Title of Invention

A PROCESS FOR PRODUCING A COMPOSITION

Abstract A process for producing a composition comprising: (a) providing a pre-dispersion of silica particles comprising hydrophobically modified fumed silica particles by stirring hydrophobically modified fumed silica particles into a solution comprising (i) a disilazane selected from hexamethyldisilazane, divinyltetramethyldisilazane, bis(3,3-triflouropropyl) tetramethyldisilazane and octamethylcyclotetrasilazane, and (ii) a first volatile solvent or solvent mixture selected from straight or branched, linear or cyclic aliphatic, or aromatic hydrocarbons with 2 to 14 carbon atoms, monovalent linear or branched alcohols with 1 to 6 carbon atoms, ketones or aldehydes with 1 to 6 car bon atoms, ethers or esters with 2 to 8 carbon atoms, or linear or cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units, wherein the concentration of the hydrophobically modified fumed silica particles in the pre-dispersiof) results in from 10 percent to 30 percent by weight of the total weight of the pre-dispersion, and wherein the concentration of the disilazane is between 0.1 and 10 percent by weight of the total weight of the pre-dispersion; and (b) mixing with a disperser said pre-dispersion to provide a process composition while reducing the particle size of said silica particles to a median particle size in the range between 100 and 4000nm.
Full Text IMPROVED PROCESSING COMPOSITIONS AND METHOD OF
FORMING THE SAME
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation-in-part of co-pending U.S. Application Serial
No. 10/740,346, filed December 18, 2003, which is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
[0002] The present invention relates to a process composition (concentrated and diluted forms)
and a method (i.e., process) for forming the same. The inventive process composition
(concentrated and diluted forms) is useful in forming a treatment composition that is capable of
forming essentially transparent, detachable and renewable protective coatings on a receptive
surface by a process of applying to the receptive surface a treatment composition comprising a
plurality of hydrophobic particles colloidally dispersed in a volatile solvent; allowing the volatile
solvent to evaporate; and thereby depositing a coating on the receptive surface that provides dirt-
and water-repellent properties, self-cleaning and easier next time cleaning benefits.
2. Description of the Related Art
[0003] The principle of self-cleaning coatings is well-known in the literature. The effect
generally requires two essential features: one being a hydrophobic surface or hydrophobic
coating on a surface; and the second being some degree of surface roughness which combine to
produce a structured "superhydrophobic" surface, exhibiting high water contact angles that act to
readily repel water and shed adherent particulate soils with even small amounts of water alone,
without requiring the use of typical cleaning agents.
[0004] The use of hydrophobic materials, such as perfluorinated polymers, to produce


hydrophobic surfaces is known. A further development of these surfaces consists in structuring
the surfaces in the µm to nm range. U.S. Pat. No. 5,599,489 discloses a process in which a
surface can be rendered particularly repellent by bombardment with particles of appropriate size,
followed by perfluorination.
[0005] A suitable combination of structure and hydrophobic properties permits even small
amounts of water moving on the surface to entrain adherent dirt particles and clean the surface
(see, for example, U.S. Pat. No. 6,660,363; and U.S. Pat. No. 3,354,022).
[0006] The prior art of EP-B-0 933 388 requires an aspect ratio >l and a surface energy of less
than 20 mN/m for these self-cleaning surfaces; the aspect ratio being defined here as the quotient
which is the ratio of the height of the structure to its width. The abovementioned criteria are
typically found in nature, for example, in the lotus leaf. The surface of the plant is composed of
a hydrophobic waxy material and has elevations separated by a few µm. Water droplets
substantially contact only the peaks of the elevations. There are many descriptions in the
literature of water-repellent surfaces of this type.
[0007] EP-A-0 909 747 teaches a process for generating a self-cleaning surface. The surface has
hydrophobic elevations whose height is from 5 to 200 µm. A surface of this type is produced by
applying a dispersion of pulverulent particles and of an inert material in a siloxane solution and
then curing. The structure-forming particles are therefore secured to the surface by way of an
auxiliary medium.
[0008] U.S. Pat. Pub. No. 2005/0136217A1 concludes that it is technically possible to render the
surfaces of articles artificially self-cleaning. The surface structures necessary for this purpose,
which are composed of elevations and depressions, have a separation in the range from 0.1 to
200 µm between the elevations of the surface structures, and have an elevation height in the
range from 0.1 to 100 µm. The materials used for this purpose are composed of hydrophobic


polymers or of lastingly hydrophobized material. Release of the particles from the carrier matrix
has to be prevented.
[0009] This principle has been borrowed from nature. Small contact surfaces lower the level of
van der Waals interaction responsible for adhesion to flat surfaces with low surface energy. For
example, the leaves of the lotus plant have elevations composed of a wax, and these reduce the
area of contact with water.
[0010] Processes for producing these structured surfaces are likewise known. Besides the use of
a master template to mold these structures in fill-in detail by an injection molding or embossing
processes, there are also known processes that utilize the application of particles to a surface.
This is disclosed, for example, in U.S. Pat. No. 5,599,489.
[0011] Recently, attempts have been made to provide self-cleaning surfaces on textiles. It has
been found that self-cleaning surfaces can be generated by applying fine-particle SiO2
(AEROSIL®) to textiles. In this process, the AEROSIL® materials are bonded into the polymer
matrix of the textile fiber, using a solvent that partially dissolves the fiber to effect adhesion
[0012] U.S. Pat. Pub. No. 2004/0154106A1 describes polymer fibers with self-cleaning surfaces.
In the prior art disclosure, the self-cleaning surface is obtained by exposure to a solvent, which
comprises structure-forming particles, using the solvent to solvate the surface of the polymer
fibers, adhesion of the structure-forming particles to the solvated surface, and removing the
solvent. The disadvantage of this process is that, during processing of the polymer fibers
(spinning, knitting, etc.), the structure-forming particles, and therefore the structure that renders
the surface self-cleaning, can become damaged or sometimes lost entirely, the result being that
the self-cleaning effect is also lost.
[0013] U.S. Pat. Pub. No. 2005/0103457A1 describes textile sheets with a self-cleaning and
water-repellent surface composed of at least one synthetic and/or natural textile base material A,


and of an artificial, at least to some extent, hydrophobic surface with elevations and depressions
composed of particles that have been securely bonded to the base material A, without adhesives,
resins, or coatings. The hydrophobic surfaces are obtained by treating the base material A with
at least one solvent that comprises the undissolved particles, and removing the solvent,
whereupon at least some of the particles become securely bonded to the surface of the base
material A. However, the disadvantage of this prior art process is the very complicated finishing
of the textile surfaces. Moreover, this prior art process requires precise matching of the solvent
to the base material of the textiles. However, in clothing there are generally mixed fabrics
present, and this matching therefore becomes more complicated. If the matching of the solvents
is not precise, the result can be irreparable damage to parts of the clothing. The textile surfaces
therefore have to be treated prior to tailoring.
[0014] U.S. Pat. No. 6,800,354 describes substrates with a self-cleaning surface and a process
for a permanent coating of the substrates providing the self-cleaning properties. The process
includes the following steps: (1) coating of the surface with a composition containing structure
forming particles and a layer forming material; (2) forming a cohesive layer that fixes the
structure forming particles firmly to the surface, and then; (3) hydrophobizing the structured
surface with a hydrophobizing agent which adheres firmly to the structured surface. The
structure forming particles preferably have an average diameter of less than 100 nm, more
preferably in the range between 5 and 50 nm. In an example, a float glass with a transparent
self-cleaning surface was produced by coating the glass with a composition by means of a screen
printing process using a 100 T screen. The composition included 0.5 wt.% boric acid and 4 wt.%
pyrogenic silica with an average diameter of the primary particles of 12 nm in a water friendly
medium. After drying, the coating was shock fired at 660°C for a duration of 4 min. The
hydrophobization of the structured surface was carried out by introducing an ethanolic solution
of tridecafluorooctyltriethoxysilane over the surface and curing at an elevated temperature. The
disadvantages of the described method is its multiple-step nature and the requirement of a high


temperature process. In addition, it results in a permanent coating which cannot be easily
detached by a simple cleaning procedure.
[0015] All of these coatings are characterized in that they are intended to be applied permanently
to the articles, and thus have the disadvantage that they cannot be simply removed and reapplied
in the event of impairment by scratching, discoloration or any other damage to the coating,
surface or coated surface structure. If this type of damage occurs, the article either has to be
freed from the surface structure by a complicated method and retreated, or has to be disposed of,
if its appearance is no longer acceptable.
[0016] U.S. Pat. Pub. No. 2005/0136217A1 describes a process for producing detachable
coatings with dirt- and water-repellent properties. These coatings of the prior art are produced
by spray-application of hydrophobic alcohols, such as nonacosan-10-ol, or of alkanediols, such
as nonacosane-5,10-diol, or of waxes. The coatings of U.S. Pat. Pub. No. 2005/0136217A1 can
be removed from articles by strong mechanical forces, e.g., scratching, brushing, or high-
pressure water treatment, or by treatment with water which comprises detergents that disperse
some of the structure-formers. A disadvantage of the prior art coatings disclosed in U.S. Pat.
Pub. No. 2005/0136217A1 is the strong forces needed for mechanical removal of the coating.
The use of strong forces for the mechanical removal of the coating runs the risk that when the
coating is removed the surface of the article itself will also be damaged. Treatment with water
that comprises detergents can likewise lead to damage to the article, depending on its nature.
[0017] U.S. Pat. Pub. No. 2004/0213904 describes a process for producing detachable dirt- and
water-repellent surface coatings on articles, wherein during the coating process, hydrophobic
particles are applied to the surface of the articles, thus generating a structure with elevations on
the surface of the articles that has dirt- and water-repellent properties, which comprises
suspending the hydrophobic particles in a solution of an alkyl-modified silicone wax in a highly
volatile siloxane, applying this suspension to at least one surface of an article, and then removing


the highly volatile siloxane. In this prior document, examples of compositions for producing
those surface coatings are given and procedures how they are made are also provided. The
compositions are dispersions of fumed silica particles present at 1 to 2 wt.% of the total weight
of the dispersion in a solution of an alkyl-modified silicone wax present at 0.5 wt.% in
decamethylcyclopentasiloxane. These compositions are produced by dissolving the alkyl-
modified silicone wax in decamethylcyclopentasiloxane and then dispersing the fumed silica in
this solution with vigorous stirring. Although the process for producing detachable dirt- and
water-repellent surface coatings provided in the aforementioned application proved to provide
better results with respect to run-off behavior of water droplets and gloss values on various
surfaces compared to processes known from the prior state of the art, it still has some
disadvantages. Especially on high gloss surfaces such as glass, brushed metal and varnished or
painted surfaces, the coating is easily perceptible as a grayish or hazy layer by the naked eye,
which is not acceptable for many applications.
[0018] The various approaches employed in the prior art are directed to modification of the
targeted surfaces to have sufficient roughness to provide a coating capable of exhibiting the
Lotus effect, and generally produce non-transparent coatings and films that suffer from poor
visual appearance, particularly on glossy, shiny and/or highly reflective surfaces. Further,
approaches that provide protective coatings with improved visual appearances rely on fixatives
to firmly attach and/or embed materials onto the treated surface, accompanied by chemical,
physical and/or thermal processes required to produce them and resulting in permanent and non-
renewable treated articles.
[0019] It is therefore an object of the present invention to provide a process to produce process
compositions (concentrated and diluted forms) to be used in treatment compositions, which can
produce essentially transparent protective surface coatings on a wide variety of materials.
[0020] It is therefore an object of the present invention to provide a process to produce process


compositions (concentrated and diluted forms) to be used in treatment compositions that can
produce detachable and renewable dirt- and water-repellent surface coatings on a receptive
surface, and which can also treat articles to give a relatively durable coating, which, however,
can be detached using simple means, without requiring any chemical or physical modification or
change to the underlying substrate, which may then be readily restored to its pristine initial state
when desired.
[0021] It is a further object of the present invention to provide a process to produce process
compositions (concentrated and diluted forms) to be used in treatment compositions that can
provide receptive surfaces with transparent, detachable and renewable protective surface
coatings on a wide variety of materials and substrates.
[0022] It is a further object of the present invention to provide a process to produce process
compositions (concentrated and diluted forms) to be used in treatment compositions which can
provide receptive surfaces with transparent, detachable and renewable protective surface
coatings, which can be easily renewed by removing the coatings by simple means and reapplying
the coatings, on a wide variety of materials and substrates.
[0023] It is yet a further object of the present invention to provide a process to produce process
compositions (in concentrated or diluted forms) to be used in treatment compositions which can
provide receptive surfaces with transparent, detachable and renewable protective surface
coatings on a wide variety of materials which thereby exhibit dirt- and water-repellency, self-
cleaning and easier next time cleaning benefits.
SUMMARY OF THE INVENTION
[0024] It was surprisingly found that detachable and renewable protective coatings which are
substantially transparent can be applied to receptive surfaces by use of a hydrophobically
modified silica particles containing treatment composition, provided said treatment composition

has been made by diluting, optionally while adding other functional ingredients, an initial
process composition, which, in turn, has been produced at a high concentration of the silica, in
the presence of an optional, yet preferable, disilazane derivative, and under high shear
conditions. It was further surprisingly found that these protective coatings can exhibit good
durability, even in the absence of conventional durability agents.
[0025] In accordance with the aforementioned surprising finding and the above objects and those
that will be mentioned and will become apparent below, one aspect of the present invention is a
process for producing a process composition to be used in treatment compositions intended for
applying a transparent, detachable and renewable protective coating on a receptive surface which
provides dirt- and water-repellency comprising:
(a) providing a pre-dispersion of silica particles comprising hydrophobically modified fumed
silica particles by stirring said silica particles into a solution comprising
(i) at least one compound of general formula (I) or (II):

wherein R1, R2, and R3 can be the same or different, and are independently selected from
hydrogen, straight or branched, saturated or unsaturated alkyl chain groups of from 1 to 8 carbon
atoms, optionally substituted with fluorine atoms, or aromatic groups of from 6 to 12 carbon
atoms, optionally substituted with fluorine atoms, R4 is hydrogen or a methyl group, and m is
from 3 to 8, and
(ii) a first volatile solvent or solvent mixture selected from straight or branched, linear or
cyclic aliphatic, or aromatic hydrocarbons with 2 to 14 carbon atoms, optionally substituted with
fluorine or chlorine atoms, monovalent linear or branched alcohols with 1 to 6 carbon atoms,


ketones or aldehydes with 1 to 6 carbon atoms, ethers or esters with 2 to 8 carbon atoms, or
linear or cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units, wherein the
concentration of the hydrophobically modified fumed silica particles in the pre-dispersion results
in from 10 percent to about 30 percent by weight of the total weight of the pre-dispersion, and
wherein the concentration of any one of compounds (I) and/or (II) is between 0.1 and 10 percent
by weight of the total weight of the pre-dispersion; and
(b) mixing with a disperser said pre-dispersion to provide a process composition while reducing
said silica particles to a median particle size in the range between 100 and 4000 nm.
[0026] In accordance with the above objects and those that will be mentioned and will become
apparent below, one aspect of the present invention is a process of forming a process
composition wherein the compounds of general formula (I) and (II) are omitted.
[0027] In accordance with the above objects and those that will be mentioned and will become
apparent below, one aspect of the present invention is a process of forming a diluted process
composition that is flowable and pumpable that comprises a dilution step (c) after mixing step
(b) wherein a second volatile solvent or solvent mixture, which is the same or different solvent or
solvent mixture as the first volatile solvent or solvent mixture, is used as the diluent to provide a
final concentration of the hydrophobically modified fumed silica particles of minimum 5 % by
weight of the total process composition. The dilution may also occur using durability agents or a
combination of durability agents and the second volatile solvent or solvent mixture.
[0028] In accordance with the above objects and those that will be mentioned and will become
apparent below, one aspect of the present invention is a process composition that comprises:

5 to 30 % by weight of hydrophobically modified fumed silica particles with a
median particle size in the range between 100 and 4000 nm;
50 to 95 % by weight of a volatile solvent or solvent mixture selected from straight
or branched, linear or cyclic aliphatic, or aromatic hydrocarbons with 2 to 14 carbon atoms,
monovalent linear or branched alcohols with 1 to 6 carbon atoms, ketones or aldehydes with 1
to 6 carbon atoms, ethers or esters with 2 to 8 carbon atoms, or linear or cyclic
polydimethylsiloxanes with 2 to 10 dimethylsiloxy units; and
0.01 to 10 % by weight of a compound of general formulas (I) or (II)

wherein R1, R2, and R3 can be the same or different, and are independently selected from
hydrogen, straight or branched, saturated or unsaturated alkyl chain groups of from 1 to 8
carbon atoms, or aromatic groups of from 6 to 12 carbon atoms, R4 is hydrogen or a methyl
group, and m is from 3 to 8.
[0029] In accordance with the above objects and those that will be mentioned and will become
apparent below, one aspect of the present invention is a process composition wherein the
compounds of general formula (I) and (II) are omitted. In some aspects of the present invention,
a durability agent can also be present in the either or both of the diluted or concentration form of
the inventive process composition.


