U.S. patent application number 09/828014 was filed with the patent office on 2002-03-07 for long lasting coatings for modifying hard surfaces and processes for applying the same.
This patent application is currently assigned to The Procter & Gamble Company. Invention is credited to Goldstein, Alan Scott, Jensen, John Michael, Liddle, Heather Anne, McDonald, Michael Ray, O'Connor, Helen Frances, Rohrbaugh, Robert Henry, Sakkab, Nabil Yaqub.
Application Number | 20020028288 09/828014 |
Document ID | / |
Family ID | 27358991 |
Filed Date | 2002-03-07 |
United States Patent
Application |
20020028288 |
Kind Code |
A1 |
Rohrbaugh, Robert Henry ; et
al. |
March 7, 2002 |
Long lasting coatings for modifying hard surfaces and processes for
applying the same
Abstract
Materials for coating, coating compositions, methods and
articles of manufacture comprising a nanoparticle system or
employing the same to impart surface modifying benefits for all
types of inanimate hard surfaces are disclosed. In some
embodiments, dispersement of nanoparticles in a suitable carrier
medium allows for the creation of coating compositions, methods and
articles of manufacture that create multi-use benefits to modified
hard surfaces. These surface modifications can produce long lasting
or semi-permanent multi-use benefits that include at least one of
the following improved surface properties: wetting and sheeting,
quick drying, uniform drying, soil removal, self-cleaning,
anti-spotting, anti-soil deposition, cleaner appearance, enhanced
gloss, enhanced color, minor surface defect repair, smoothness,
anti-hazing, modification of surface friction, release of actives
and transparency, relative to hard surfaces unmodified with such
nanoparticle systems. Actively curing the coating composition on
the hard surfaces, including, but not limited to by radiative
heating the air surrounding the hard surface with the coating
thereon can be used to increase the durability of the hard surface
coating.
Inventors: |
Rohrbaugh, Robert Henry;
(Hamilton, OH) ; Goldstein, Alan Scott; (Blue Ash,
OH) ; McDonald, Michael Ray; (Middletown, OH)
; O'Connor, Helen Frances; (Loveland, OH) ;
Liddle, Heather Anne; (Cincinnati, OH) ; Jensen, John
Michael; (Wyoming, OH) ; Sakkab, Nabil Yaqub;
(Cincinnati, OH) |
Correspondence
Address: |
THE PROCTER & GAMBLE COMPANY
PATENT DIVISION
IVORYDALE TECHNICAL CENTER - BOX 474
5299 SPRING GROVE AVENUE
CINCINNATI
OH
45217
US
|
Assignee: |
The Procter & Gamble
Company
|
Family ID: |
27358991 |
Appl. No.: |
09/828014 |
Filed: |
April 6, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60265059 |
Jan 30, 2001 |
|
|
|
Current U.S.
Class: |
427/180 ;
427/372.2; 427/402 |
Current CPC
Class: |
C09D 7/68 20180101; C09D
1/00 20130101; Y02W 10/37 20150501; B01J 39/05 20170101; C08K 3/22
20130101; C11D 3/1213 20130101; C11D 3/14 20130101; C02F 2001/425
20130101; C11D 11/0023 20130101; C11D 3/1253 20130101; C11D 11/0058
20130101; B08B 3/026 20130101; C08K 3/346 20130101; C02F 2001/422
20130101; C09D 7/67 20180101; C02F 1/42 20130101; C11D 17/0013
20130101; C11D 3/1266 20130101; C09D 7/61 20180101; B01J 39/05
20170101; B01J 41/07 20170101 |
Class at
Publication: |
427/180 ;
427/372.2; 427/402 |
International
Class: |
B05D 003/02; B05D
001/36; B05D 007/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 14, 2000 |
US |
PCT/US00/16349 |
Claims
What is claimed is:
1. A method of forming a substantially clear hard surface coating
on a hard surface, said method comprising: (a) applying a material
for coating a hard surface to a hard surface, said material
comprising an effective amount of non-photoactive nanoparticles;
and (b) actively curing said material on said hard surface.
2. The method of claim 1 wherein a substantially clear, hydrophilic
coating is formed on said hard surface.
3. The method of claim 1 wherein the step (a) of applying a
material for coating a hard surface comprises applying a plurality
of non-photoactive nanoparticles directly to said hard surface.
4. The method of claim 1 wherein the step (a) of applying a
material for coating a hard surface comprises applying a plurality
of non-photoactive nanoparticles to said hard surface through the
use of a carrier medium.
5. The method of claim 4 wherein the carrier medium comprises a
gas.
6. The method of claim 4 wherein the carrier medium comprises a
liquid.
7. The method of claim 6 wherein the carrier medium is aqueous.
8. The method of claim 6 wherein the carrier medium is
nonaqueous.
