polydimethyl
siloxane
Silwet L-7604 24.8 Union Carbide Polvalkylene
oxi~e modified
polydimethyl
siloxane
The superwetting agent provides improved wetting or uniformity of the coating
composition. The superwetting agent alone or in combination with other
superwetting agents is present in an amount of less than 10% by weight based
upon the weight of the coating composition. The preferred range is about 0.01 toabout 10% by weight. with the ranges of about 0.05 to 5% by weight, about 0.1 to5% by weight. and about 0.1 to about 2% by weight being further plel~lled. DC
Q2-5211 is a silicone glycol copolymer, with poly-oxyethylene-modified
polydimethyl-siloxane and is preferred for silicone oil emulsions, while Zonyl
1 ~ FSP superwetting agent is preferred for solvent solutions.
The rheology modifying agent is used in amount of about 0.001 to about
10% by weight based upon the weight of the coating composition. The range of
about 0.01 to about 5% by weight is preferred, with the range of about 0.05 to
about 1% by weight being further preferred. The rheology modifying agent can
~0 be a natural or modified natural polymer, such as gums (e.g., xanthan gum),
cellulosics, modified cellulosics, starches, other polysaccharides and the like, or a
synthetic polymer, such as a homopolymer or a copolymer of an olefinically
unsaturated carboxylic acid or anhydride monomers cont~ining at least one
CA 02219619 1997-10-29
activated carbon to carbon olefinic double bond and at least one carboxyl group.The copolymers are preferably of a polycarboxylic acid monomer and a
hydrophobic monomer. The plc~llcd carboxylic acid is acrylic acid. The
homopolymers and copolymers preferably are crosslink~ d Cros~link~d
polyacrylic acid copolymers are further prefell~d since, in addition to modifying
the rheology of the coating composition, they can fi~nction as the primary
~mul~ifier or suspending agent for the active which is being emulsified or
suspended.
Homopolymers of polyacrylic acid are described, for example, in U.S.
Patent No. 2,798,053. Examples of homopolymers which are useful include
Carbopol~ 934, 940, 941, Ultrez 10, ETD 2050, and 974P polymers, which are
available from The BF Goodrich Company. Hydrophobically modified
polyacrylic acid polymers are described, for example, in U.S. Patent Nos.
3,915,921, 4,421,902. 4,509,949, 4,923,940, 4,996,274, 5,004,598, and
I ~ 5~349.030. These polymers have a large water-loving hydrophilic portion (thepolyacrylic acid portion) and a smaller oil-loving hydrophobic portion (which can
be derived from a long carbon chain acrylate ester). The polymers can be
dispersed in water and neutralized with base to thicken the aqueous composition,form a gel, or emulsify or suspend the deliverable. Useful polymers are sold as
'0 Carbopol~ 1342 and 138~ and Pemulen~ TR-l, TR-2, 1621, and 1622, all
available from BFGoodrich. Other polycarboxylic acid polymer compositions
which can be employed include~ for example, crosslinked copolymers of
acrylates, (meth)acrylic acid, maleic anhydride, and various combinations thereof.
Commercial polymers are avalable from Rheox Inc., Highstown, N.J. (such as
~~ Rheolate~ 5000 polymer), 3V Sigma, Bergamo, Italy (such as Stabyln 30
polymer, which is an acrylic acid/ vinyl ester copolymer, or Polygel polymer,
which are acrylic acid polymers and copolymers), BF Goodrich (such as
Carbopol EP-l thickener, which is a acrylic emulsion thickener), or Rohm and
Haas (such as Acrysol~ ICS-l thickener, which is an alkali-soluble acrylic
polymer emulsion. Preferred are the Carbopol0 and Pemulen~ polymers,
CA 02219619 1997-10-29
generally. The choice of the specific polymer to be employed will depend upon
the type of active being delivered.