[0030] Further features and advantages of the present invention will become apparent to those of
ordinary skill in the art in view of the detailed description of preferred embodiments below,
when considered together with the attached drawings and claims.
BRIEF DESCRIPTION OF THE ACCOPANYING DRAWINGS
[0031] The foregoing aspects and others will be readily appreciated by the skilled artisan from
the following description of illustrative embodiments when read in conjunction with the
accompanying drawings.
[0032] Figure 1 is a scanning electron micrograph (SEM) image of a conventional Lotus effect
coating formulation obtained according to the methods described in U.S. Pat. Pub. No.
2004/0213904, corresponding to Comparative process example H, diluted to 0.75 wt.% as active
silica with Dow Corning DC 245 fluid (comparative example 21), and applied to an automotive
test panel using a PreVal Sprayer according to the test methods described herein below.
[0033] Figure 2 is an SEM image of one embodiment of an inventive treatment composition
containing about 0.5 wt.% active silica processed according to the methods of the present
invention according to inventive treatment composition example 15, applied to a black
automotive test panel according to the methods of the present invention as described herein
below.
[0034] Figure 3 is an atomic force microscope (AFM) topographical image of a treated black
paint panel bearing a renewable coating applied according to the present invention.
[0035] Figure 4 is an AFM topographical image of the untreated black paint panel prior to
treatment showing the original, unmodified surface.
[0036] Figure 5 is a plot of the rheological profile of a dispersion with a representative


embodiment of inventive process compositions R and U, processed with and without
hexamethyldisilazane, respectively. G' and G" refer to the viscous and elastic components of
the complex rheological response curves as measured in units of Pascal (Pa) as a function of the
oscillation frequency in Hertz (Hz), measured under the conditions indicated in the process
description for the example compositions.
DETAILED DESCRIPTION
[0037] Before describing the present invention in detail, it is to be understood that this invention
is not limited to particularly exemplified systems or process parameters that may, of course,
vary. It is also to be understood that the terminology used herein is for the purpose of describing
particular embodiments of the invention only, and is not intended to limit the scope of the
invention in any manner.
[0038] All publications, patents and patent applications cited herein, whether supra or infra, are
hereby incorporated by reference in their entirety to the same extent as if each individual
publication, patent or patent application was specifically and individually indicated to be
incorporated by reference.
[0039] It must be noted that, as used in this specification and the appended claims, the singular
forms "a," "an" and "the" include plural referents unless the content clearly dictates otherwise.
Thus, for example, reference to a "surfactant" includes two or more such surfactants.
[0040] Unless defined otherwise, all technical and scientific terms used herein have the same
meaning as commonly understood by one of ordinary skill in the art to which the invention
pertains. Although a number of methods and materials similar or equivalent to those described
herein can be used in the practice of the present invention, the preferred materials and methods
are described herein.


[0041] In the application, effective amounts are generally those amounts listed as the ranges or
levels of ingredients in the descriptions, which follow hereto. Unless otherwise stated, amounts
listed in percentage ("%'s") are in weight percent as indicated as "wt.%", (based on 100 wt.%
active) of the total composition or formulation described.
[0042] As used herein, the term "particle" is intended to include any discrete particle, primary
particle, aggregate and/or aggregated collection of primary particles, agglomerate and/or
agglomerated collection of aggregates, and/or colloidally dispersed particles, aggregates,
agglomerates and/or loose assemblies of particulate materials, and combinations thereof.
[0043] It is noted that particle size determination provides an average of particle sizes, generally
calculated as a median particle size, of a selected distribution obtained by measuring a sample of
material either in the form of an aliquot of a liquid composition, and/or a sample of material in-
situ as present as an applied surface coating on a surface. Measurement techniques to determine
the particle size differ on the nature of the material, providing for some variability in measured
particle size distributions, mean, median and average particle size parameters, and the like.
Measured particle sizes thus typically indicate an average value and distribution of all the various
particulate structures present in the measured system, providing an average particle size whose
value reflects some proportional contribution from all primary, aggregated and/or agglomerated
particulate structures present.
[0044] The median particle size (mass median particle diameter), also referred to as "D50", is the
particle diameter that divides the frequency distribution in half; fifty percent of the mass has
particles with a larger diameter, and fifty percent of the mass has particles with a smaller
diameter. According to this definition, the median particles size as such does not specify
whether the particle size distribution curve is monomodal, biomodal or multimodal.
[0045] "Specific surface area" means the surface area per unit weight of a particulate solid, e.g.


as determined by the B.E.T. (Brunauer, Emmett, and Teller) method.
[0046] As stated above, one aspect of the present invention relates to a process composition and
a method (i.e., process) of forming the same. The process composition of the present invention
which, may or may not be in a diluted form, can be formulated into a treatment composition that
forms a detachable and renewable protective coating on a respective surface which provides
water and dirt repellency. In accordance with the present invention, the detachable coating is
substantially transparent and results in a change of less than 3.0 Delta E units to the respective
surface measured before and after deposition of the coating. It is noted that the diluted process
composition provides a dispersion that is flowable and pumpable that is more desirable in some
applications than the undiluted process composition of the present invention.
[0047] The process composition of the present invention includes from 5 to 30 %, preferably 5 to
25 %, even more preferably 5 to 15 %, and most preferably 5 to 10 % by weight of
hydrophobically modified fumed silica particles (to be described in greater detail hereinbelow)
with a median particle size in the range between 100 and 4000 nm, preferably between 100 to
3000 nm, and even more preferably between 100 to 1000 nm. The process composition of the
present invention also includes from 50 to 95 %, preferably from 75 to 95 %, and even more
preferably from 90 to 95 %, by weight of a volatile solvent or solvent mixture (to be described in
greater detail herein below). The volatile solvent or solvent mixture present in the process
composition of the present invention has been added during the formation of the pre-dispersion
(e.g., a first volatile solvent or solvent mixture) and partly may have been added after formation
of the process composition as a diluent (e.g., a second volatile solvent or solvent mixture). Of
the various volatile solvents or solvent mixtures which are mentioned hereinbelow, it is preferred
in one embodiment that the volatile solvent or solvent mixture comprises a linear
polydimethylsiloxane with 2 to 10 dimethylsiloxy units. In yet another embodiment, it is
preferred that the volatile solvent or solvent mixture within the inventive process composition

comprises a cyclic polydimethylsiloxane with 3 to 6 dimethylsiloxy units. One highly preferred
volatile solvent that is present in the inventive process composition is
decamethylcyclopentasiloxane.
[0048] In some embodiments of the present invention, the process composition may optionally
include from 0.01 to 10 %, preferably from 0.01 to 5%, and even more preferably from 0.01 to 1
%, by weight of a compound of general formulas (I) or (II)

wherein R1, R2, and R3 can be the same or different, and are independently selected from
hydrogen, straight or branched, saturated or unsaturated alkyl chain groups of from 1 to 8 carbon
atoms, optionally substituted with fluorine atoms, or aromatic groups of from 6 to 12 carbon
atoms, optionally substituted with fluorine atoms, R4 is hydrogen or a methyl group, and m is
from 3 to 8.
[0049] In embodiments wherein compounds of formula (I) and (II) are present, it is preferred
that R4 is hydrogen, R1 and R2 are methyl, and R3 is hydrogen, straight or branched, saturated or
unsaturated alkyl chain groups of from 1 to 8 carbon atoms, optionally substituted with fluorine
atoms, aromatic groups of from 6 to 12 carbon atoms, optionally substituted with fluorine atoms,
R is a hydrogen or a methyl group, and m is from 3 to 8. More preferably, and when
compounds of formula (I) and (II) are present in the inventive process composition, R4 is
hydrogen, R1 and R2 are methyl, and R3 is independently hydrogen or methyl. Even more
preferably, compounds of formula (I) and (II) in which R4 is hydrogen, R1, R2, and R3 are methyl
can optionally be present.

[0050] In yet another embodiment of the present invention, an optional durability agent (to be
described in greater detail hereinbelow) can also be present in the process composition of the
present invention. It is noted that although the present invention contemplates the use of a
durability agent, the applicants of the present application have surprisingly discovered that the
durability of protective coatings obtained using treatment compositions derived from the
inventive process compositions (diluted or undiluted) which contain a disilazane derivative is
substantially no different than compositions of the prior art that include a durability agent. It is
noted that when a durability agent is used it may be added during the initial stage of providing a
pre-dispersion or after mixing. When present, the durability agent is present in the inventive
process composition in a concentration from 0.01 to 10 % by weight, more preferably from 0.01
to 5 % by weight, and even more preferably from 0.01 to 1 % by weight, based on the total
process composition.
[0051] The inventive process composition described hereinabove is formed by first providing a
pre-dispersion of silica particles comprising hydrophobically modified fumed silica particles by
stirring the silica particles into a solution comprising
(i) optionally at least one compound of general formula (I) or (II):

wherein R1,R2,R3,R4 and m are as defined herein above, and
(ii) a first volatile solvent or solvent mixture selected from straight or branched, linear or
cyclic aliphatic, or aromatic hydrocarbons with 2 to 14 carbon atoms, optionally substituted with
fluorine or chlorine atoms, monovalent linear or branched alcohols with 1 to 6 carbon atoms,
ketones or aldehydes with 1 to 6 carbon atoms, ethers or esters with 2 to 8 carbon atoms, or


linear or cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units, wherein the
concentration of the hydrophobically modified fumed silica particles in the pre-dispersion results
in from 10 percent to about 30 percent by weight of the total weight of the pre-dispersion. In
accordance with the present invention, and when compounds of formula (I) and (II) are used, the
concentration of any one of compounds (I) and/or (II) is between 0.1 and 10 percent, preferably
between 0.1 to 5 percent, and even more preferably between 0.1 to about 3 percent, by weight of
the total weight of the pre-dispersion. An optional durability agent can also be used in providing
the pre-dispersion. The amounts of the silica particles, optional disilazane derivatives, first
volatile solvent or solvent mixture, and optional durability agent are within ranges that provide
the above stated amounts of each component within the final process composition. Stirring is
achieved at this point of the present invention by using conventional stirring equipment that is
well known in the art.
[0052] After providing the pre-dispersion, the pre-dispersion is then mixed with a disperser to
provide the inventive process composition while reducing the silica particles to a median particle
size in the range between 100 and 4000 nm, more preferably between 100 and 3000 nm, and
even more preferably between 100 and 1000 nm. The conditions and disperser used in this step
of the present invention will be described in greater detail hereinbelow.
[0053] The above mentioned steps provide a process composition of the present invention that is
concentrated, i.e., undiluted. Dilution of the inventive process composition can be performed by
adding, with stirring, a second volatile solvent or solvent mixture and/or a durability agent
therein. The second volatile solvent or solvent mixture can comprise the same or different
volatile solvent or solvent mixture than used in forming the pre-dispersion. It is noted that the
section including the description of the volatile solvent provided hereinbelow is intended to
include both the first and second volatile solvents. Dilution of the hydrophobically modified
fumed silica particles containing process composition to a minimum final concentration of 5%


by weight can be achieved. This provides a process composition that is generally more flowable
and pumpable, i.e., easier processability, than a concentrated form of the inventive process
composition.
Hydrophobically modified silica
[0054] Suitable hydrophobically modified fumed silica particles that may be used in the present
invention include silica particles that have been hydrophobicized by any means known in the art.
In some embodiments of the invention, the silicon dioxide utilized is a colloidal silicon dioxide.
Colloidal silicon dioxide is a generally fumed silica prepared by a suitable process to reduce the
particle size and modify the surface properties. A common process in the art to modify the
surface properties is to produce fumed silica, for example by production of the silica material
under conditions of a vapor-phase hydrolysis at an elevated temperature with a surface
modifying silicon compound, such as silicon dimethyl dichloride. Such products are
commercially available from a number of sources, including Cabot Corporation, Tuscola, IL
(under the trade name CAB-O-SIL) and Degussa, Inc., Piscataway, NJ (under the trade name
AEROSIL).
[0055] Suitable hydrophobically modified firmed silica particles include, but are not limited to:
those commercially available from Degussa Corporation, Parsippany, NJ, as designated under
the R Series of the AEROSIL® and AEROXIDE® LE trade names. The different AEROSIL® R
and AEROXIDE® LE types differ in the kind of hydrophobic coating, the BET surface area, the
average primary particle size and the carbon content. The hydrophobic properties are a result of
a suitable hydrophobizing treatment, e.g., treatment with at least one compound from the group
of the organosilanes, alkylsilanes, the fluorinated silanes, and/or the disilazanes. Commercially
available examples include AEROSIL® R 202, AEROSIL® R 805, AEROSIL® R 812,


AEROSIL® R 812 S, AEROSIL® R 972, AEROSIL® R 974, AEROSIL® R 8200, AEROXIDE®
LE-1 and AEROXIDE® LE-2.
[0056] Other silica materials are also suitable when hydrophobically modified by use of
hydrophobizing materials capable of rendering the surfaces of the silica particles suitably
hydrophobic. The suitable hydrophobizing materials include all those common in the art that are
compatible for use with the silica materials to render their surfaces suitably hydrophobic.
Suitable examples, include, but are not limited to: the organosilanes, alkylsilanes, the fluorinated
silanes, and/or the disilazanes. Suitable organosilanes include, but are not limited to:
alkylchlorosilanes; alkoxysilanes, e.g., methyltrimethoxysilane, methyltriethoxysilane,
ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-
propyltrimethoxysilane, i-propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane,
hexyltrimethoxysilane, octyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, n-
octyltriethoxysilane, phenyltriethoxysilane, polytriethoxysilane; trialkoxyarylsilanes;
isooctyltrimethoxy-silane; N-(3-triethoxysilylpropyl) methoxyethoxyethoxy ethyl carbamate; N-
(3-triethoxysilylpropyl) methoxyethoxyethoxyethyl carbamate; polydialkylsiloxanes including,
e.g., polydimethylsiloxane; arylsilanes including, e.g., substituted and unsubstituted arylsilanes;
alkylsilanes including, e.g., substituted and unsubstituted alkyl silanes including, e. g., methoxy
and hydroxy substituted alkyl silanes; and combinations thereof. Some suitable
alkylchlorosilanes include, for example, methyltrichlorosilane, dimethyldichlorosilane,
trimethylchlorosilane, octylmethyldichlorosilane, octyltrichlorosilane,
octadecylmethyldichlorosilane and octadecyltrichlorosilane. Other suitable materials include, for
example, methylmethoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane and
trirnethylmethoxysilane; methylethoxysilanes such as methyltriethoxysilane,
dimethyldiethoxysilane and trimethylethoxysilane; methylacetoxysilanes such as
methyltnacetoxysilane, dimethyldiacetoxysilane and trimethylacetoxysilane; vinylsilanes such as
vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane,


vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane,
vinyltriethoxysilane, vinylmethyldiethoxysilane and vinyldimethylethoxysilane.
[0057] Disilazanes, which can be employed in the present invention as processing aid, are well
known in the art. Suitable disilazanes include for example, but are not limited to:
hexamethyldisilazane, divinyltetramethyldisilazane and bis(3,3-
trifluoropropyl)tetramethyldisilazane. Cyclosilazanes are also suitable, and include, for example,
octamethylcyclotetrasilazane. It is noted that the aforementioned disilazanes and cyclosilazanes
typically have the basic formula (I) and (II) described above. Thus, these disilazanes and
cyclosilazanes can be used as either or both as hydrophobizing material for hydrophobically
modifying fumed silica particles and as a processing aid in forming the pre-dispersion mentioned
supra.
[0058] Suitable fluorinated silanes include the fluorinated alkyl-, alkoxy-, aryl- and/or alkylaryl-
silanes, and fully perfluorinated alkyl-, alkoxy-, aryl- and/or alkylaryl-silanes. Examples of
fluoroalkyl silanes include, but are not limited to: those marketed by Degussa under the trade
name of Dynasylan. An example of a suitable fluorinated alkoxy-silane is perfluorooctyl
trimethoxysilane.
Process Equipment
[0059] Suitable equipment for effectively dispersing the hydrophobically modified fumed silica
particles of the present invention include any kind of device which is capable of applying high
enough shear forces to a concentrated particulate slurry and thus being effective at decreasing the
average particle size distribution of particles within the slurry down to 100 to 4,000 nanometers
where initial particle sizes range from about 1000 to 1,000,000 nanometers can be employed
according to the methods of the present invention. Suitable examples include, but are not limited
to: mixers and/or dispersers based on the rotor stator principle such as the L4RT type available

from Silverson Machines, Waterside at Chesham Bucks, England. Further suitable examples are
mixers using dissolver or dispenser blades, such as the CV type available from Dispermat (BYK-
Gardner, Geretsried, Germany), and/or the H-Trieb 4REB/L model available from Heynau
Getriebe, Landshut, Germany. Effective dispersing can also be achieved with a horizontal mill,
one suitable example being the MH2P type from OKK USA Company, Glendale Heights, IL.
Durability Agent
[0060] A durability agent may optionally be included in the process and/or treatment
compositions of the present invention. When included, one possible embodiment is to include
the durability agent during the processing step. Suitable durability agents may be selected from
the group of alkoxysilanes of the general formula (III)

wherein R5 is a straight or branched, saturated or unsaturated alkyl chain group of from 1 to 16
carbon atoms, optionally substituted with fluorine atoms, hydroxyl, amino, mercapto, or epoxy
groups, R6 is an alkyl chain of 1 to 2 carbon atoms, a is 1 or 2; or selected form the group of
alkyl-modified linear or cyclic polydimethylsiloxanes of the general formulas (IV) and (V)

wherein R7 is an alkyl chain group of from 6 to 24 carbon atoms, n is from 1 to 100, o from 1 to
40, p from 0 to 7, q from 1 to 7, provided that the sum (p + q) is at least 3.
Additional durability agents suitable for use herein include those previously disclosed in U.S.


Pat. Pub. No. 2004/0213904A1.
[0061] The level of durability agent employed herein is typically between 0.1 and 10 percent by
weight of the total weight of the composition.
Volatile Solvent
[0062] A volatile solvent is employed in the inventive process and/or treatment compositions in
the capacity of a liquid carrier for methods of delivering and effectively applying the treatment
compositions to a receptive surface in a manner capable of forming a functional protective
coating on the surface.
[0063] Suitable volatile solvents are selected from the group of aromatic, branched, cyclic,
and/or linear hydrocarbons with 2 to 14 carbon atoms, optionally substituted with fluorine or
chlorine atoms, monovalent linear or branched alcohols, aldehydes or ketones with 1 to 6 carbon
atoms, ethers or esters with 2 to 8 carbon atoms, linear or cyclic polydimethylsiloxanes with 2 to
10 dimethylsiloxy units, or mixtures thereof. Examples of suitable volatile solvents include, but
are not limited to: n-propane, n-butane, n-pentane, cyclo-pentane, n-hexane, cyclo-hexane, n-
heptane, isododecane, kerosene, methanol, ethanol, 1-propanol, isopropanol, 1-butanol,
dimethylether, diethylether, petroleum ether and ethylacetate, octamethyltrisiloxane, marketed
under the trade name Dow Corning 200 Fluid lest, decamethylcyclopentasiloxane, marketed
under the trade name Dow Corning 245 (available from Dow Chemical), TEGO® Polish Additiv
5 (available from Degussa), perfluorinated solvents, and other halogenated materials such as
chlorinated solvents are also suitably employed where their use is appropriate.
[0064] Additional solvents that may be employed include those organic solvents having some
water solubility and/or water miscibility, and at least some ability to couple with water or
moisture that may be present or become incorporated into the inventive treatment compositions
through processing, packaging and during application. These are generally added in addition to

3
the more volatile solvent, although they may be employed alone as well as in any suitable
combination or mixture capable of stabilizing the dispersion of the hydrophobically modified
silica particles during processing, packaging, storage and use.
[0065] Suitable organic solvents include, but are not limited to: C1-6 alkanols, C1-6 diols, C1-10
alkyl ethers of alkylene glycols, C3-24 alkylene glycol ethers, polyalkylene glycols, short chain
carboxylic acids, short chain esters, isoparafinic hydrocarbons, mineral spirits, alkylaromatics,
terpenes, terpene derivatives, terpenoids, terpenoid derivatives, formaldehyde, and pyrrolidones.
Alkanols include, but are not limited to: methanol, ethanol, n-propanol, isopropanol, butanol,
pentanol, and hexanol, and isomers thereof. Diols include, but are not limited to: methylene,
ethylene, propylene and butylene glycols. Alkylene glycol ethers include, but are not limited to:
ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl
ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol
monohexyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol
n-propyl ether, propylene glycol monobutyl ether, propylene glycol t-butyl ether, di- or tri-
polypropylene glycol methyl or ethyl or propyl or butyl ether, acetate and propionate esters of
glycol ethers. Short chain carboxylic acids include, but are not limited to: acetic acid, glycolic
acid, lactic acid and propionic acid. Short chain esters include, but are not limited to: glycol
acetate, and cyclic or linear volatile methylsiloxanes.
[0066] Organic solvents that are less volatile can optionally be included in combination with the
more volatile solvent for the purpose of modifying evaporation rates. Suitable examples of less
volatile organic solvents are those with lower vapor pressures, for example those having a vapor
pressure less than 0.1 mm Hg (20 °C) which include, but are not limited to: dipropylene glycol
n-propyl ether, dipropylene glycol t-butyl ether, dipropylene glycol n-butyl ether, tripropylene
glycol methyl ether, tripropylene glycol n-butyl ether, diethylene glycol propyl ether, diethylene
glycol butyl ether, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate,


and diethylene glycol butyl ether acetate (all available from ARCO Chemical Company).
[0067] The volatile solvent is typically present at a level between 50 to 90 weight percent in the
inventive process composition.
[0068] As stated above the process composition of the present invention can be formulated into a
treatment composition which may comprise, in addition to the inventive process composition,
additional additives including a suspending agent, functional adjunct, and propellant, which are
described in greater detail herein below.
Propellant
[0069] Propellants which may optionally be used in conjunction with the inventive treatment
compositions are those well known and conventional in the art and include, for example, a
hydrocarbon, of from 1 to 10 carbon atoms, such as n-propane, n-butane, isobutane, n-pentane,
isopentane, and mixtures thereof; dimethyl ether and blends thereof as well as individual or
mixtures of chloro-, chlorofluoro- and/or fluorohydrocarbons- and/or hydrochlorofluorocarbons
(HCFCs). Useful commercially available compositions include A-70 (Aerosol® compositions
with a vapor pressure of 70 p.s.i.g. available from companies such as Diversified and Aeropress)
and Dymel 152a (1,1-difluoroethane from DuPont). Also suitable as propellants are
compressed gases such as carbon dioxide, compressed air, nitrogen, and possibly dense or
supercritical fluids may also be used, either alone or in combination, and alternatively in
combination with other propellant types.
[0070] In dispensing applications employing a propellant, the inventive treatment composition is
dispensed by activating the actuator nozzle of an aerosol type container onto the area in need of
treatment, and in accordance with the application manner as described herein, the area is treated
when the inventive treatment composition is deposited onto the surface, the propellant normally
dissipating during the dispensing step so that minimal residue of the propellant remains


associated with the inventive treatment composition as it impinges the surface to be treated. The
nature of the atomization by extremely rapid propellant dissipation is believed to produce
extremely fine droplets of the inventive treatment compositions to aid in producing an even spray
pattern and allow deposition of a uniform and consistent film of the liquid inventive treatment
composition onto the surface, although alternative non-propellant assisted delivery means may
also be suitably employed.
[0071] If a propellant is used, it will generally be in an amount of from about 1 wt.% to about 75
wt.% of the aerosol formulation. Generally, the amount of a particular propellant employed
should provide an internal pressure of from about 20 to about 150 p.s.i.g. at 70°F in order to
provide good atomization and delivery of the inventive treatment compositions.
Suspending Agent
[0072] Suspending agents may optionally be included in the inventive treatment compositions to
improve the suspension and/or dispersion properties of the inventive compositions. Suspending
agents when employed, may function to improve the suspension and dispersion properties of the
hydrophobically modified fumed silica particles, other solid particulate additives, and other
optional agents and functional adjuvants included in the treatment composition. They are
generally employed at levels sufficient for stabilization and so that when present, the level of
usage does not negatively impact the beneficial transparent properties of films provided by use of
the inventive treatment compositions containing them.
[0073] Suitable suspending agents include polymers and surfactants, and combinations thereof.
[0074] Polymer type suspending agents include anionic, cationic and nonionic polymers.
Examples include, but are not limited to: vinyl polymers such as, cross linked acrylic acid
polymers with the CTFA name Carbomer, cellulose derivatives and modified cellulose polymers
such as, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl


cellulose, nitro cellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, crystalline
cellulose, cellulose powder, polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl
guar gum, xanthan gum, arabia gum, tragacanth, galactan, carob gum, guar gum, karaya gum,
carrageen, pectin, agar, quince seed (Cydonia oblonga Mill), starch (rice, corn, potato, wheat),
algae colloids (algae extract), microbiological polymers such as, dextran, succinoglucan,
pulleran, starch-based polymers such as, carboxymethyl starch, methylhydroxypropyl starch,
alginic acid-based polymers such as, sodium alginate, alginic acid propylene glycol esters,
acrylate polymers such as, sodium polyacrylate, polyethylacrylate, polyacrylamide, and
polyethyleneimine.
[0075] Other optional suspending agents include anionic, cationic, nonionic, amphoteric and
zwitterionic surfactants. Examples of surfactants that are useful as particle suspending agents,
which can be categorized as acyl derivatives, include long chain amine oxides, and mixtures
thereof. Exemplary suspending agents of this type are described in U.S. Pat. No. 4,741,855.
Additional suitable suspending agents include ethylene glycol esters of fatty acids, preferably
having from about 16 to about 22 carbon atoms. Also suitable are the ethylene glycol stearates,
both mono and distearate; alkanol amides of fatty acids, for example, stearic monoethanolamide,
stearic diethanolamide, stearic monoisopropanolamide and stearic monoethanolamide stearate;
long chain acyl derivatives including long chain esters of long chain fatty acids, for example,
stearyl stearate and cetyl palmitate; long chain esters of long chain alkanol amides, for example,
stearamide diethanolamide distearate, stearamide monoethanolamide stearate); and glyceryl
esters, for example, glyceryl distearate, trihydroxystearin, a commercial example of which is
Thixin available from Rheox, Inc. Also suitable are long chain acyl derivatives, ethylene glycol
esters of long chain carboxylic acids, long chain amine oxides, and alkanol amides of long chain
carboxylic acids.


[0076] Other long chain acyl derivatives suitable for use as suspending agents include N,N-
dihydrocarbyl amido benzoic acid and soluble salts thereof including for example the sodium
and potassium salts; N,N-di(hydrogenated) C16, C18 and tallow amido benzoic acid species of
this family, which are commercially available from Stepan Company (Northfield, III., USA).
[0077] Examples of suitable long chain amine oxides for use as suspending agents include
longer chain alkyl dimethyl amine oxides, for example, stearyl dimethyl amine oxide.
[0078] Other suitable suspending agents include primary amines having a fatty alkyl moiety
having about 12 or more carbon atoms, examples of which include palmitamine or stearamine;
and secondary amines having two fatty alkyl moieties each having at least about 12 carbon
atoms, examples of which include dipalmitoylamine or di(hydrogenated tallow)amine. Still
other suitable suspending agents include di(hydrogenated tallow)phthalic acid amide, and
crosslinked maleic anhydride-methyl vinyl ether copolymer.
[0079] In addition, other polymer and surfactant materials known in the art may also be suitably
employed in the inventive treatment compositions provided that they do not negatively impact
the performance of the protective films when applied to a receptive surface.
[0080] When included, the suspending agent is typically employed at a level of about 0.001 to 5
wt.% of the finished treatment composition, or at a level that does not impact the desirable
beneficial optical properties of the films provided by use of the present invention.
Functional Adjunct
[0081] Treatment compositions, methods and treatment kits of the present invention may
optionally further include one or more functional adjuncts. Functional adjuncts may be
combined with the inventive treatment compositions, combined during processing of the
concentrated process materials or process compositions, or alternatively post added or delivered


simultaneously during dispensing and application of the inventive treatment compositions
according to the methods and treatment kits described herein.
[0082] Functional adjuncts are optionally included to provide at least one additional beneficial
property, functional and/or corollary benefit, or aesthetic enhancement to the treatment
compositions, or the resultant protective coatings provided by use of the treatments compositions
and/or kits employing them. The functional property can be one that provides enhanced product
properties owing to improved storage stability, and thus incorporating for example, but not
limited to: phase stabilizers, corrosion protection agents, dispersants, and the like, including
combinations thereof for improving treatment composition storage properties when packaged.
Additionally, functional adjuncts that provide enhanced dispensing properties, including, for
example, flow agents, atomization aids, wetting agents, spreading agents, evaporation modifiers,
solvent couplers, drying aids, azeotropic cosolvents, droplet-size modifiers, and the like,
including combinations thereof for improving the step of application wherein the treatment
compositions are dispensed and applied to the targeted surface to provide the inventive
protective properties described herein.
[0083] Further functional adjuncts may be included that provide enhanced protective benefits
and/or corollary benefits to the protective films present on receptive surfaces treated by use of
the inventive treatment compositions. Suitable functional adjuncts providing such enhanced
protective benefits and/or corollary benefits may be selected from ultraviolet light absorbers,
ultraviolet light blockers, free-radical scavengers, fluorescent whitening agents, colorants, dyes,
pigments, photoactive particles, color changing dyes, color fading dyes, bleaching agents,
fixative agents, perfume, fragrance, odor control agents, anti-static agents, and combinations
thereof.
[0084] When included, the functional adjunct is typically employed at a level of about 0.001 to 5
wt.% of the finished treatment composition, or at a level that does not impact the desirable


beneficial optical properties of the films provided by use of the present invention.
Water
[0085] Since the inventive treatment compositions described herein are generally non-aqueous,
water is generally excluded from the composition, and materials employed, including optional
functional adjuncts, are selected which are free of excessive water and/or moisture. The
inventive treatment compositions and methods of application described herein may tolerate some
water, particularly if a coupling solvent, selected from a water miscible, water soluble, and/or
partially water soluble solvent or combination thereof, is employed as an optional functional
adjunct in the treatment composition. If water is present, it may be de-ionized, industrial soft
water, or any suitable grade of water for the particular application.
[0086] For non-aqueous treatment compositions, water is preferably limited to levels of less than
5% by weight or volume, more preferably less than 2% by weight or volume and most preferably
less than 1% by weight or volume. When coupling solvents are employed, water may be present
at significantly higher levels, any level being suitable provided that the level of water and any
necessary coupling agent does not interfere with the ability of the inventive treatment
compositions to form transparent, renewable and durable surface protective coatings on the
receptive surfaces to which they are applied.
Areas of Use
[0087] The methods, treatment compositions and treatment kits employing the inventive
treatment compositions and methods according to the present invention may be used to treat a
receptive surface of a substrate, material, article, and/or object, wherein the respective surfaces
are receptive to treatment and capable of hosting the durable and non-permanent deposited film
comprising the hydrophobically modified fumed silica particles in the form of silica particle
agglomerates on the surface.