9. The method of claim 1 wherein the material applied in step (a)
comprises a hard surface coating composition comprising an
effective amount of non-photoactive nanoparticles and a carrier
medium.
10. The method of claim 3 wherein said hard surface is charged to
facilitate attraction and adherence of said non-photoactive
nanoparticles thereto.
11. The method of claim 1 wherein the step (b) of actively curing
said material on said hard surface comprises thermally curing said
material.
12. The method of claim 1 wherein the material applied in step (a)
comprises an agent that is incorporated therein for accelerating
the curing of the material, and the step (b) of actively curing the
material comprises allowing said agent to cure said material.
13. The method of claim 9 wherein the hard surface coating
composition in step (a) comprises a pre-mixed solution.
14. The method of claim 9 wherein the hard surface coating
composition in step (a) is formed by: (i) providing a concentrated
hard surface coating composition; and (ii) diluting said
concentrated hard surface coating composition.
15. The method of claim 14 wherein the step (ii) comprises diluting
said concentrated hard surface composition with deionized
water.
16. The method of claim 14 wherein the hard surface coating
composition comprises a dispersing agent, and the step (ii)
comprises diluting said concentrated hard surface composition with
tap water.
17. The method of claim 11 wherein the material is applied at an
ambient temperature, and the step (b) of thermally curing said
material comprises heating the air surrounding said material and
said hard surface to a temperature of greater than or equal to
ambient temperature.
18. The method of claim 11 wherein the step (b) of thermally curing
said material comprises heating the air surrounding said material
and said hard surface to a temperature of greater than or equal to
about 50.degree. C.
19. The method of claim 1 wherein the temperature to which the air
surrounding said material is heated is no greater than about 1
80.degree. C.
20. The method of claim 1 wherein said hard surface has an
appearance, and the appearance of said hard surface remains
substantially unchanged after inspection to the unaided human eye
after said material is cured.
21. The method of claim 1 wherein the surface with the hard surface
coating thereon has a transmittance to light of greater than or
equal to about 75%.
22. The method of claim 9 wherein the concentration of
nanoparticles in said coating composition prior to application to
said hard surface is less than about 50% by weight of the coating
composition.
23. The method of claim 9 wherein the coating composition is in the
form of a liquid for spray on application, and the concentration of
nanoparticles in said coating composition prior to application to
said hard surface is less than about 20% by weight of the coating
composition.
24. The method of claim 9 wherein the coating composition is in the
form of a liquid for spray on application, and the concentration of
nanoparticles in said coating composition prior to application to
said hard surface is less than about 0.5% by weight of the coating
composition.
25. The method of claim 9 wherein the viscosity of said coating
composition is less than or equal to about 1,000 Cps.
26. The method of claim 9 wherein the viscosity of said coating
composition is less than or equal to about 100 Cps.
27. The method of claim 9 wherein the viscosity of said coating
composition is less than or equal to about 40 Cps.
28. The method of claim 1 wherein said hard surface is selected
from the group consisting of fiberglass, plastics, metals, glass,
dishware, ceramic, wood, stone, concrete, asphalt, mineral, painted
surfaces, and mixtures thereof.
29. The method of claim 1 wherein said hard surface is selected
from the group consisting of: exterior panels of vehicles, exterior
panels of aircraft; exterior of watercraft; glass; skis; and the
interior of pipes.
30. The method of claim 1 wherein said hard surface comprises an
automobile body panel.
31. The method of claim 30 which is applied prior to, during, or
after a process of painting and/or applying a clear coat to the
automobile body panel.
32. The method of claim 31 wherein said process comprises painting
and subsequently applying a clear coat to an automobile body panel,
and comprises one or more of the steps of: (i) applying one or more
coats of primer to said automobile body panel; (ii) applying one or
more coats of paint to said automobile body panel; (iii) applying
one or more coats of clear coat to said automobile body panel; and
(iv) heating said automobile body panel after any of one or more of
said coats of primer, coats of paint, or coats of clear coat are
applied.
33. The method of claim 32 wherein the material is applied after
said one or more coats of paint are applied to said automobile body
panel.
34. The method of claim 32 wherein the material is applied during
the step (iii) of applying one or more coats of clear coat to said
automobile body panel.
35. The method of claim 32 wherein the material is applied after
said one or more coats of clear coat are applied to said automobile
body panel.
36. A method of treating a hard surface comprising: a) providing a
hard surface coating composition comprising an effective amount of
non-photoactive nanoparticles, tap water, and a dispersing agent;
and b) applying said coating composition to modify said hard
surface.
37. The method of claim 36 further comprising a step (c) of
allowing said coating composition to dry.
38. The method of claim 36 further comprising a step (c) of
actively curing said coating composition.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of the filing dates of
PCT application Serial No. US00/16349, filed Jun. 14, 2000, and
U.S. Provisional patent application Serial No. 60/265,059, filed
Jan. 30, 2001.