The carboxyl co~ polymers.are prepared from monomers
co,.l~;--ing at least one activated vinyl group and a carboxyl group. Such
polymers are homopolymers of ~ls~ dled, polymerizable carboxylic monomers
such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic
anhydride, and the like, and copolymers of polymerizable carboxylic monomers
with acrylate esters, acrylamides, alkylated acrylamides, olefins, vinyl esters,vinyl ethers, or styrenics. The carboxyl co.~t~ g polymers have molecular
weights greater than about 500 to as high as several million. usually greater than
about 10,000 to 900,000 or more.
Representative higher alkyl acrylic esters are decycl acrylate, lauryl
acrylate, stearyl acrylate, behenyl acrylate and melissyl acrylate~ and the
corresponding methacrylates. These polymers are characterized in that they are
1~ prepared in a reaction medium containing an organic solvent and a hydrocarbon
solvent in respective weight ratio of 95/5 to 1/99, the organic solvent being
selected from ketones. esters~ ethers and alcohols having solubility parameter in
the range of 8 to 16 and the hydrocarbon solvent being selected from aliphatic
and cyclic aliphatic alkanes containing 4 to 12 carbon atoms and non-benzene
aromatics of 7 to 9 carbon atoms. The amounts of the carboxylic monomer and
the acrylate ester or vinyl ester or ether or styrenic are based on the combinedweight of both components. It should be understood that more than one
carboxylic monomer and more than one acrylate ester or vinyl ester or ether or
styrenic can be used in the monomer charge. Also useful are interpolymers of
2~ hydrophobically modified monomers and steric stabilizing polymeric surface
active agents having at least one hydrophilic moiety and at least one hydrophobic
moiety or a linear block or random comb configuration or mixtures thereof
Examples of steric stabilizers which can be used are Hypermer~, which is a
poly(12-hydroxystearic acid) polymer, available from Imperial Chemical
Industries Inc. and Pecosil~, which is a methyl-3-polyeLhoxypropyl siloxane-Q-
- . -
CA 02219619 1997-10-29
phosphate polymer, available from Phoenix Chemical, Somerville, New Jersey.
These are taught by US patent Nos. 4,203,877 and 5,349,030, the disclosures of
which are incorporated herein by reference.
The polymers can be cro~.~link~d in a manner known in the art by
inc!uding, in the monomer charge, a suitable crosslinker in amount of about 0.1 to
4%, preferably 0.2 to 1% by weight based on the combined weight of the
carboxylic monomer and the comonomer(s). The crosslinker is selected from
polymerizable monomers which contain a polymerizable vinyl group and at least
one other polymerizable group.
Polymerization of the carboxyl-co.~ monomers is usually carried
out in a catalyzed, free radical polymerization process, usually in inert diluents, as
is known in the art.
The combination of a rheology modifying polymer and superwetting
agent can be used in a variety of aqueous coating compositions to deliver the
I 5 active ingredient. The aqueous coating composition can be solutions, oil-in-water
emulsions, or water-based suspensions of the active ingredient.
Examples of actives include solvents (mineral spirits, mineral oil, naptha,
petroleum distillants, alcohols, glycols, polar solvents, non-polar solvents, d-limonene), surfactants (including anionic, nonionic, and zwitterionic surfactants),
'0 various polymers~ such as low molecular weight acrylic polymers, alkyds, and
urethanes, oils (natural and synthetic), waxes, ultra violet absorbers, builders,
dispersants, oxidizing agents. such as sodium hypochlorite or hydrogen peroxide,abrasives, pigments~ inks, dyes, fragrances, enzymes, and various other actives.See, for example, U.S. Patent No. ~,534,198.
'5 When the coating composition is an oil-in-water emulsion having water as
the continuous phase and a discontinuous oil phase, the active will be droplets of
a composition such as film forming organic silioxanes, dimethicone, esters,
natural and synthetic waxes, mineral oil, naphthenic or paraffinic hydrocarbons,solvents, nonvolatile organic water repellant compositions, low viscosity silicone
fluids, reactive and non-reactive amino functional polysiloxanes, and mixtures
CA 02219619 1997-10-29
- 10-
thereof. The oil phase is present in an amount of about 0.001 to about 80% by
weight based upon the weight of the coating composition. The ranges of about 5
to 50% by weight and 10 to 40% are prefell~d.