[0088] The treatment compositions of the present invention can be used for treating a variety of
receptive surfaces of inanimate articles, including non-porous and porous surfaces comprising
automotive and household materials, and their respective surfaces. Examples of suitable
automotive surfaces and articles include, but are not limited to: wheels, wheel trim, wheel
covers, removable wheel covers, splash guards, car panels and painted surfaces, clear-coated car
surfaces, metal, painted metal fixtures, chromed articles, bumpers, bumper stickers, bug
deflectors, rain deflectors, vinyl materials including car boots, wheel covers, convertible tops,
camper awnings, sun shades, vehicle covers, license plates, plastic articles, lens covers, signal
light lens covering, brake light lens covering, headlamp and fog light lens covering, and the like.
Examples of suitable interior automotive surfaces include, but are not limited to: vinyl and
upholstery surfaces, dashboard, dash instrument lens covering, seats, carpet, floor runners,
speaker covers, and the like.
[0089] Treatment compositions of the present invention can be used on articles and surfaces
found inside and outside the home, including for example, kitchen and bathroom areas, living
areas, interior and exterior surfaces. Suitable surfaces include both porous and non-porous
surfaces, materials and substrates. Non-limiting examples of non-porous surfaces include
metals, metal oxides, aluminum, anodized aluminum, painted substrates, stainless steel, chrome,
clear-coated automotive surfaces, ellastomers, vinyl, plastics, polymers, sealed wood, laminates,
composites, and the like. Non-limiting examples of porous surfaces include fibers, textiles, non-
wovens, woven materials, foam substrates, cloth, clothing, leather, upholstery, carpet, curtains,
marble, granite, grout, mortar, concrete, spackling, plaster, adobe, stucco, brick, unglazed tile,
tile, unglazed porcelain, porcelain, clay, wallpaper, cardboard, paper, wood, and the like.
[0090] Examples of suitable surfaces and articles found in and around a home dwelling include,
but are not limited to: ceilings, walls, wallpaper, floors, counter tops, sinks, backsplashes,
cabinets, wood paneling, laminates, stone, granite, marble, limestone, tile, porcelain, plastics,


polymers, coated materials, caulking, grout, spackling, shower walls, shower enclosures, shower
curtains including cloth, plastic and laminated, toilets, bidets, and the like. Suitable articles and
materials that may be treated according to the present invention further include carpet, furniture,
drapes, curtains, blinds, vinyl blinds, pull-shades, rugs, upholstered items, and the like.
[0091] Surfaces and materials exterior to the home on which the present invention may be used
include exterior walls, trim, doors, gutters, windows, screens and window coverings, and the
like. Materials of construction suitable for treatment include wood, painted surfaces, metal
surfaces, vinyl, receptive glass, polymeric substrates, including plastic materials, and porous
materials such as adobe, clay, concrete, stone, brick, mortar, stucco, siding, and the like that are
located in an exterior environment.
Polymeric Substrates
[0092] Articles treated according to the inventive methods and compositions as described herein
may be selected from those articles of construction comprising polymeric substrates that
normally exhibit hydrophobic surface properties in that they exhibit the tendency to collect dirt
and/or bead water when water is applied to their untreated surfaces. Articles include those
wholly constructed of, laminated with, and/or coated with a polymeric substrate, film, or coating.
[0093] Polymeric substrates include condensed polymers which are rendered into materials of
construction having at least one treatable or receptive surface. These polymeric substrates can be
in any physical form, for example, but are not limited to: panels, molded forms, foams, sheets,
solid surfaces, laminated films and coatings on a secondary substrate, and the like. The
polymeric substrates may have any desired physical properties, for example, but not limited to:
forms that are substantially elastic, non-elastic, flexible, compressible, or essentially rigid, and
combinations thereof.
[0094] Suitable articles of the present invention include those constructs and articles of


construction typically found in and around the home and commercial environments featuring at
least one treatable surface comprising a hydrophobic polymeric substrate, including for example,
but are not limited to: plastics, elastomers and laminates used in the construction of floors, tiles,
panels, walls, doors, ceilings, bathtubs, shower stalls, sinks, cabinets, countertops, fixtures, and
the like.
[0095] Suitable polymeric substrates and articles constructed thereof, include, but are not limited
to: polyethylene terephthalate, polyamide, polyurethane, polyester, polyethylene, polyvinyl
chloride (PVC), chlorinated polyvinylidene chloride, polyacrylamide, polystyrene,
polypropylene, polycarbonate, polyaryletherketone, poly(cyclohexylene dimethylene
cyclohexanedicarboxylate), poly(cyclohexylene dimethylene terephthalate), poly(cyclohexylene
dimethylene terephthalate) glycol, polyetherimide, polyethersulfone, poly(ethylene terephthalate)
glycol, polyketone, poly(oxymethylene), polyformaldehyde, poly(phenylene ether),
poly(phenylene sulfide), poly(phenylene sulfone), polystyrene, polysulfone,
polytetrafluoroethylene, polyurethane, poly(vinylidene fluoride), polyamide, polyamide
thermoplastic elastomer, polybutylene, polybutylene terephthalate, polypropylene terephthalate,
polyethylene naphthalate, polyhydroxyalkanoate, polyacrylate, poly(methyl)methacrylate
(PMMA), polytrimethylene terephthalate, polyvinylidene chloride and combinations thereof.
[0096] Suitable polymeric substrates and articles constructed thereof further include copolymeric
materials made of one or more monomers selected from acrylate, acrylonitrile, butadiene,
ethylene, formaldehyde, maleic anhydride, melamine, methacrylate, methyl methacrylate,
phenol, propylene, styrene, urethane, and vinyl acetate. Specific examples of these copolymeric
materials (and their common industrial acronyms) include acrylonitrile:butadiene:styrene (ABS),
acrylonitrile:styrene:acrylate (ASA), ethylene propylene (E/P), ethylene: vinyl acetate (EVAC),
methyl methacrylate:acrylonitrile:butadiene:styrene (MABS), methacrylate:butadiene:styrene
(MBS), melamine:formaldehyde (MF), melamine:phenol:formaldehyde (MPF),


phenol:formaldehyde (PF), styrene:butadiene (SB), styrene:maleic anhydride (SMAH),
styrene:acrylonitrile (SAN), styrene:butadiene (SBC), vinyl acetate ethylene copolymer (VAE),
and combinations thereof.
[0097] Also suitable are polymeric substrates and articles constructed of thermoplastic
elastomers including, but not limited to, copolyester thermoplastic elastomer (TPC), olefinic
thermoplastic elastomer (TPO), styrenic thermoplastic elastomer (TPS), urethane thermoplastic
elastomer (TPU), thermoplastic rubber vulcanisate (TPV), neoprene, vinyl, silicone elastomer,
and combinations thereof.
Methods of Use
[0098] Treatment compositions of the present invention are generally applied in a manner so as
to deposit fine droplets of the liquid composition comprising the colloidally dispersed
hydrophobically modified fumed silica particles in a volatile solvent as a continuous coating
upon a receptive surface such that the droplets completely cover the surface to effectively merge
to form a thin continuous liquid film upon initial deposition. This first manner of application is
generally preferred for a single treatment application. Alternatively, the liquid treatment
compositions can be applied in a manner to uniformly coat the area of the surface to a nearly
complete extent as an array of fine droplets arranged in high density, but finely separated so as
not to form a continuous liquid film. In this latter method of application, depending on the
degree of surface protection desired, a single application, or multiple repeated applications of the
inventive treatment compositions can be applied to produce the desired level of surface coverage.
[0099] Following this application step of applying the liquid treatment composition to the
surface, the volatile solvent is left to evaporate in the second step of the process, effectively
leaving a deposited film of particles in the form of silica particle agglomerates than is essentially


transparent. The evaporation of the volatile solvent results in a thin, macroscopically uniform
and essentially transparent film on the receptive surface that is detachable and renewable, and
exhibits excellent dirt-repellency, and also water-repellency owing to high water contact angles
sufficient to effect beading water incident on the surface so that the deposited film exhibits
provides soil- and water-repellency, and the ability of the soiled surface to be self-cleaning, and
readily cleanable with only the application of water.
[00100] Without being bound by theory, it is believed that the evaporation of the volatile
solvent of the present invention provides for some relative ordering and separation of the
particles across the area of the treated surface following application, without significant
clumping or association between the particles and/or agglomerates, which likely results in a
mono-layer of deposited particles having favorable optical properties owing to the absence of
significant scattering centers due to otherwise unfavorable clustering of agglomerates. Thus,
treatment compositions of the present invention tend to form essentially transparent films on the
treated surfaces that are nearly invisible to the human eye, even when applied to particularly
glossy or highly reflective surfaces where surface defects or other coatings in the art are readily
discemable. Without being bound by theory, it is further believed that the volatile solvent serves
to effect reversible attachment of the particles to the receptive surfaces by weaker, non-covalent
binding forces by enabling the particles during the evaporation step to settle onto the surfaces in
their lowest energetically favorable binding states with maximum surface contact. Owing to the
extremely small particle sizes, and the ability of the particle agglomerates to adopt the most
favorable positions during solvent evaporation, binding forces owing to hydrophobic-
hydrophobic interactions and van der Waals forces are sufficient to enable the hydrophobically
modified silica particles to bind tightly enough to suitably receptive surfaces to effectively resist
displacement even under flowing water and/or air, yet be readily removed when desired by
moderate means.


[00101] Thus, the films produced by the treatment compositions and methods of the present
invention are detachable and may be readily removed by physical means, such as by abrasion,
rubbing or wiping using some appropriate physical tool or wiping article and/or by chemical
means, such as by use of a surface active agent, dispersant and/or solvent, or some suitable
combination of these to overcome the relatively weak binding energies of the particles and
displace them from the surface. It is noted that water alone under typical temperatures and
pressures, such as rain water, splashed water and a moderate water spray using a home garden
hose, and further, even water with significant soil load and contaminants present, is not effective
in displacing the films of the present invention, thus enabling them to act as detachable but
durable protective coatings on receptive substrates that favorably repel dirt, and owing to their
hydrophobic nature and high water contact angles are water-repellent and capable of being
cleaned of any adhering soil or dirt using water alone. The treated surfaces also exhibit a
surprising ability to repel and resist the adhesion of dry soils and particulate matter, such as
brake-dust and household dust, and the surfaces bearing the protective films according to the
present invention can be cleaned using a gentle stream of air alone, or if a vertical surface the use
of a gentle tapping, shaking or slight percussive motion to displace particulate soils. Thus,
receptive materials treated according to the methods and treatment compositions of the present
invention exhibit dirt-repellency, are self-cleaning, and their favorable repellency properties
provide easy cleaning using water alone. Further, treated materials exhibit easier cleaning and
easier next-time cleaning in that non-removable and/or excessive soil load that may adhere to the
film are prevented from associating with the underlying surface, and thus are more readily
removed from the surface during a cleaning step employing a cleaning agent, such as a surfactant
solution, owing to the films being detachable in nature and thus acting as a removable sacrificial
barrier in protecting the treated surface from soil adhesion and build-up, while still providing
self-cleaning characteristics to the surface. Surfaces thus cleaned to remove a previously applied
protective film, may then be reprotected by a fresh application of the present inventive treatment


compositions to restore the self-cleaning and easier next time cleaning benefits. Thus, the
surface treatment and resulting protective benefit is infinitely renewable in that the surface may
subsequently be retreated periodically, or at any desired interval without any harm or degradation
of the original surface.
[00102] In addition, an inventive protective coating on a previously treated surface may be
renewed by repeated application of the inventive treatment compositions, without prior removal
of the protective coating, even if the coating is partially worn away or damaged. Generally, it is
desirable to remove a prior coating, particularly if the surface becomes damaged and/or
excessively soiled between treatments, but this is not a requirement. Without being bound by
theory, it is believed that reapplication of the inventive treatment compositions to a previously
treated surface, owing to the reintroduction of the solvent carrier and an additional fresh aliquot
of the hydrophobic silica agglomerates, results in sufficient resuspension and redistribution of
the inventive materials across the surface in a manner that essentially renews the protective
coating while preventing excessive build-up that would otherwise diminish the superior optical
properties exhibited by the inventive treatment compositions.
Application Means
[00103] Application of the inventive treatment compositions to a receptive surface may be
achieved by use of an application device employing any suitable means known in the art capable
of producing a fine distribution of fine liquid droplets and directing them to the surface to be
treated. The application device can be an aerosol or non-aerosol device. Treatment
compositions can be sprayed using any suitable type of sprayer. One suitable type of sprayer is
an aerosol pressurized package using a propellant. If an aerosol sprayer is used, it can use any
suitable type of propellant. The propellant can include hydrocarbon propellants, or non-


hydrocarbon propellants. A non-hydrocarbon propellant may include, but is not limited to: a
compressed and/or liquefiable gas. Suitable compressed gases include, but are not limited to:
compressed air, nitrogen, inert gases, carbon dioxide, etc., and suitable liquefiable volatile
materials include, but are not limited to: propane, butane, pentane, and materials selected from
hydrocarbons, fluorocarbons, perfluorocarbons, chlorofluorocarbons, and mixtures thereof.
[00104] In one embodiment, a pressurized aerosol package is employed, using the liquid
treatment compositions of the present invention, optionally pressurized by use of a suitable
pressurized gas, compressible liquid and/or liquid propellant, and/or gaseous propellant or
combination thereof, in combination with a dispensing valve capable of suitably dispensing the
liquid treatment composition in the form of a plurality of fine droplets.
[00105] Suitable aerosol delivery includes the Truspray® system (available from Boehringer
Ingelheim-Steag microParts, Dortmund, Germany) which employs capillary atomization
technology to deliver fine atomization with reduced propellant and solvent levels, enabling more
concentrated colloidal dispersions and/or thickened treatment compositions according to the
present invention to be suitably dispensed.
[00106] Also suitable are application devices and/or dispensing devices not requiring the use of
a pressurization means and/or propellant means.
[00107] One suitable example disclosed in U.S. Pat. 6,708,852 describes a mechanically
pressurized dispensing system that offers an alternative to chemically pressurized aerosol
dispensers. The system is fitted over a standard container holding a liquid product, and includes
a dip tube assembly to draw liquid into the dispensing head assembly, where the contents are
released through the dispensing head assembly, via the nozzle and valve. A twist of the threaded
cap raises a piston, thereby opening a charging chamber within the dispensing head assembly.
This creates a vacuum with the resulting suction pulling the product up through the dip tube to


fill the charging chamber. Twisting the cap in the opposite direction lowers the piston in a down
stroke, which closes the charging chamber, forcing the product into the expandable elastic
reservoir where it is then discharged through the nozzle.
[00108] Also suitable are applicator devices in which the container encloses the liquid treatment
composition present in a separate pouch, either foiled or foil-less bag, that is surrounded by
propellant within the container and surrounding the inner sealed pouch. Examples include those
disclosed in U.S. Pat. 6,196,275, U.S. Pat. 4,308,973, and U.S. Pat. 5,730,326 describing a
rechargeable container. U.S. Pat. App. 2003/0102328 describes an aerosol container lacking a
return spring and product dip tube. For some applications, a dip tube may still be appropriate.
The valve may have multiple product delivery openings. The container may use a propellant
driven piston to dispense the product or the product may be in a collapsible, flexible bag.
[00109] U. S. Pat. 5,111,971 describes a pressurized liner-sleeve assembly that can be fitted
with an aerosol valve, and requires no propellant.
[00110] Elimination of the chemical propellant can reduce or eliminate volatile organic content
(VOC) to allow compliance with various state and federal regulations designed to reduce green-
house gas emissions. Alternatives to chemically pressurized dispensers include various
mechanically pressurized models that obtain prolonged spray time by storing a charge without
the use of chemical propellants. Such "stored charge" dispensers include types that are
mechanically pressurized at the point of assembly, as well as types that may be mechanically
pressurized by an operator at the time of use. Stored charge dispensers that are pressurized at the
point of assembly often include a bladder that is pumped up with product. Examples include
those described in U.S. Pat. 4,387,833 and 4,423,829.
[00111] Stored charge dispensers that are pressurized by an operator at the time of use typically
include charging chambers that are charged by way of screw threads, cams, levers, ratchets,