The use of a nonvolatile organic water repellant active in the compositions
of the invention is done in a conventional manner, such as in U.S. Patent No.
5,462,587. Actives which themselves are liquids (e.g., linseed oil) can be used.In addition, actives which are normally solids can be dissolved in an organic
solvent or heated to their softening point to forrn the n~cçc~y liquid for the
formation of an emulsion with water.
Natural and synthetic waxes are useful and can be ~alafrlnic waxes,
microcrystalline waxes, mineral waxes, vegetable waxes, animal waxes,
hydrocarbon waxes, organometallic waxes (such as allllninllm stearates, sodium
stearates, and zinc stearates), polyoxoaluminl-m monostearate, hydrogenated oil
waxes~ chlorinated waxes, and mixtures of such waxes. Paraffin waxes generally
I ~ contain about 14 different straight chain and branched hydrocarbons ranging from
C,8H38 to C3,H66 and solidify between about 27~C and about 70~C (between about
80~F and about 158~F). According to this invention, the pl~f~ d paraffin waxes
have melting points in the range of about 50 C to about 70 C, more preferably
from 55 C to 65~C. for long-term durability of water-repellant properties. Also
~0 included are hydrocarbon resins as inert hydrophobic fillers to provide the coating
composition with an additional solid base and binder for the wax or other
components. Such a hydrocarbon resin imparts the coating composition with
long term durability. Among the hydrocarbon resins which can be used in the
invention, there can be mentioned aromatic hydrocarbon resins, aliphatic resins
" and mixtures thereof. Typical aromatic resins include indene, styrene,
methylindenes and methyl styrene. Typical aliphatic resins include cis-and trans-
piperylene. Polyisobutylene, a highly viscous hydrocarbon, can be used as a filler
and provides long term durability and flexibility to the coatings made from the
compositions of the invention. Preferred hydrocarbon resins include a
hydrogenated C5 hydrocarbon resin with a dropping point t~l,lpeldtLlre of about
CA 02219619 1997-10-29
- 11 -
140 C, which are well known commercially available compositions. The
preferred C5 resin is Escarez~ 5340 available from Exxon Chemical. Other
useful C5 resins include Eastotac0 resins available from Eastman Chemical
Company and Nevrez~ resins available from Neville. Mixtures of hydrocarbon
S resins are also useful. Particularly pl~fellcd are mixtures of hydrogenated C5
resins and polyisobutylene.
Other nonvolatile organic water repellant compositions that can be used
include silicone resins (for example, Corning Fluid 200), fluoroalkyl resins, such
as Dupont Zonyl~ PHS, alkyds, including long oil and medium oil alkyds, and
drying oils such as linseed oil and tung oil.
The coating compositions can also include preservatives such as 3-iodo-2-
propenyl butyl carbamate (commercially available as PolyphyseX P100 available
from Troy Chemical Co.), copper n~th~n~te, zinc n~th~n~te, chlorothalanil
(tetrachloroisophthalonitrile) and 2-(thiocyanomethylthio) benzothiazole. UsefulI ~ preservatives include those above which provide for preservation of the coated
composition against for example, mildew, as well as bacteriostatic preservativeswhich protect the composition in the container before application. A particularly
useful bacteriostatic preservative is a bicyclic oxazolidines solution,
commercially available as Nuosept~ 95 available from Huls America Inc. This
'0 active also serves the function of neutralizing the rheology modifying polymer.
Other materials. which are not actives, that can be added to the
compositions. as is common to such compositions, include fragrances, dyes,
pigments, colorants, fluorescent whitening agents, neutralizing agents, buffers,chelating agents, and alkalinity adjusting agents. Useful pigmentc include red
'5 iron oxide, yellow iron oxide, titanium dioxide, and brown iron oxide. These other materials are present in conventional amounts.
The coating composition can include other agents, such as linear
carboxylic acid polymers, such as Good-rite~ K-702 or K-752 polymers,
available from The BF Goodrich Company, wetting performance enhancers such
as glycol or other polyhydric alcohols, ultraviolet (UV) light absorbers,
- - CA 02219619 1997-10-29
- 12-
fragrances, such as pine oil, benzaldehyde, or lemon oil, or other typical coating
composition modifiers.
The coating compositions are made by blending the ingredients. There is
no criticality in the order of addition of the ingredients, but the composition can
be made by adding the polymer to the water, then adding the oil phase, and then
adding the superwetting agent. If a W absorber is incorporated, it can be added
to the oil phase component.
There is no criticality in the particle size of the droplets which comprise
the oil phase. However, it is possible to adjust the particle size using high kinetic
energy devices such as high-p,es~ homogt;lli;~ , microfluidizers, ultrasonic
wave generators, and colloid mills which tend to reduce the particle size. Such
techniques are taught in U.S. Patent No. 5,338,345.
EXAMPLES
In order to illustrate the present invention, examples of aqueous coating
compositions were made and tested to determine the characteristics of the
coating, especially the wetting character or uniformity of the coating. The
following examples are provided to show various aspects of the present inventionwithout departing from the scope and spirit of the invention. Unless other~,vise'0 indicated, all parts and percentages used in the examples are by weight based
upon the total weight of the composition. In the Examples, the viscosities
reported were run at 20~C on a Brookfield Viscometer Model RVT-DV-II+ with
the a~lop,iate spindle at 20 rpm. The particle size of the droplets reported in the
Examples can be measured in a conventional manner, such as light microscopy,
'5 preferably using a Leeds and Northrop FRA analyzer. The surface tension ofthe
various super-wetting agents reported in the Examples was measured by the
DuNouy method at 0.1% surfactant concentration using a Kruss K-12
tensiometer. The surface tension of the final composition also was measured by
the DuNouy method.
-
CA 02219619 1997-10-29
EXAMPLE 1
This Example illustrates the benefits of the present invention in a silicone
emulsion composition which is especially useful for use on rubber surfaces, suchas automotive tires. The base formula is as follows:
s
Ingredients % by Weight
Water balance to 100%
Hydrophobically modified
polyacrylic acid copolymer ' 0.20
l O l O0 centistoke (cSt) silicone oil 2 20.00
Superwetting Agent (see Table 1)0.50
Triethanolamine to pH 6
Na2 EDTA 0.20
1S lOo.oo
' Pemulen 1622 from BFGoodrich
2 DC 200 Fluid from Dow Corning
'0 The composition was prepared by first dispersing the hydrophobically modified
polyacrylic acid copolymer into the water. This was followed by the addition of
the silicone oil and the super-wetting agent with good agitation. The composition
was then neutralized with triethanolamine to the target pH. The viscosity of thecomposition was then reduced via the addition of Na, EDTA. All formulas
showed good emulsion characteristics. The composition was then placed into a
bottle with a spray applicator and sprayed onto automobile tires. The
composition was not rubbed or buffed in any manner. Visual observations were
made as to the surface wetting characteristics of the composition. The results for
compositions containing various types of super wetting agents are listed in Table
30 l.
. CA 02219619 1997-10-29
- 14-
TABLE 1
Superwetting Droplet Size
Composition Agent (micron)Application result
1 None beading
2 DC Q2-5211 ' 7-8complete, unifomn
wetting
3 Zonyl FSO 2 15-60beading
4 Fluorad FC-171 3 10-35beading
' DowComing
' E.I. DuPont
3 3M Corp.
EXAMPLE 2
This Example illustrates the use of the present invention in a silicone emulsioncomposition which is useful for use on automotive interior vinyl surfaces, but
which can be used for other surfaces. It also illustrates the use of the presentinvention in a coating composition having a relatively low viscosity. The base
formula is as follows:
'0 Ingredients % by Weight
Water balance to 100%
Hydrophobically modified
polyacrylic acid copolymer ' 0.20
100 cSt silicone oil ' 20.00
'5 Superwetting Agent (see Table 2) 0.50
Triethanolamine to pH 6
Good-Rite K-752 3 0.25
1 00.00
Pemulen 1622 from BFGoodrich
' DC 200 Fluid from Dow Coming
3 BFGoodrich
The composition was prepared by first dispersing the hydrophobically modified
polyacrylic acid copolymer into the water. This was followed by the addition of
the silicone oil and the super wetting agent with good agitation. The composition
was then neutralized with triethanolamine to the target pH. The viscosity of thecomposition, which was 3300 cP, was then reduced via the addition of the Good-
- CA 02219619 1997-10-29
Rite K-752 polymer to 750 cP. All formulas showed good emulsion
characteristics. The composition was then placed onto various types of surfaces:rubber, vinyl, and maple wood. The application was rubbed onto the rubber
surface and drawn down to forrn a 0.01 mm film on the vinyl and wood surfaces.