gears, and other constructions providing a mechanical advantage for pressurizing a product
contained within a chamber. This type of dispenser is generally be referred to as a "charging
chamber dispenser." Many ingenious charging dispensers have been produced. Examples
include those described in U.S. Pat. 4,872,595, U.S. Pat. 4,222,500, U.S. Pat. 4,174,052, U.S.
Pat. 4,167,941, and U.S. Pat. 5,183,185, which are expressly incorporated by reference herein.
[00112] U.S. Pat. App. 2005/0035213 describes an ultrasonic spray coating system comprising
an ultrasonic transducer with spray forming head, integrated fluid delivery device with air and
liquid supply passage ways, support brackets and an ultrasonic power generator. The ultrasonic
transducer consists of an ultrasonic converter that converts high frequency electrical energy into
high frequency mechanical energy. The converter has a resonant frequency. A spray forming
head is coupled to the converter and is resonant at the same resonant frequency of the converter.
The spray forming head has a spray-forming tip and concentrates the vibrations of the converter
at the spray-forming tip. The separate passage ways for air and the liquid supply allows the
treatment compositions to remain separated from potential contaminants until used. The
ultrasonic transducer can produce a fine mist or a spray as the transducer is adjusted. Additional
ultrasonic spray devices are described in U.S. Pat. App. 2004/0256482 and U.S. Pat. 6,651,650,
which describes an ultrasonic atomizer for pumping up a liquid from a liquid vessel by an
ultrasonic pump and atomizing the liquid by passing it through a mesh plate formed to have
multiplicity of minute holes. The device can be controlled for automatic, manual, or intermittent
operation.
[00113] Another non-limiting example is the TrueSpray™ (TTP Group, The Technology
Partnership) and TouchSpray™ (ODEM affiliates of TTP, Bespak PLC and PARI GmbH,
Germany) atomization devices which both employ a microdroplet generating system based on a
perforated membrane that is vibrated at selected frequencies to convert a continuous flow of an
atomizable liquid composition on one side of the membrane into a fine spray of liquid droplets


emanating from the opposite side. The system employs an electrical means using either a battery
or other electronic power supply and a circuit to control the vibrational frequencies, amplitudes
and duration of membrane oscillation in order to control liquid flow and dispensing rates as well
as droplet size, distribution, velocity and atomization rate. A favorable property of this
application means is the tendency of the system to produce smaller liquid droplet sizes on the
order of 10 to 100 microns in diameter, with a majority of the liquid droplets of a size within
several standard deviations of the mean liquid droplet size, thus producing a homogeneous
distribution of fine liquid droplets of uniform size, which would be capable of forming a more
uniform surface film of applied material when used to deposit the inventive treatment
compositions onto a receptive surface.
[00114] Also suitable are electrostatic applicators, which may be employed as a delivery means
that combines any suitable atomization means with a dispenser capable of imparting a unipolar
charge on the dispensed liquid droplets, which may be selected to be net positive or net negative
depending on the conditions desired and target substrate. Imparting a unipolar charge to the
dispensed droplets acts to disperse them during atomization, as the like-charged droplets tend to
repel one another so that coherence of the spray pattern of the plurality of droplets is maintained
while the droplets are in flight. The unipolar charge, suitably selected, may also act to
accelerate, attract and/or adhere the charged droplets onto either a neutral, polarizable or
oppositely charged surface to effectively increase deposition efficiency and further decrease
overspray and droplet bounce from the target surface, as well as producing more uniform films
on the surface.
Treatment Kits
[00115] The inventive treatment compositions, suitably packaged in a dispensing and/or
applicator means for direct application to a receptive surface, may be combined in the form of a
treatment kit. The treatment kit may further contain instructions for use of the inventive


treatment compositions, including a list of suitable surfaces and substrates that may be treated,
application techniques and application instructions illustrating use of and most suitable means of
applying the compositions to surfaces, pre-cleaning instructions, drying instructions, and post-
treatment cleaning instructions, and the like.
[00116] Generally, it is desirable to treat a surface that has been previously cleaned so as to
form a first protective coating on a cleaned receptive surface. This is typically done for most
surfaces by washing with a detergent, hard surface cleaner, soap or some similar cleaning agent
followed by either rinsing with water and allowing to dry, or wiping dry directly, or wiping dry
after rinsing with water. Generally, it is desirable to remove all trace residue of water, cleaning
agent and other adherent materials before treatment. The inventive treatment compositions may
be applied to damp or slightly wetted surfaces, but generally a substantially dry surface, such as
one free of adherent water droplets, to which the inventive treatment compositions are applied
provides for the most appealing aesthetic surface treatment. Thus, treatment kits according to the
present invention may optionally include a drying article, such as for example, but not limited to:
an absorbent material, a drying aid, and/or combinations thereof. Examples of suitable absorbent
materials that may be used as a drying article include, but are not limited to: a woven, non-
woven, sponge, polymeric foam, microfiber, paper towel, paper pad, tissue or other similar
absorbent article or wiping article capable of effectively absorbing and/or removing water from a
wetted surface prior to application of the inventive treatment compositions. Other alternative
drying articles include drying aids. Examples of suitable drying aids include for example, but
are not limited to: a compressed gas source, infrared heat generating device, forced air device,
such as a powered fan, combinations thereof, and the like.
Preparation of Treatment Compositions
[00117] Treatment compositions according to the present invention may be prepared by a
variety of methods well known in the art depending on the quantity and scale desired. For the


purpose of consistency in preparing small batches for testing and evaluation, inventive treatment
compositions were prepared using process compositions, i. e., concentrated hydrophobically
modified fumed silica dispersions as indicated, produced according to the inventive process
described herein, and then further processed in the following manner described below suitable
for obtaining quantities of 100 to 5,000 grams of a finished or ready-to-use treatment
composition. First, a major aliquot, or total desired level of the volatile solvent is weighed into
a plastic vessel, optionally with a remaining minor aliquot of the volatile solvent retained in
order to later rinse the walls of the mixing vessel, if desired. Stirring is then begun using a
conventional motorized mixer using a mechanical stirring rod of suitable size, operated at a
speed of about 300 to 400 r.p.m. sufficient to create a smooth vortex without splashing of the
volatile solvent. Addition of the optional dispersing agent, and/or addition of the optional
durability agent, if any, is performed by slowly adding each separately in turn and mixing
sufficiently to achieve a uniform solution and/or suspension of the agents in the volatile solvent,
generally following about 5 to 10 minutes mixing duration. The process composition is then
added slowly to the solution, and after complete addition, any remaining aliquot of the volatile
solvent added in such a manner as to rinse any adhering particles on the mechanical stirring rod
and/or sides of the mixing vessel into the bulk liquid. The mixing speed is generally maintained
at 400 r.p.m., but may optionally be increased to about 1000 r.p.m., if desired, and stirring
continued for a time sufficient to produce a homogeneous dispersion of the particles, which can
be as short as a minute or so, or longer if additional materials are to be added. Alternatively, the
optional dispersing agent, and/or optional durability agent may be added at this stage of the
mixing to produce a final treatment composition.
[00118] This approach produces suitable treatment compositions of colloidal dispersions of the
hydrophobically modified fumed silica particles according to the present invention in a volatile
solvent, which may then be combined with a suitable applications means to provide for suitable
dispensing onto a target surface. In one embodiment, for example, the treatment compositions


may be packaged into a suitable aerosol container (i.e., a conventional pressurized spray can with
pin hole nozzle) as an application means combined in the form of a treatment kit, and optionally
combined with a propellant or compressible gas to provide for suitable dispensing by
atomization.
[00119] In another embodiment, treatment compositions may be processed further with addition
of, and/or dilution with additional volatile solvent, and/or additional optional suspending
agent(s), and/or additional optional functional adjuncts, and/or optional propellant prior to
packaging or use. In yet another alternative embodiment, the colloidal dispersion of the
hydrophobically modified fumed silica particles may be packaged or associated with a non-
aerosol applicator for dispensing by suitable means not requiring direct pressurization and/or use
of a propellant.
[00120] For testing purposes, treatment compositions prepared from the process compositions
described herein comprising dispersions of the hydrophobically modified fumed silica particles
in the volatile solvent were applied using the PreVal™ system commercially available from
Precision Valve (New York, NY).
Preparation of Samples for Particle Size Analysis
[00121] Particle size analysis of the hydrophobically modified fumed silica particles was
performed following application to a treated surface by use of scanning electron microscopy
(SEM) to image and evaluate particle size, distribution and coverage of the particles present in-
situ on the surface. Representative substrates were tested, including plastic and metal surfaces,
by employing flat plastic and aluminum test panels, respectively, of approximately 1" x 1" size
that are carefully cleaned with anhydrous isopropanol and dried prior to use. Coated test panels
are prepared by first covering one-half of the panel (approximately ½" x 1" portion) with heavy
stock paper or suitable barrier that will not wet through or overspray during application of test


formulations, which are then sprayed manually in essentially the same manner as used in
applying a spray paint to a surface, by evenly spraying the treatment compositions onto the test
panel surface using a smooth uninterrupted linear motion during spraying, with the nozzle
located approximately 6" from the surface, with the spraying action commencing a short time
prior to reaching the one edge of the test panel and continuing for a short time after passing the
second edge of the test panel in order to produce a uniform coating. The treated panel is allowed
to dry with the partial cover paper attached, and then mounted onto a carrier sheet, e.g. a thicker
piece of paper stock by using double sticky tape, and the sample stored under a dust cover prior
to imaging to preserve the treated surface.
[00122] The surface morphology of the test panels coated with the inventive treatment
compositions were examined using a Hitachi S-4300SE SEM (Hitachi USA) operated at an
accelerating voltage of 2 kilovolts (KV). The test panels were dried at room temperature and no
additional coating was performed prior to the examination.
[00123] Results of the SEM imaging are shown in the accompanying Figs. 1 and 2. In Fig. 1, a
black test panel was treated with a conventional Lotus effect coating formulation prepared
according to the methods described in U.S. Pat. Pub. No. 2004/0213904, corresponding to
Comparative Example 21 as referenced herein. By eye, the panel treated by the comparative
material appeared visually hazy and the SEM image shows a generally uneven (non-
homogenous) surface covered by small particles presumed to be larger silica agglomerates and/or
clumps of agglomerated material. In Fig. 2, a black test panel was treated with the inventive
treatment composition (Example 15) employing means of application according to the methods
of the present invention, but otherwise prepared, treated and evaluated in an identical manner as
the first test panel. By eye, the panel was extremely glossy and reflective, no noticeable film or
haziness being apparent on the surface under normal lighting conditions. The SEM image in Fig.
2 reveals an extremely smooth and uniform film of particulate materials on the surface of the


panel, evidence of a very isotropic and homogeneous surface morphology. The scale of both
SEM images is about 200 µm, corresponding to an effective magnification of about 250x.
Atomic Force Microscopy
[00124] Atomic force microscopy (AFM) was used to determine the extent and nature of the
renewable surface modification effects according to the materials, treatment compositions and
methods of application of the present invention. The AFM technique allows virtual imaging of
the surface at a scale fairly comparable to that of the applied deposited materials so that surface
topography can be ascertained to a high degree of precision. AFM images were obtained using a
Digital Instruments Nanoscope III in non-contact mode with Olympus Tapping Etched Silicon
Problem Aluminum-coated (OTESPA) sensing tips. Images were acquired from the center of
each one inch square segment of panel. Although phase data was simultaneously acquired, no
significant phase difference in the topography were detected, so images were generated without
including this factor. Photomicrographs of the AFM data generated images are presented herein
with appropriate vertical height scales indicated by the relative intensity of the image at the
indicated coordinates, scaled from black (0) to white (1) on a relative basis with respect to the
relative vertical height range indicated in the key insert accompanying the photomicrograph, and
the horizontal length scale length is indicated on the borders in units of micrometers (µm). Fig. 3
shows typical topographical images obtained on a treated black paint panel after treatment with a
treatment composition applied according to the present invention, compared to Fig. 4 of an
untreated black paint panel.
Preparation of Coated Paint Panels
[00125] Treatment compositions of the present invention were applied to a variety of surfaces
for testing and evaluation, using representative materials selected for convenience of testing
under controlled conditions including a clear coated black painted metal rectangular test panel


obtained from ACT Laboratories Co., Hillsdale, Michigan, designated APR41841, Batch
50505412, having an exceptionally high gloss surface owing to clear-coating finish R10CG060Z
UreClear. Test panels were first thoroughly cleaned with isopropyl alcohol (IPA), washed with a
soap and water solution, and finally rinsed with IP A, rinsed with de-ionized water, wiped dry
with a dry lint-free paper towel. Visual inspection of each panel was performed to insure
cleanliness and panels were handled by the edges to prevent fingerprints from marring the
surface. Selected portions of the panel were masked to produce control and treatment areas, the
middle roughly 1/3 area section being masked by use of a folded paper covering the center of the
test panel or temporary barrier when sprayed to prevent overspray. Samples were placed in a
holder so that they could be sprayed while in a vertical orientation. After masking, the exposed
right and left side sections were treated by spraying test formulas using the PreVal™ sprayer
system, held about 8 to 10 inches above the panel surface with spraying times of about 3
seconds, in a consistent overlapping spray pattern with motion from top to bottom of the panel,
repeated consistently for every panel in the set, which usually included three sets of panels and
four replicates per set per treatment composition under evaluation. Following spraying, test
panels are either dried at 80°C for 15 minutes (accelerated drying), followed by at least 5 minutes
of cooling time, or allowed to dry at room temperature or about 70°F overnight or until dry by
appearance (typically 5-30 minutes depending on the surface and up to one to two hours for
heavy applications on some non-porous surfaces).
[00126] The first set of panels was used for evaluation of hydrophobic surface modification
with respect to water repellency ("Roll Off Test"), appearance evaluation with a haze meter
instrument ("Chrome Test"), and gloss-meter instrument, and durability testing under repeated
water rinse conditions ("Durability Test"). The second set of panels were used to evaluate self-
cleaning soil repellency characteristics measured both qualitatively by visual rankings using
trained evaluators and/or quantitatively using a combined gloss-meter and colorimeter
instrument.


Roll Off Test
[00127] To measure the ability of treated surfaces to repel water, contact angle measurements
and visual evaluation of the behavior of a water droplet was performed. A single drop of tap
water (roughly 0.05 mL) was applied to the test panel surface held in a horizontal position.
Contact angles were measured using an N.R.L. Model C.A. 100-00 goniometer (Rame-Hart,
Mountain Lake, NJ).
[00128] Surface behavior of the water droplet was observed while the panel was moved and
rocked gently while held by hand in a generally horizontal position, and a rating score assigned
to the treated panel based on the behavior of the water droplet as described below:
Rating Description of Visual Behavior
1 "Marble on a surface" - water droplet rolls easily
2 Rolls easily, but sticks occasionally
3 Rolls freely but sticks some times
4 Rolls freely but sticks more often
5 Remains mostly in place with hardly any movement
6 Water droplet remains fixed in place (untreated surface)
Roll Off Height Test
[00129] In addition to visually assessing roll off behavior, a "roll off height" measurement was
performed to determine the height of inclination required for water to roll off from a panel
following a surface treatment to be evaluated. Panels were prepared using the same approach as
described in the preceding Roll Off Test herein.
[00130] Panels to be evaluated are then placed on a flat or elevated flat surface in a horizontal


position, with one side of the panel, and if rectangular in shape this being one of the short sides
of the rectangular panel, placed in close proximity to a vertically positioned scaled ruler placed
perpendicular to the flat or elevated surface such that the height of the selected edge as it is
displaced from the horizontal position can be readily measured by comparing the edge to the
markings on the scale.
[00131] With the panel in the initial horizontal position, from about three to five independent
drops of water (about 0.1 mL each) are gently pipetted onto the panel in an approximately
straight line located approximately parallel to the selected edge and located approximately 1 inch
from the selected edge. The panel is then lifted so as to elevate the selected edge of the panel in
an upward vertical direction slowly and smoothly to prevent any undesirable motions, until all of
the water droplets "break free of the surface" and/or begin to move or roll down the inclined
surface of the panel. The height at which the drop begins to roll off is obtained from the scale,
being the "Roll Off Height", and generally expressed in centimeters (cm).
[00132] Any residual liquid (spotting or trailing) after the drops have rolled off is noted.
Additional replicates or measurements of the Roll Off Height are obtained by rotating the test
panel 180° and repeating the test again.
Chrome Test
[00133] All appearance measurements under identical conditions were taken either before and
after treatment, or taken from treated and untreated (masked) sections of the test panel, with the
difference between these measurements calculated to determine changes as a result of the
treatment or soiling test employed. Colorimetric, gloss and haze measuring instrumentation and
techniques can be employed to demonstrate the surprisingly transparent nature of the surface
protective films and coatings formed onto receptive surfaces by means of employing the
inventive treatment compositions.