Visual observations were made as to the surface wetting characteristics of the
composition. The results for various types of super wetting agents are listed inTable 2.
TABLE 2
Superwetting
Composition Agent Rubber Vinvl Maple Wood
DC Q2-5211 ' uniform uniform wetting uniform
wetting wetting
6 Zonyl FSO ' beading uniform wetting uniform
wetting
1 5 7 Fluorad FC- 171 3 beading beading, beading
pocketing
8 Tween 20 ~ beading beading, beading
pocketing
Dow Corning
' E.I. DuPont
3 3M Corp.
ICI (Sorbitan monolaurate; surface tension = 37
dynes/cm at .1% actives)
EXAMPLE 3
This Example illustrates the use of the present invention in a silicone emulsion'5 composition which also is useful for use on automotive interior vinyl surfaces and
which uses a higher viscosity silicone oil than in Example 2. The base formula is
as follows:
' CA 02219619 1997-10-29
- 16-
Composition 9
Ingredients % bv Weight
Water balance to 100%
Cro.~slink~d polyacrylic acid
homopolymer ' 0.40
350 cSt silicone oil 7 20.00
DC Q2-5211 Superwetting Agent 3 0.50
Triethanolamine to pH 6.78
Good-RiteK-752 4 2.50
100.00
' Carbopol 941 from BFGoodrich
2 DC 200 Fluid from Dow Corning
3 Dow Corning
4 BFGoodrich
The composition was prepared by first dispersing the polyacrylic acid
homopolymer into the water. This was followed by the addition of the silicone
oil and the super wetting agent with good agitation. The composition was then
'0 neutralized with triethanolamine to the target pH. The viscosity of the
composition was then reduced from 3600 cP to 420 cP via the addition of the
Good-Rite K-752 polymer. The composition showed good emulsion
characteristics. The product was stable for over 4 weeks at 50~C and passed 5
freeze/thaw cycles.
'5
EXA~PLE 4
This Example illustrates a high loading silicone emulsion cont~ining a Super-
Wetting Agent. This composition may be useful in its high active form as a
polish. It can also be diluted with water to lower the viscosity and allow the
composition to be easily sprayed.
CA 02219619 1997-10-29
- 17 -
Composition 10
Ingredients % by Weight
Water balance to 100%
Hydrophobically modified
polyacrylic acid copolymer ' 0.15
350 cSt silicone oil 2 60.00
DC Q2-5211 3 0.50
Triethanolamine to pH 6.7
loo.oo
product as is
pH 6.7
viscosity 6,200 cP
1 :2 dilution with water
pH 6.9
viscosity 75 cP
' Pemulen 1622 from BFGoodrich
2 DC 200 Fluid from Dow Corning
3 Dow Corning
The composition was prepared by first dispersing the Hydrophobically modified
2 ~ polyacrylic acid copolymer into the water. The silicone oil was then addedfollowed by the DC Q2-5211 superwetting agent with good agitation. The
composition was then neutralized with triethanolamine to the target pH. For
dilution, I part product was added to 2 parts water with gentle mixing.
EXAMPLE 5
This Example illustrates the effect of EDTA on reducing the viscosity of
emulsions while maintaining good product stability. The base formula is as
follows:
CA 02219619 1997-10-29
-18-
Ingredients % bv Weight
Water balance to 100%
Hydrophobically modified
polyacrylic acid copolymer ' 0.20
100 cSt silicone oil 220.00
DC Q2-5211 3 0.50
Triethanolamine to pH 6
Na2EDTA (see Table 3)0.00 to 0.60
1 00.00
' Pemulen 1622 from BFGoodrich
2 DC 200 Fluid from Dow Corning
3 Dow Corning
The composition was prepared by first dispersing the hydrophobically modified
polyacrylic acid copolymer into the water. This was followed by the addition of
the silicone oil and the DC Q2-5211 superwetting agent with good agitation. The
composition was then neutralized with triethanolamine to the target pH. The
~0 viscosity of the composition was then reduced via the addition of EDTA as
shown in Table 3. The surface wettability of all of the compositions was very
~ood, comparable to Composition 1. The compositions were also subjected to
freeze / thaw stability testing to determine product phase stability. The
composition was placed into a 0 C freezer for 24 hours. The product was then
'~ removed from the freezer and allowed to equilibrate to room temperature, ~20 C.
Visual observations of the product were recorded.
TABLE 3
Na~EDTA Viscosity Droplet Freeze / Thaw
Composition (% bv wt.)(cP! ~ Size Stability
(micron)
Il 0.00 3,300 6.25<7 pass I cycle
12 0.20 950 6.20<7 pass 1 cycle
13 0.40 450 6.15<7 pass 1 cycle
3~ 14 0.50 350 6.10<7 pass 1 cycle
0.60 450 6.05<7 fail
- CA 02219619 1997-10-29
- 19-
EXAMPLE 6
This Example illustrates the effect of linear polyacrylate polymers on reducing
the viscosity of emulsions while mAintAining good product stability. The base
formula is as follows:
Ingredients % by Weight
Water balance to 100%
Hydrophobically modified
polyacrylic acid copolymer ' 0.20
100 cSt silicone oil 2 20.00
DC Q2-5211 3 0.50
Triethanolamine to pH 6
linear polyacrylate 45 (see Table 4) 0.20 and 0.50
100.00
l Pemulen 1622 from BFGoodrich
2 DC 200 Fluid from Dow Corning
3 Dow Corning
4 Good-Rite K-752 from BFGoodrich (2,100 MW)
5 Good-Rite K-702 from BFGoodrich (240,000
MW)
The composition was prepared by first dispersing the hydrophobically modified
polyacrylic acid copolymer into the water. This was followed by the addition of
the silicone oil and the DC Q2-5211 superwetting agent with good agitation. The
composition was then neutralized with triethanolarnine to the target pH. The
viscosity of the composition was then reduced via the addition of the linear
polyacrylate polymer as shown in Table 4. The surface wettability of all of the
compositions was very good compared to Composition 1.
CA 02219619 1997-10-29
- 20 -
TABLE 4
Composition PolyacrylateType %by Viscosity
weight(cP)
11 none 0.003,300
16 Good-Rite K-752 0.20 710
17 Good-Rite K-752 O.S0 lS0
18 Good-Rite K-702 0.201~010
19 Good-Rite K-702 O.S0 280
EXAMPLE 7
This Example illustrates a silicone emulsion. This composition may be
homogenized in order to reduce the product viscosity for low viscosity
applications.
Composition 20
Ingredients % by Weight
Water balance to 100%
Hydrophobically modified
'0 polyacrylic acidcopolymer ' 0.30
1000 cSt silicone oil ' 30.00
DC Q2-5211 3 0.30
- Triethanolamine O.S0
1 00.00
'5
product as is
pH 7.5
viscosity 2,740 cP
Pemulen 1622 from BFGoodrich
' DC 200 Fluid from Dow Corning
3 Dow Corning
The composition was prepared by first dispersing the hydrophobically modified
polyacrylic acid copolymer into the water. The silicone oil was then added
followed by the DC Q2-5211 superwetting agent with good agitation. The
composition was then neutralized with triethanolamine to the target pH. The
product was then homogenized using a High Pressure APV Rannie laboratory
- CA 02219619 1997-10-29
homogenizer. The effect on the product viscosity as a function of
homogenization pressure and the number of cycles is presented in Table 5.