[00134] Colorimeter measurements were performed using a Minolta spectrophotometer, Model
CM-508D, Serial No. 15711032, with an illuminating/viewing geometry selected to compensate
for specular reflection, SCE (specular component excluded), obtained from Konica Minolta
Photo Imaging Inc. Instruments Systems Division, Mahwah, NJ.
[00135] Measurements before and after treatment or soiling were taken as described above,
although tests can be done in different order to enable sequential testing against the various test
methods for convenience. All measurements are generally replicates of duplicate or additional
trials that are then averaged, differences before and after treatment being reported at Delta E,
which is the total color difference between the sample and a reference sample, or alternatively
the initial untreated and final post-treated sample after treatment was applied. To determine the
major contribution to the Delta E value, Delta L and the colorimetric "a" and "b" parameters
were examined and Delta L was found to best represent, and be most sensitive to changes in the
visually appearance of treated materials, likely owing to the colorimetric "L" parameter being the
parameter that tracks total neutral shade values from pure black (L=0) to pure white (L=100) in
the absence of any color contributions. Similar measurements were also employed to measure
the relative influence on Delta E and Delta L following application and removal of soil to
provide an approach to measuring comparative soil removal. Visual evaluation of the surfaces
held at a reflective angle to a light source (a suitable example being normal overhead fluorescent
room lighting, incandescent lamp and outdoor sunlight) was also performed to judge aesthetic
characteristics of treated surfaces, in particular appearance associated with common visual
descriptors including: "uneven" and/or "streaky", "hazy", cloudy" and/or "dull", "pearlescent"
and/or "rainbow effect", and "clear" and/or "glossy". Here, both "pearlescent" and "rainbow
effect" refer to the tendency of thin transparent films, depending on their thickness, regularity of
thickness and the substrate to which applied, produce interference and diffraction effects upon
reflection of incident white light which are perceived as a plurality of colored patterns and
colored bands, respectively.


[00136] Haze measurements were performed using a Haze Gloss Meter, Model No. 4606,
available form BYK Gardner, Silver Spring, MD, U.S.A calibrated with a haze-gloss standard
reference No. 195829312 providing a haze set point value corresponding to H'(20°) = 463. Haze
Unit measurements obtained were uncompensated (indicated as "nc") values determined after
calibration. Delta Haze Units corresponded to the difference in measured Haze obtained by
subtraction of haze values obtained before and after treatment of a chromed panel, or between an
untreated control panel and a treated panel, or between an untreated and treated portion of the
same panel, as indicated. Generally, Delta Haze Unit measurements using the same panel before
and after treatment and other test procedures as described herein are preferred for improved
accuracy, with a multiple number of replicate readings taken across the surface to enable an
average value to be calculated.
[00137] Delta Haze Unit measurements were made on the treated surfaces to correlate the level
of haze associated with the typical ability of the human eye to discern noticeably perceptible
visual change in the surface appearance of treated substrates viewed under normal room lighting.
A highly polished mirror finished reflective chromed test panel was selected as a preferred
surface for the purposes of testing and demonstrating the advantageous optical properties of
surface protective films provided by use of the instant treatment compositions, as the chrome
surface showed a high sensitivity to changes in surface appearance and measured haze
parameters. The chrome test panels, 4" x 8" in size are designated SAE-1010 CR with 1/8" hole
for suspension, Chrome Plated Steel, available from Metaspec, Inc., San Antonio, TX. Thus the
Chrome Test, conducted to provide a Delta Haze Unit measurement on treated chrome, provides
a convenient means of measuring the surprisingly improved transparent protective films
produced by the inventive treatment compositions.
[00138] Generally, the inventive treatment compositions when applied to the polished chrome
test panels produced transparent and nearly invisible surface coatings that demonstrated the


beneficial protective properties as described herein. Haze measurements confirmed that Delta
Haze Unit values of below around 250 as measured according to the Chrome Test methodologies
described hereinabove are readily achievable by use of the inventive compositions, these Delta
Haze Unit values corresponding to a change in the measured haze value wherein the level of
haze produced on the surface is barely, if at all perceptible to the human eye.
Substantivity and Durability Test
[00139] Substantivity testing was also performed to determine the ability of the treated surfaces
to maintain their beneficial properties following treatment, and the durability of the beneficial
properties following challenge by soils, dirt, water, mechanical abrasion and action of cleaning
solutions. These substantivity and durability tests provide a measure of the inventive treatment
compositions utility for treated interior and exterior surfaces, and materials likely to be exposed
to a variety of typical environmental challenges.
[00140] Panels previously used for the Roll Off Test may be employed, or newly prepared
panels, placed and held in an approximately vertical position. For substantivity testing, panels
are sprayed over an approximately 3" x 6" area, using an electrosprayer charged with regular tap
water (Febreze Power Sprayer, carefully cleaned and rinsed with water before use, distributed by
the Procter and Gamble Company, Cincinnati, Ohio) for 15 seconds of continuous spray,
measured using a timer.
[00141] Following spraying, the surface of the panel is visually evaluated to determine the
tendency of any water drops to remain on the surface, which would be indicative of a loss of the
protective benefit, compared to an untreated control panel. The number of drops and surface
appearance of the panels following the rinsing are collectively assigned a visual substantivity
grading score being an integer from 0 to 10, using the following scale as guidance, with
intermediate assignments possible:

Rating Description of Visual Behavior ( Water Adhesion)
10 No observed water droplets
7 Small number of water droplets
5 Some water droplets
3 Numerous water droplets
1 Appearance similar to untreated control
0 Appearance worse than untreated control
Durability Test
[00142] Durability testing is performed in a similar manner as the substantivity test described
hereinabove, with the substantivity test procedure repeated a multiple number of times (cycles)
until a visual grading score of approximately 5 is observed, at which point the number of cycles
is recorded as the Durability Test Score. This Durability Test Score essentially represents the
number of water rinses over which the protective benefit may be observed, with a higher number
of cycles representing both increased substantivity (the effect) and persistence of effect
(duration) of the surface protective benefit at an acceptable level of performance (about 5 on the
substantivity visual grading scale). Durability Test Scores of at least 1 are suitable for sacrificial
surface protective coatings that will provide durability following at least one rinse event using
water to remove incidental soil, dirt and grime from a protected surface to which the inventive
treatment compositions are applied. Higher durability scores are more suitable for detachable,
yet more durable surface coatings that can provide multiple rinse cleaning cycles using water. A
Durability Duration value (in units of seconds) can also be calculated by multiplying the total
number of cycles determined according to the durability test (Durability Test Score) times the
individual spray time used (15 seconds per spray in the test method) to determine a Durability
Duration time for the inventive films present on a treated surface according to the methods
described herein.


Self Cleaning Test (Qualitative)
[00143] Self cleaning performance testing (designated "SCL Test") is done to determine the
ability of treated panels to be cleaned of adhering soil, dust, grime and the like following simple
mechanical tapping or rinsing by water alone (soil-repellency and self-cleaning performance, and
easier cleaning performance). Treated panels are first exposed to a soil laden environment, or
may be soiled artificially to mimic such exposure in the following manner: Treated panels and
control panels are positioned on a flat or inclined surface, depending on the surface to be
modeled or for worst case testing positioned in a horizontal orientation. Powdered soil of choice
is shaken onto the panels to produce a thin uniform coating, the panel is re-orientated into a
vertical position so that excess (non-adherent) soil will fall away. To simulate brake-dust as a
test soil, brake fines obtained from replacement brake pads as described below were combined to
obtain a dry free flowing finely powdered dust. The brake dust thus obtained was placed into a
large cheese shaker can with fine holes on the top, inverted and applied evenly across the test
panel surfaces by hand.
[00144] Brake-dust test soil was prepared by finely grinding down the top three purchased
brands of brake pads obtained from Grand Auto, a national retailer with branches throughout the
United States, corresponding to Honda Accord front new pads #45022-S84-A02, Honda Accord
rear new pads#43022-SY8-A01, VW Jetta front new pads #1SATZ 1-J0698 151 J, VW Jetta rear
new pads #1 SATZ 1J0698 451 D, Ford Taurus front new pads # 2F1Z-2001-AA, and Ford
Taurus rear new pads # F8DZ-2200-AA. All pads were individually ground down to a fine dust,
which was then sieved through a 325 mesh screen on a conventional Rotap™ machine to collect
only the fines below that mesh size. For an approximately 30 gram portion of finished brake-
dust test soil, about 3 grams each of the back brake pad fines and about 7 grams each of the front
brake pad fines (the front pads wearing faster during typical use) were combined to produce a
representative test soil that closely resembled that observed on actual vehicle wheels produced

during normal operation.
[00145] Once the soiled panel is prepared, it is rated using the description of visual behavior
scale presented herein below, and is then mounted in either an inclined or vertical position. In
dry soil resistance testing, the panel is lightly tapped once and the appearance evaluated to
determine dry soil repellency/resistance. In a wet soil resistance test, the panel is sprayed with
water in a manner as described above in the Substantivity Test Method, using tap water in the
electronic sprayer operated for about 15 seconds over the entire surface. For either test, a
duplicate replicate panel is treated in an identical manner and reserved as a control for
subsequent comparisons. After the test panels are treated, visual surface appearance of the
panels are assigned a Self Cleaning Performance score using the following scale as guidance,
either in reference to a treated but unsoiled panel (unsoiled control) that is rinsed according to the
procedure above, or in reference to an untreated but soiled panel. The visual scale employed is as
follows:
Rating Description of Visual Behavior (Dry or Water Rinse Test)
-3 most/all soil removed (resembles unsoiled control)
-1 slightly less soil sticks or remains
0 no change (untreated soiled panel control)
+1 slightly more soil remains
+3 most/all soil remains
Self Cleaning Test (Quantitative)
[00146] Quantitative measurements of the self-cleaning performance may be performed by
conducting haze test measurements on panels employed as described above in the "SCL Test"
procedure. Haze measurements of untreated panels, treated panels, tapped soil-treated panels
post testing, and soil-treated rinsed panels and rinsed treated panels are obtained by measuring

haze at 20° using a Haze-Gloss BYK Gardner Model 4606 instrument, and averaging four
readings per test panel or duplicate readings on at least three replicates panels.
Uniformity Appearance Rating (Qualitative)
[00147] A surface appearance uniformity ranking (designated "Chrome Test") are performed by
measuring treatments applied to a glossy and reflective surface such as a mirror or high gloss
chromed metal substrate. After treatment and drying times as described hereinabove, the highly
reflective substrates are view by eye and a qualitative visual score assigned based on general
appearance and uniformity of the surface over about a 3.5" x 4" size treatment area.
Rating Description of Visual Behavior
6 white haze - significant cloudy and/or dull appearance
5 some hazy appearance
4 uneven appearance and/or streaks observed
3 some distortion but mostly clear with high gloss appearance
2 slight distortion with overall clear and glossy appearance
1 no distortion or visual change (resembles untreated surface)
[00148] Ratings are assigned according to the above scale and closest appearance to the
description of visual behavior noted, using these actual textual descriptions for judges to consider
when viewing and rating the panels.
General Components of Inventive Process Compositions
[00149] Applicants have determined the shear rate dependent viscosity of the inventive process
compositions (at various ranges of silica content and disilazane) as well as prior art
compositions. From this study, it was apparent that the amount of disilazane had no influence on
the flow behavior in a concentration range between 0.5-3.0%. This supports the finding in Table
1 presented hereinbelow that the amount of disilazane has only a minor impact on the achieved

median particle size.
[00150] Applicants further note that increasing the amount of silica (5-15%) had a dramatic
impact on the viscosity. Doubling of the concentration from 5% to 10% raises the viscosity by
approximately one order of magnitude. Increasing the concentration to 15% silica, raises the
viscosity by an additional half an order magnitude.
[00151] Additionally, the general flow behavior is dramatically influenced by the amount of
silica. A particle load of 5% can be regarded as a very low concentration since the flow behavior
is that of an ideal (i.e., Newtonian) liquid. At a concentration of 15% silica, however, a
decreasing viscosity with increasing shear rate can be observed that increases again at high shear
rates (dilatant peak). These results support the finding in Table 1 presented hereinbelow that the
amount of silica has a dramatic impact on the achieved median particle size.
EXAMPLES
Process Compositions
[00152] Examples A through OO in Table 1 are representative embodiments of materials
prepared in the form of process compositions according to the processes of the present invention.
Example H is a comparative example prepared in a manner outside the scope of the present
invention.
Example A
[00153] A quantity of 10.0 g of hexamethyldisilazane (DYNASYLAN® HMDS) was dissolved
in 140 g of decamethylcyclopentasiloxane (TEGO® Polish Additiv 5, also designated as siloxane
"D 5"). 50.0 g of a commercially available, hydrophobized fumed silica with a BET surface area
of 220 m2/g (AEROSIL® R 812 S) was slowly dispersed in this solution with gentle stirring at

2,000 r.p.m. After all fumed silica had been added, the mixing speed of the Dispermat (single
rotating shaft, outfitted with saw-tooth blade proportional to mixing vessel where blade is half
the diameter of vessel) was increased to 10,000 r.p.m. and kept operating at this speed for 15
min.
Examples B-OO
[00154] Preparation of examples B through OO follows the same procedure as for example A
except using otherwise specified parameters as shown in Table 1 below.


1.10). This instrument measures the size and distribution of particles suspended in liquid
using laser diffraction.
(2) Examples F, G, H and 00 were unable to be processed at 10,000 r.p.m..
(3) Example H additionally contains 2 wt.% of TEGOPREN® 6814, an alkyl-modified
polydimethylsiloxane, as a durability agent and thus is a representative example of the
process compositions obtained by following the process disclosed in U.S. Pat. Pub. No.
2004/0213904A1.
[00155] Examples I through PP are examples of process compositions obtained by further
diluting some of the process compositions in Table 1 with TEGO® Polish Additiv 5.