TABLE 5
Viscosity After Homo~enization (cP)
Cvcle 3.000PSI 6~000PSI 9.000PSI
0 2,740 2,740 2,740
410 178 142
2 212 148 124
3 174 130
6 166 114 92
8 158 116 70
158 102 66
EXAMPLE 8
This Example illustrates a silicone emulsion at a high concentration. This
composition may be useful as a polish or it can be diluted with water for low
viscosity applications.
0 Composition 21
Ingredients % by Weight
Water balanceto 100%
Hydrophobically modified
2~ polvacrylic acid copolymer '0.35
1000 cSt silicone oil ' 60.00
Glycerine 2.00
Diethylene glycol 2.75
DC Q2-5211 3 2.00
Triethanolarnine to pH 6.6
Good-RiteK-752 4 BOO
100.00
product as is
pH 6.6
viscosity 6,000 cP
I :2 dilution with water
pH 7.4
viscosity 50 cP
- CA 02219619 1997-10-29
Pemulen 1622 from BFGoodrich
2 DC 200 Fluid from Dow Corning
3 Dow Corning
4 BFGoodriCh
The composition was l,le~d by first dispersing the hydrophobically modified
polyacrylic acid copolymer into the water. The silicone oil was then added
followed by the glycerine and diethylene glycol with good mixing. The DC Q2-
5211 superwetting agent was then added with good agitation. The composition
was then neutralized with triethanolamine to the target pH followed by the
addition of the Good-Rite0 K-~52. The product was then homogenized using a
High Pressure APV Rannie laboratory homogenizer at 6,000 PSI for 1 cycle. For
the dilution, the product was diluted in a 1 :2 ratio with water (reducing the
silicone concentration to 20%). Both the concentrated and diluted product were
stable for 4 weeks at 50~C and both passed 5 freeze/thaw cycles. Application of
both products to a rubber surface resulted in a smooth and uniform film.
EXAMPLE 9
'0 - This Example illustrates a silicone emulsion cont~inin~ a UV absorber. Thiscomposition is especially useful for interior automotive vinyl surfaces where
added protection from UV degradation is beneficial:
Composition 22
2~ Ingredients % by Weight
Water balance to 100%
Hydrophobically modified
polyacrylic acid copolymer ' 0.15
C2-0563 Repellent 2 1.80
Tinuvin 328 3 0.20
1000 cSt silicone oil 420.00
DC Q2-5211 5 0.50
Triethanolamine to pH 6.2
linear polyacrylate 6 0.25
100.00
- CA 02219619 1997-10-29
Pemulen 1622 from BFGoodrich
2 Dow Corning
3 CibaGeigy
4 DC 200 Fluid from Dow Corning
5 Dow Corning
6 Good-Rite K-752 from BFGoodrich (2,100
MW)
The composition was prepared by first dispersing the hydrophobically modified
polyacrylic acid copolymer into the water. The W absorber, Tinuvin 328, was
then dissolved in the C2-0563 Repellent. This premix was then added to the
silicone oil. The silicone oil-W absorber blend was then added to the water-
polymer mixture followed by the DC Q2-5211 superwetting agent with good
agitation. The composition was then neutralized with triethanolamine to the
target pH. The viscosity of the composition was then reduced via the addition ofthe linear polyacrylate. The surface wettability of all of the compositions was
very good, comparable to Composition l. The viscosity was less than 300 cP.
The product passed I freeze / thaw stability cycle.
'O
EXAMPLE 10
This Example illustrates a composition which is useful as an all-purpose
detergent cleaner~ especially for use on glass and windows.
" In~redients %bv Weight
Water balance to 100%
Hydrophobically modified
polyacrylic acid copolymer '0.10
Isopropanol 5.00
Ammonium hydroxide to pH 9.5
Wetting Agent (see Table 6)0.25
Propylene glycol methyl ether 2 2.00
100.00
Carbopol ETD 2623 from BFGoodrich
' Dowanol PM from Dow Chemical
- CA 02219619 1997-10-29
- 24 -
The composition was prepared by first dispersing the hydrophobically modified
polyacrylic acid copolymer into the water. This was followed by the addition of
the isoprol anol, ammonium hydroxide, superwetting agent, and the propylene
glycol methyl ether.
The compositions were then sprayed on to a vertical glass window. The surface
film characteristics (wetting, uniformity, texture, clarity, etc.) were observed and
recorded. The wet films were rank ordered and are presented below in the order
of worst to best (Composition 23 had the worst surface film and Composition 33
had the best). Note also that Composition 24 contains no wetting agent and no
polymer.
TABLE 6
Wetting
Agent
Surface Composition
Tension Surface WetFilm
Composition Wettin~ Agent Type (cP! Tension (cP~ Characteristics
23 none -- 51.2 very rough, orange
peel
'0 24 none and no -- 47.6 beaded instantly
polymer
sodium lauryl 35.8 35.4 very foamy, pockets
sulfate
26 alkyl benzene 34.0 35.2 very foamy,pockets
sulfonate
27 Tween 20 ' 36.6 32.6 orange peel, clear
film
28 TergitolX 15-S-7 ~ 27.3 28.2 smoothandclear
'~ 29 Fluorad FC-120 3 22.4 26.0 smooth, clear
pockets
DC Q2-5211 4 21.1 21.6 smooth but hazy
31 SilwetL-7600 5 25.2 21.4 smoothbuthazy
32 ZonylFSO 6 19.0 15.8 smoothbuthazy
33 Zonyl FSP 6 24.4 13.3 smooth and clear
CA 02219619 1997-10-29
34 Fluorad FC-171 3 20.0 -- orange peel, did not
level, formulation
went cloudy (an
indication that this
Fluorad was not
soluble in the
system)
' ICI
2 Union Carbide
3 3M
4 Dow Corning
5 Union Carbide
6 EI DuPont
EXAMPLE 11
This Example illustrates improved wetting characteristics of this present
invention across different types of polymeric additives.
Ingredients % by Weight
Water balanceto 100%
Polymeric Additive (see Table 7)see below
Isopropanol 5.00
Ammonium hydroxide to pH 9.5
Wetting Agent (see Table 7) 0.25
~0 Propylene glycol methyl ether -'2.00
1 00.00
Dowanol PM from Dow Chemical
_
The composition was prepared by first dispersing the polymeric additive into thewater. This was followed by the addition of the isol.lopal.ol. The composition
was then neutralized to pH 10 with ammonium hydroxide. The wetting agent and
the propylene glycol methyl ether were then added. The compositions were then
sprayed on to a vertical glass window. The surface film characteristics (wetting,
uniformity, texture, clarity, etc.) were observed and recorded.
CA 02219619 1997-10-29
- 26 -
TABLE 7
Polymeric
Additive Wet Film
Composition Polymeric Additive Wetting Ayent (% by wt.) Characteristics
CarbopolETD2623 ' BiosoftS-100 3 0.1O veryfoamy,
pockets
36 Carbopol941 ' BiosoftS-100 3 0.1O veryfoamy,
pockets
37 AccusolICS-1 2 BiosoftS-100 3 0.40 veryfoamy,
pockets
38 CarbopolETD2623 ' ZonylFSP 4 0.1O smoothandclear
39 Carbopol941 ' ZonylFSP 4 0.10 smoothandclear
AccusolICS-l ~ ZonylFSP 4 0.40 smoothandclear
' BFGoodrich
' Rohm & Haas
3 alkyl benzene sulfonate from Stepan Company
4 E.I. DuPont
The above examples illustrate that the present invention can be used to
deliver actives in the form of solutions, suspensions, and emulsions, at variousviscosities. The above examples also illustrate that the present invention can be
'O used to produce coatings exhibiting vertical cling, as well as improved coating
and'filming characteristics.
The foregoing embodiments of the present invention have been presented
for purposes of illustration and description. These description and embodiments
are not intended to be exhaustive or to limit the invention to the precise form
disclosed, and obviouslv many modifications and variations are possible in lightof the above disclosure. The embodiments were chosen and described in order to
best explain the principle of the invention and its practical applications to thereby
enable others skilled in the art to best utilize the invention in its various
embodiments and with various modifications as are suited to the particular use
contemplated. lt is intended that the invention be defined by the following
claims.