[00156] By comparing Delta Haze values in Table 14 with particle sizes of the corresponding
process compositions, it can be concluded that a particle size of approximately 4,000 nm or less
is necessary to achieve Delta Haze values of 250 or less which was found to be the Haze value
from which on the coatings of the present invention start to be percieved as a visible film by the
human eye on a highly polished chrome test substrate according to the methods described
hereinabove. Table 1 shows that several parameters of different weighting play a role in order to
achieve a targeted particle size of 4000 nm or less. It can be concluded from Table 1 that the


concentration of silica (AEROSIL®) in the process compositions is by far the most important
factor and that a concentration of 10 wt.% seems to be a lower practical limit. With 5 wt.% for
example (Comparative example H) a more than tenfold larger median particle size is obtained. It
became also obvious that the viscosity of the process composition during mixing is critical and
needs to be in a defined range (see also chapter hereinabove on "General Components of
Inventive Process Compositions"). On the one hand, the process liquid needs to have a high
enough viscosity for adequate energy transmission throughout the bulk solution to produce the
requisite shear forces needed to effectively reduce particle size to the targeted median range. On
the other hand, the process liquid must not be too viscous in order to be still processable in the
mixing equipment.
[00157] It was surprisingly found that these counteracting effects during the process can be
balanced by the use of a disilazane derivative. The impact of hexamethyldisilazane, as one
representative embodiment according to the present invention, on the rheological behavior of
highly concentrated silica dispersions is shown in Fig. 5. Fig. 5 shows that a dispersion with 25
wt.% silica and without hexamethyldisilazane (Process Composition U) exhibits a yield point
indicated by G' > G", which means it shows a solid-like behavior, whereas a dispersion with 25
wt.% silica and with 5 wt.% hexamethyldisilazane (Process Composition R) does not have a
yield point. Process composition U demonstrates that it was basically possible to process a
dispersion of silica at 25 wt.% without a disilazane derivative, but much more effort was
required to get this amount of silica incorporated into the solvent, and the viscosity was too high
for proper processing. The disilazane derivative not only helps to keep the process viscosity at a
practical level for convenient processing, but also helps to wet and disperse the silica in the
solvent more easily. Besides the silica concentration, mixing process parameters such as stirrer
speed and mixing duration have a significant impact on the particle size results as well, even
though they are not as important as the silica concentration. Obviously it makes a big difference
whether a disilazane derivative is present or not with respect to ease of processing, but the

absolute amount present seems to be of lesser importance. In addition, it was observed that
samples processed with a disilazane derivative show a retarded settlement of silica particles
compared to those samples processed without the disilazane derivatives. In summary, it was
surprisingly found that the combination of high silica concentration with a sufficiently high
mixing speed or mixing power is critical to achieve the desired reduction to the desirable median
particle size range of the present invention, and that the presence of a disilazane derivative as a
processing aid facilitates the process dramatically.
[00158] The following examples O and P are further representative embodiments of materials
prepared in the form of process compositions according to the processes of the present invention.
Example O
[00159] A quantity of 5 kg of hexamethyldisilazane (DYNASYLAN® HMDS) was dissolved in
70 kg of decamethylcyclopentasiloxane (TEGO® Polish Additiv 5, D 5). 25 kg of a
commercially available, hydrophobized fumed silica with a BET surface area of 220m2/g
(AEROSIL® R 812 S) was added and passed repeatedly through a horizontal mill until the
desired particle size had been achieved.
[00160] Preparation of example P follows the same procedure as for example O except using
otherwise specified parameters as shown in Table 3 below.


(1) Particle size distribution analysis was performed with a Horiba LA 910 (use of 1.0
micron polystyrene dispersion as calibration standard, measurement of sample
dispersions diluted with isopropyl alcohol and with Relative Refractive Index =
1.10). This instrument measures the size and distribution of particles suspended in
liquid using laser diffraction.
[00161] Example Q is an example of a diluted process composition obtained by further diluting
process composition O with TEGO® Polish Additiv 5.

[00162] The following examples R through V are representative embodiments of process
compositions prepared according to the methods of the present invention. Preparation of
examples R through V follows the same procedure as for example A except otherwise specified
parameters in the table below. Examples A and R demonstrate the variance in the median
particle size achievable under identical process parameters.


(1) Particle size distribution analysis was performed with a Horiba LA 910 (use of 1.0 micron
polystyrene dispersion as calibration standard, measurement of sample dispersions diluted
with isopropyl alcohol and with Relative Refractive Index =
1.10). This instrument measures the size and distribution of particles suspended in liquid
using laser diffraction.
(2) It was extremely difficult to stir in the AEROSIL® into TEGO® Polish Additiv 5.
(3) In example V isododecane was used as solvent instead of decamethylcyclopentasiloxane.
Examples W through BB are examples of a diluted process composition obtained by further
diluting some process compositions in Table 5 with TEGO Polish Additiv 5.


[00163] Examples CC through HH are further representative embodiments of materials
prepared in the form of process compositions according to the processes of the present invention.
They were prepared following the same procedure as for example A.

[00164] Examples II through NN are examples of diluted process compositions obtained by
further diluting the process compositions in Table 7.


Treatment Compositions
Non-Porous Surface Modification
[00165] Examples of embodiments of the inventive treatment compositions suitable for use in
modification of receptive surfaces, including non-porous surfaces and substrates, are provided in
Table 9. The treatment compositions in these examples are prepared in the form of diluted silica
dispersions for use with a suitable delivery means capable of applying the treatment
compositions for surface modification of a variety of substrates and general usage on automotive,
home and textile surfaces.

[00166] Additional embodiments of examples of suitable inventive treatment compositions for
surface modification use are provided in Table 10, further including some optional functional
adjuncts to provide additional benefits to the treatment compositions and improved methods of
application onto targeted surfaces. Examples 9 and 10 are representative embodiments
formulated as ready-to-use propellant-based aerosol treatment compositions.


[00167] Further embodiments of the inventive treatment compositions prepared to determine the
dependence of properties of the protective coating on compositional variations were explored
using a design of experiments model to vary component levels of the functional and optional
ingredients as shown in Table 11. All treatment compositions were stable during spraying
application, and were applied using a PreVal sprayer.


[00168] Measurements of the example embodiments were conducted according to the test
procedures described hereinabove on high gloss black clear-coated automotive test panels, with
test data presented in Table 12, and on the high-gloss mirror chrome panels. Results show that a
clean, untreated black panel is fairly hydrophobic owing to the nature of the clear-coat finish and
exhibits a water droplet contact angle of about 79.6°. Spraying of the panels according to the
methods disclosed above with Example treatment compositions 2, 7, 11-14, 17, 18 and 22
provided treated test panels all exhibiting high water contact angles sufficient to repel water.
After application of the inventive treatment compositions 2, 7, 17, 18 and 22 to chrome panels,

treated sections of the panels were found to be nearly identical in appearance to untreated or
control sections of the panels previously masked prior to spray treatment to prevent deposition of
the inventive treatment compositions. A six person group visually evaluated the panels
(corresponding to treatment with treatment compositions 2, 7, 17, 18 and 22 according to the
"Chrome Test" appearance ranking and assigned scores on double-blind panel sections to
prevent bias, with averaged scores obtained presented in Table 12. Results show that treatment
according to methods of the present invention provided essentially clear surface coatings that did
not detract from observed shine of the panels, and which were not readily discernable to the
human eye, producing slight distortion or at worst some distortion while maintaining an overall
clear and glossy appearance.
[00169] The ability of the treated black panels to shed water was measured using the roll-off
height test, the height of the inclined panel from a flat horizontal position in centimeters at which
water drops begin to move as shown in Table 12. Results show a tendency for the untreated
panel, despite its moderate hydrophobic properties, to "pin" the water droplet in place, required a
fairly large tilt angle (here in excess of 45°) and Roll-Off Height greater than 20 cm for water
droplets to move. In contrast, the treated panels exhibited the ability to bead the water droplets,
and essentially enable the water droplets to be completely shed from the surface with only a
slight angle as the panels were inclined to a height of less than 1 cm to about 1.5 cm, which
corresponded to an angle of less than 10° inclination from the horizontal.
[00170] Colorimeter test measurement of the treated panels are also shown in Table 12 as the
component contributions Delta E and Delta L illustrating differences before and after treatment
with the inventive treatment compositions. Changes in the control panel measured value (A)
merely reflect the instrumental uncertainty and repeatability of the test. As discussed above,
Delta E measurement reflect the total color difference between panels before and after treatment,
while Delta L measurements best represent changes in white to black color scale "whiteness" of

the panels, an indication of any whitish film attributable to haze seen on the panels after
treatment. A higher, or positive Delta L value then corresponds to a greater observed visual haze
on the panel surface, and conversely, a lower or negative Delta L number indicates a sample is
darker than the untreated control. The inventive treatments are seen to affect the measured color
minimally, as expected from the highly transparent nature and lack of visual indication of the
film present on the treated panel surfaces. Colorimeter test measurements employing both Delta
E and Delta L components show that the inventive treatments, which have a minimal impact on
visual appearance, correspondingly exhibit very small changes in both of these parameters,
showing a minimal effect on color (total energy of reflectance, E) and negligible contribution to
haze (white component of reflectance, L).



[00171] The durability and self cleaning ability of surfaces treated using several example
embodiments was tested using treated black automotive panels exposed to water and/or brake
dust, with results presented in Table 13.
[00172] In one test, panels treated with the inventive treatment compositions were first tested
for dry dirt repellency. In a second test, the panels were then exposed to a continuous spray of
water and the time at which the panels first showed an indication to form adherent droplets and
hold beads of water on the surface was noted to the nearest 15 second interval to determine
durability of the coating to a water spray. Alternatively, panels were treated with a 15 second
water spray and the surface appearance ranked by visual inspection according the visual ranking
scale described hereinabove to measure the appearance with respect to any adherent water
droplets. All treatment examples provided an initial benefit in readily shedding water from the
surface compared to an untreated control panel. It needs to be emphasized that all treatment
compositions in Table 13 do not contain a durability agent and yet provide good to excellent
durability of the protective coating. The SCL Brake Dust test results demonstrate the ability of
the dry treated surface to resist adhesion of dry brake-dust without the use of any water or
cleaning action. Here, after exposure to the dry brake-dust test soil according to the methods
described herein above, a single tap was sufficient to remove most if not all of the brake-dust
present on the black test surface treated with the inventive treatment compositions indicated in
Table 13. These test results demonstrate that a deposited film of hydrophobically modified
fumed silica delivered via use of a treatment composition according to the present invention is
capable of providing both wet and dry surface protective benefits, producing a treated article
with the protective film deposited thereon, that exhibits self-cleaning and easier cleaning
benefits.


Haze Test Results
[00173] Measurements of the example embodiments were taken according to the Chrome Test
procedures described hereinabove on the high shine chrome test panels, with results presented in
Table 14. The chrome test panels have mirror-like finishes and any surface distortion or residue
is readily perceivable by eye, as well as instrumentally, where the Haze measurement technique

appears to be the most suited for quantifying very slight changes in appearance. Treatment
weight recorded in Table 14 reflects the amount of applied treatment composition, obtained by
weighing the aerosol can containing the respective treatment before and after controlled
dispensing onto the test panel. Compositions had comparable level of the silica active, so that
the amount of deposited silica materials would be comparable. Application of the comparative
example 21 produced a visually hazy and non-uniform coating on the chrome test panel that was
not acceptable, and had a very large Delta Haze Unit value of 288. In comparison, inventive
treatment compositions, Examples 16, 20 and 22, when applied resulted in transparent and barely
perceptible coatings on the chrome surface, all with very low Delta Haze Unit values. Example
16 produced an invisible coating that could not be discerned by the eye, yet exhibited the full
range of protective performance benefits demonstrated by use of the present invention. A variety
of tests on the polished chrome revealed that an preferred transparent surface coatings could be
obtained from inventive treatment compositions providing a measured Delta Haze Unit value of
equal to or less than about 250, as determined by following the Chrome Test procedure as
described hereinabove.


[00174] Thus, surprisingly low Delta Haze Units below around 250 before and after treatment
are demonstrated by the inventive treatment compositions even on highly polished chrome,
corresponding to a surface protective treatment that is transparent and nearly invisible to the eye,
and yet maintain the surface protective benefits desirable in a protective film that still retains
effectiveness in resisting and repelling dirt, water and soil, yet can be easily removed from the
treated surfaces. The noted decrease in observable haze corresponds to the reduced particle size,
suggesting that Delta Haze values below 25, which is essentially invisible, are possible when the
median particle size is reduced to below 1000 nanometers. In addition, using colorimetric
measurements, very low Delta E values below around 3.0 as measured on shiny black metal test
panels demonstrate the ability of the inventive methods and treatment compositions to exhibit
self-cleaning capability and ability to maintain visual appearance close to that of the treated
surface prior to soiling and application of the inventive treatments, thus providing a means for
nearly invisible surface protection applicable to a wide variety of surfaces, including glossy and
reflective surfaces.
Treatment of wood panels
[00175] The ability of an example embodiment of the inventive treatment composition in a
convenient aerosol form (using example 23 below) to provide water roll-off properties to a
commercially available varnished wood panel was tested.
Treatment Composition Example 23
Ingredient Wt.%
Process Composition I 5.0
DYNASILAN® OCTEO 2.0
DC 245 43.0
ATI Propellant 50.0


[00176] The finished wood substrate was a 3 " x 6" section of tongue and groove wood flooring
purchased from Home Depot, with a factory applied coating of an OEM polyurethane finish,
which being hydrophobic in nature provides the wood with high water resistance. Half of the
surface of the sample was treated by spraying with the aerosol treatment composition from a
distance of 6", with the sample lying horizontally, with the second half was masked to prevent
overspray. The sample was then allowed to dry overnight at ambient conditions.
[00177] The roll-off behavior of several water drops placed on the surface in a horizontal
position was tested, comparing the treated and untreated regions of the surfaces. Surface
behavior of multiple water droplets on the surface were observed using and found to provide a
Roll-off test rating of 2 on the treated side, and a rating of 6 on the untreated side. Visual
comparison of the treated and untreated areas provided a uniformity appearance rating of 2 for
the side treated with the inventive treatment compositions, which provided a clear, transparent
protective coating on the finished wood surface.
[00178] In a demonstration of the removability of the treatment, the treated surface was wiped
three times with a dry paper towel. This dry wiping was effective at removing the inventive
treatment compositions, as evidenced by a repeated Roll-off test performed thereafter that
provided equivalent ratings of 6, respectively on both the previously treated, yet cleaned, and
original untreated control side of the wood panel.
[00179] Thus, the utility of the inventive treatment compositions to provide protection of
varnished decorative household surfaces against accidental splashes of water is demonstrated. In
addition, the easy removal of the treatment without special chemical means is also demonstrated
here.


Treatment of Plastic Surfaces
[00180] The ability of the inventive treatment composition exampled above to provide water
roll-off properties to commercially available plastics was then tested. Plastic sheet materials,
obtained from McMaster - Carr, were cut into 4" x 4" sections. Two types of materials were
investigated: a black "acrylic" plastic and a gray "PVC" (polyvinyl chloride) plastic. Each test
treatment was conducted at least on duplicate samples.
[00181] The plastic panels were cut, and cleaned briefly by wiping with a paper towel
moistened with isopropanol (IPA). After drying completely, the panels were treated with the
aerosol formulation sprayed from a distance of 6" for 3 seconds, with the panels in a horizontal
position. The panels were then allowed to dry overnight, before testing.
[00182] The behavior of several water drops placed on the surface in a horizontal position was
tested comparing treated and untreated surfaces as control. Surface behavior of several water
droplets on the treated surfaces of the black acrylic plastic achieved a Roll-off test rating of 2,
while the untreated acrylic control exhibited a rating of 6, even though the water did not "wet"
the surface of the untreated hydrophobic plastic. Surface behavior of several water droplets on
the treated surfaces of the gray PVC plastic also achieved a Roll-off test rating of 2, while the
untreated PVC control exhibited a rating of 6. The uniformity appearance ratings of both the
treated acrylic test panel, and the treated PVC panel both gave a rating of 2 in comparison to
their respective controls, thus providing a clear, invisible protective coating on the plastic
surfaces.
[00183] To test the removability of the inventive treatment from these plastic treatments, the
treated panels were wiped three times with a dry paper towel and retested as to their water roll-of
properties. As with the wood paneling, behavior reverted to that observed on the original
untreated panels. This further demonstrates the utility of the inventive treatment compositions in


providing non-durable protection to plastic surfaces and materials. In addition, the easy removal
of the treatment without special chemical means is also demonstrated on these materials.
Textile Surface Modification
[00184] Example embodiments of the present invention were also tested for their ability to
impart water roll-off properties to woven porous textiles typically used in the manufacture of
clothing.
[00185] In this example, testing employed approximately 3" x 5" swatches of white (undyed
and non-brightened) 100% cotton fabric, white 100% Nylon 6.6 knit fabric, white 50-50 (%)
cotton-polyester fabric, navy colored 100% Dacron 56 polyester texturized double knit heat set
fabric dyed with Disperse Blue 167, Style No. TIC-720H and a dark blue colored 100% nylon
texturized Nylon 6.6 knit fabric dyed with Acid Blue 113, Style No. TIC-314, all obtained from
Textile Innovators Co., Windsor NC.
[00186] The swatches were hung vertically and then treated with the same inventive aerosol
treatment composition as used above to treat plastic substrates. Treatment was accomplished by
spraying the fabrics at a distance of 6 inches for about 3 seconds each, after which the swatches
were allowed to dry overnight under ambient conditions. Three swatches of each type were
treated, and the results obtained from each replicate were averaged.
[00187] The ability of the inventive treatment to produce water roll-off from the swatches was
tested as follows. The swatches were placed on a hard flat surface which was inclined from the
horizontal by about 20°. Using a pipette, 6 drops of de-ionized water (approximately 200
microliters each) were allowed to fall onto the swatch from a height of 6 inches. In this manner,
the effect of the momentum of the falling drops on their ability to wet and penetrate the swatches
is compared. Simple placement of the water drops onto fabric swatches can sometimes yield
false positives, in that the water droplets tend to remain on the surface for a variable and non-

reproducible period of time before finally wicking into, or through the fabric. It was thus found
that with some momentum, the force of the water drop impacting the surface of the fabric results
in the fabric exhibiting its ultimate water wicking, and/or water resistive nature more
reproducibly for the purposes of test comparisons.
[00188] Fabrics with and without the inventive treatment were tested by the above method, and
a Repellency Score was assigned by visually observing and counting the number of repetitive
water droplets impacting on the same spot of the fabric required to produce wetting of the fabric
at that spot. The Repellency Score is the average number of water drops out of 18 (6 drops, three
replicates of each swatch) that rolled off the fabric without sticking or wicking into the fabric.
Thus, treatments with higher scores represent the ability of the fabric to resist wetting by water
and repel water droplets. Fabric test results are presented in Table 15.

[00189] Results show that the inventive treatment compositions are most effective on porous
textile materials having at least some synthetic fibers present, as performance on the 100%
cotton (a natural, fairly hydrophilic biopolymer) was marginal at best in repelling water
following treatment.

[00190] The white fabrics were used to screen for any negative effects of the inventive
treatments on yellowing or staining the fabrics. No yellowing or staining of the white fabrics
was observed. The dark blue fabrics were used to observe whether use of the inventive
treatments resulted in any appearance of visual fading, discoloration or greying of the fabrics.
No fading, discoloration or greying effects were noted after application to the dark fabrics. It
was noted however that use of the inventive treatments on dark fabrics was observed to make
them very slightly darker in appearance when observed side by side with an untreated fabric test
swatch. Colorimetric measurements revealed that use of the inventive treatments yielded a Delta
L value well below 3 units, and with the dark fabrics a small negative Delta L value was
observed, corresponding to the very slightly darker appearance noted by eye. This effect, though
slight, is generally beneficially perceived as a color enhancement on darker fabrics, since fading
due to wear, abrasion, washing, surface fiber damage and subsequent dye loss, otherwise
produces changes in L resulting in larger positive Delta L changes, generally observable by eye
when positive Delta L values exceed a value of greater than 5, the effect generally being
attributed to overall "fading." Thus, the inventive treatment compositions tend to exhibit a slight
anti-fading benefit on darker fabrics, and are essentially invisible on white and lighter-colored
fabrics when applied according to the methods of application described herein.



[00191] These last few examples further demonstrate the utility of the inventive treatment
compositions to be used to treat a wide variety of both hard, non-porous materials such as
plastics, wood, metal painted paneling, chrome and the like, as well as porous materials such as
textiles, and to provide clear, protective coatings that repel water and dirt readily from the
surfaces of the treated materials, substrates and articles treated according to the methods
disclosed herein.
[00192] While the present invention has been shown and described in accordance with practical
and preferred embodiments thereof, it is recognized that departures from the instant disclosure
are contemplated within the spirit of the invention and, therefore, the scope of the invention
should not be limited except as defined within the following claims as interpreted under the
doctrine of equivalents.

WE CLAIM:
1. A process for producing a composition comprising:
(a) providing a pre-dispersion of silica particles comprising hydrophobically
modified fumed silica particles by stirring hydrophobically modified fumed silica
particles into a solution comprising
(i) a disilazane selected from hexamethyldisilazane,
divinyltertramethyldisilazane, bis(3,3-triflouropropyl) tetramethyldisilazane
and octamethylcyclotetrasilazane, and
(ii) a first volatile solvent or solvent mixture selected from straight or
branched, linear or cyclic aliphatic, or aromatic hydrocarbons with 2 to 14
carbon atoms, monovalent linear or branched alcohols with 1 to 6 carbon
atoms, ketones or aldehydes with 1 to 6 carbon atoms, ethers or esters
with 2 to 8 carbon atoms, or linear or cyclic polydimethylsiloxanes with 2
to 10 dimethylsiloxy units,
wherein the concentration of the hydrophobically modified fumed silica particles
in the pre-dispersion results in from 10 percent to 30 percent by weight of the
total weight of the pre-dispersion, and wherein the concentration of disilazane is
between 0.1 and 10 percent by weight of the total weight of the pre-dispersion;
and
(b) mixing with a disperser said pre-dispersion to provide a process composition
while reducing the particle size of said silica particles to a median particle size
in the range between 100 and 4000nm.

2. The process as claimed in claim 1, wherein said solution further comprises a
durability agent selected from alkoxysilanes of general formula (III)
R5aSi(OR6)4-a (Ml)
wherein R5 is a straight or branched, saturated or unsaturated alkyl chain group of
from 1 to 16 carbon atoms, R6 is an alkyl chain of 1 to 2 carbon atoms, and a is 1
or 2; or alkyl-modified linear or cyclic polydimethylsiloxanes of general formula (IV)
or(V)
(CH3)3 SiO[(CH3)2SiO]n[(CH3)R7SiO]0Si(CH3)3 (IV)
-[(CH3)2SiO]p[CH3)R7SiO]q-(cyclo) (V)
wherein R7 is an alkyl chain group of from 6 to 24 carbon atoms, n is from 1 to 100,
o is from 1 to 40, p from 0 to 7, and q is from 1 to 7, provided that the sum (p+q) is
at least 3;
whereby the concentration of the durability agents (III) and/or (IV) and /or (V) is
between 0.1 and 10 percent by weight of the total weight of the pre-dispersion.
3. The process as claimed in claim 1 or 2, further comprising diluting the process
composition with a second volatile solvent or solvent mixture selected from straight
or branched, linear or cyclic aliphatic, or aromatic hydrocarbons with 2 to 14
carbon atoms, monovalent linear or branched alcohols with 1 to 6 carbon atoms,
ketones or aldehydes with 1 to 6 carbon atoms, ethers or esters with 2 to 8 carbon
atoms, or linear or cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units to
a final concentration of the hydrophobically modified fumed silica particles of
minimum 5% by weight of the total weight of the process composition.


4. The process as claimed in any of the preceding claims, wherein the first volatile
solvent or solvent mixture is selected from straight or branched, linear or cyclic
aliphatic or aromatic hydrocarbons with 2 to 14 carbon atoms, monovalent linear or
branched alcohols with 1 to 6 carbon atoms, or linear or cyclic
polydimethylsiloxanes with 2 to 10 dimethylsiloxy units.
5. The process as claimed in claim 4, wherein the first volatile solvent or solvent
mixture comprises a linear polydimethylsiloxane with 2 to 10 dimethylsiloxy units or
a cyclic polydimethylsiloxane with 3 to 6 dimethylsiloxy units.
6. A composition obtainable by a process as claimed in any one of claims 1 to 5
comprising:
5 to 30% by weight of hydrophobically modified fumed silica particles with a
median particle size in the range between 100 and 4000 nm; and
50 to 95% by weight of a volatile solvent or solvent mixture selected from straight
or branched, linear or cyclic aliphatic, or aromatic hydrocarbons with 2 to 14
carbon atoms, monovalent linear or branched alcohols with 1 to 6 carbon atoms,
ketones or aldehydes with 1 to 6 carbon atoms, ethers or esters with 2 to 8 carbon
atoms, or linear or cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy units.
7. The composition as claimed in claim 6, further comprising 0.01 to 10% by weight of
a disilazane selected from hexamethyldisilazane divinyltetramethyldisilazane,
bis(3,3-triflouropropyl) tetramethyldisilazane and octamethylcyclotetrasilazane.

8. The composition as claimed in claims 6 or 7, further comprising 0.01 to 10% by
weight of a durability agent selected from alkoxysilanes of general formula (III)
R5aSi(OR6)4-a (III)
wherein R5 is a straight or branched, saturated or unsaturated alkyl chain group of
from 1 to 16 carbon atoms, R6 is an alkyl chain of 1 to 2 carbon atoms, and a is 1 or
2;
or alkyl-modified linear or cyclic polydimethylsiloxanes of general formula (IV) or (V)
(CH3)3SiO[(CH3)2SiO]n[(CH3)R7SiO]0Si(CH3)3 (IV)
-[(CH3)2SiO]p[(CH3)R7SiO]q-(cyclo) (V)
wherein R7 is an alkyl chain group of from 6 to 24 carbon atoms, n is from 1 to 100,
o is from 1 to 40, p from 0 to 7, and q is from 1 to 7, provided that the sum (p+q) is at
least 3.
9. The composition of any one of claims 6 to 8, wherein the volatile solvent or solvent
mixture comprises a linear polydimethylsiloxane with 2 to 10 dimethylsiloxy units or a
cyclic polydimethylsiloxane with 3 to 6 dimethylsiloxy units.


A process for producing a composition comprising: (a) providing a pre-dispersion of silica
particles comprising hydrophobically modified fumed silica particles by stirring
hydrophobically modified fumed silica particles into a solution comprising (i) a disilazane
selected from hexamethyldisilazane, divinyltetramethyldisilazane, bis(3,3-triflouropropyl)
tetramethyldisilazane and octamethylcyclotetrasilazane, and (ii) a first volatile solvent or
solvent mixture selected from straight or branched, linear or cyclic aliphatic, or aromatic
hydrocarbons with 2 to 14 carbon atoms, monovalent linear or branched alcohols with 1
to 6 carbon atoms, ketones or aldehydes with 1 to 6 car bon atoms, ethers or esters with
2 to 8 carbon atoms, or linear or cyclic polydimethylsiloxanes with 2 to 10 dimethylsiloxy
units, wherein the concentration of the hydrophobically modified fumed silica particles in
the pre-dispersiof) results in from 10 percent to 30 percent by weight of the total weight of
the pre-dispersion, and wherein the concentration of the disilazane is between 0.1 and 10
percent by weight of the total weight of the pre-dispersion; and (b) mixing with a disperser
said pre-dispersion to provide a process composition while reducing the particle size of
said silica particles to a median particle size in the range between 100 and 4000nm.

Documents:

01704-kolnp-2008-abstract.pdf

01704-kolnp-2008-claims.pdf

01704-kolnp-2008-correspondence others.pdf

01704-kolnp-2008-description complete.pdf

01704-kolnp-2008-drawings.pdf

01704-kolnp-2008-form 1.pdf

01704-kolnp-2008-form 2.pdf

01704-kolnp-2008-form 3.pdf

01704-kolnp-2008-form 5.pdf

01704-kolnp-2008-gpa.pdf

01704-kolnp-2008-international publication.pdf

01704-kolnp-2008-international search report.pdf

01704-kolnp-2008-pct request form.pdf

01704-kolnp-2008-priority document.pdf

1704-KOLNP-2008-(25-01-2012)-CORRESPONDENCE.pdf

1704-KOLNP-2008-ABSTRACT-1.1.pdf

1704-KOLNP-2008-ABSTRACT-1.2.pdf

1704-KOLNP-2008-ABSTRACT.pdf

1704-KOLNP-2008-AMANDED CLAIMS-1.1.pdf

1704-KOLNP-2008-AMANDED CLAIMS-1.2.pdf

1704-KOLNP-2008-AMANDED CLAIMS.pdf

1704-KOLNP-2008-ASSIGNMENT.pdf

1704-KOLNP-2008-CORRESPONDENCE 1.3.pdf

1704-KOLNP-2008-CORRESPONDENCE OTHERS 1.1.pdf

1704-KOLNP-2008-CORRESPONDENCE OTHERS 1.2.pdf

1704-KOLNP-2008-CORRESPONDENCE-1.4.pdf

1704-KOLNP-2008-CORRESPONDENCE-1.5.pdf

1704-KOLNP-2008-CORRESPONDENCE-1.6.pdf

1704-KOLNP-2008-DESCRIPTION (COMPLETE)-1.1.pdf

1704-KOLNP-2008-DESCRIPTION (COMPLETE)-1.2.pdf

1704-KOLNP-2008-DESCRIPTION (COMPLETE).pdf

1704-KOLNP-2008-DRAWINGS-1.1.pdf

1704-KOLNP-2008-DRAWINGS-1.2.pdf

1704-KOLNP-2008-DRAWINGS.pdf

1704-KOLNP-2008-EXAMINATION REPORT.pdf

1704-KOLNP-2008-FORM 1-1.1.pdf

1704-KOLNP-2008-FORM 1-1.2.pdf

1704-KOLNP-2008-FORM 1.pdf

1704-kolnp-2008-form 18.pdf

1704-KOLNP-2008-FORM 2-1.1.pdf

1704-KOLNP-2008-FORM 2-1.2.pdf

1704-KOLNP-2008-FORM 2.pdf

1704-KOLNP-2008-FORM 3.pdf

1704-KOLNP-2008-FORM 5.pdf

1704-KOLNP-2008-GPA.pdf

1704-KOLNP-2008-GRANTED-ABSTRACT.pdf

1704-KOLNP-2008-GRANTED-CLAIMS.pdf

1704-KOLNP-2008-GRANTED-DESCRIPTION (COMPLETE).pdf

1704-KOLNP-2008-GRANTED-DRAWINGS.pdf

1704-KOLNP-2008-GRANTED-FORM 1.pdf

1704-KOLNP-2008-GRANTED-FORM 2.pdf

1704-KOLNP-2008-GRANTED-SPECIFICATION.pdf

1704-KOLNP-2008-OTHERS-1.1.pdf

1704-KOLNP-2008-OTHERS-1.2.pdf

1704-KOLNP-2008-OTHERS-1.3.pdf

1704-KOLNP-2008-OTHERS-1.4.pdf

1704-KOLNP-2008-OTHERS.pdf

1704-KOLNP-2008-PCT REQUEST FORM 1.1.pdf

1704-KOLNP-2008-PETITION UNDER RULE 137.pdf

1704-KOLNP-2008-REPLY TO EXAMINATION REPORT-1.1.pdf

1704-KOLNP-2008-REPLY TO EXAMINATION REPORT.pdf


Patent Number 251698
Indian Patent Application Number 1704/KOLNP/2008
PG Journal Number 13/2012
Publication Date 30-Mar-2012
Grant Date 28-Mar-2012
Date of Filing 28-Apr-2008
Name of Patentee EVONIK DEGUSSA GMBH
Applicant Address RELLINGHAUSER STRASSE 1-11, 45128 ESSEN
Inventors:
# Inventor's Name Inventor's Address
1 DR. THOMAS DIETZ FRÜHLINGSTRAßE 4 63808 HAIBACH
2 MARIA R. NARGIELLO 1330 WEATHERVANE LAM APT. AKRON, NEW JERSEY 44273
3 JODI LYNN RUSSEL C/O CLOROX SERVICES COMPANY, P.O. BOX 493, PLEASANTON, CALIFORNIA 94588-8004
4 ASHOT K. SEROBIAN C/O CLOROX SERVICES COMPANY, P.O. BOX 493, PLEASANTON, CALIFORNIA 94588-8004
5 PATRICK WINTER PEISBERG 27 45473 MÜLHEIM
6 DR. FELIX MÜLLER MEISENSTR. 9 42555 VELBERT
PCT International Classification Number C09C 1/30
PCT International Application Number PCT/EP2006/067760
PCT International Filing date 2006-10-25
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 11/263,284 2005-10-31 U.S.A.