FIELD OF THE INVENTION
[0002] The present invention relates to coatings, compositions,
methods and articles of manufacture comprising a nanoparticle
system or employing the same to impart surface modifying benefits
for all types of inanimate hard surface applications.
[0003] The use of non-photoactive nanoparticles allows for the
creation of coatings, compositions, methods and articles of
manufacture that create multi-use benefits to modified hard
surfaces. These surface modifications can produce durable, long
lasting or semi-permanent multi-use benefits that include at least
one of the following improved surface properties: wetting and
sheeting, quick drying, uniform drying, soil removal,
self-cleaning, anti-spotting, anti-soil deposition, cleaner
appearance, enhanced gloss, enhanced color, minor surface defect
repair, smoothness, anti-hazing, modification of surface friction,
release of actives, and transparency (e.g., in the case of glass
and the like), relative to hard surfaces unmodified with such
nanoparticle systems.
BACKGROUND OF THE INVENTION
[0004] There have been many problems associated with developing
hard surface coatings that provide a beneficial layer with the
desirable properties and which minimize the disadvantages, such as
a limit to single use protection, insufficient coverage, roughness
and/or flaking of coating during use, or in contrast, the inability
to remove once applied (when a more temporary coating is desired),
a limit on surfaces that can be modified, photoactive damage and
degradation of the surface.
[0005] The current approach to solving the coating problem is with
the use of surfactants, film-forming polymer coatings,
clay-containing-film-formi- ng polymer coatings and photoactive
inorganic metal oxide coatings. However, the substantivity of the
film-forming polymers (e.g. alkoxylated silicones,
poly(N-vinyl-2-pyrrolidones, poly(N-vinyl-imidazoles, diblock
copolymers of poly(ethylene oxide) and poly(lactide)) is poor such
that its wetting/sheeting effect is short-lived, with
spotting/residue negatives returning within 1-2 rinses, exposures
to the elements (e.g., rain, etc.), or conditions (e.g., water in a
shower). Elevating the levels of polymers is not the solution to
this problem. This is especially evident on automobile surfaces,
residential windows, building exteriors, shower units and dishware
where elevated levels of polymers result in unacceptable residue
problem. In the case of clay-containing, film-forming polymer
coatings, the nanoparticles are rheology agents for the
formulations and do not themselves impart the benefit disclosed.
One example of this approach is disclosed in U.S. Pat. No.
5,429,999, titled "Organoclay Compositions Containing Two Or More
Cations And One Or More Organic Anions", wherein preparation and
use in non-aqueous systems of an organophilic clay gellant is used
in a non-aqueous fluid system such as paints, inks, and coatings to
provide improved rheological properties. Other related patents
include: U.S. Pat. No. 05,785,749, titled "Method For Producing
Rheological Additives And Coating Compositions Incorporating Same";
U.S. Pat. No. 5,780,376, titled "Organoclay Compositions"; U.S.
Pat. No. 5,739,087, Titled "Organoclay Products Containing A
Branched Chain Alkyl Quaternary Ammonium Ion"; U.S. Pat. No.
5,728,764, titled "Formulations Including Improved Organoclay
Compositions"; and U.S. Pat. No. 6,036,765, titled "Organoclay
Compositions And Method Of Preparation".
[0006] Another approach to this problem is disclosed in U.S. Pat.
No. 4,597,886, titled "Dishwashing Compositions", wherein an
inclusion of an effective level of a layered clay (e.g. a synthetic
hectorite) in an enzymatic dishwashing composition is introduced to
reduce the formation of spots and films on the cleaned objects.
U.S. Pat. No. 4,591,448, titled "Dishwashing Compositions",
discloses the use of a layered clay in a non-enzymatic dish-washing
composition with a reduced pH of 9-11 to provide for a reduction of
spot and film formation on the cleaned articles. See also U.S. Pat.
No. 4,591,449. EP. Pat. No. 139,330 B1, titled "Rinse Aid"
discloses the use of a layered clay as a rinse aid or rinse
component for the aqueous rinsing step of a machine dishwashing
process to provide anti-spotting benefits. In the abovementioned
dishware care patents, the layered clay is introduced in the
machine dishwashing detergent or rinse aide as a single-use
application to prevent spotting and film formation during that
particular wash cycle. These patents do not disclose a nanoparticle
coating system requirement which is preventative in nature, unlike
the present invention. Furthermore, they do not disclose multi-use
benefits (such as, anti-spotting, anti-hazing, soil removal and
minor surface defect repair) without additional treatment between
uses.
[0007] The photoactive metal oxide approach using nanoparticles,
such as zinc oxide (ZnO.sub.2) and titanium dioxide (TiO.sub.2),
have serious limitations and harmful deleterious surface effects to
overcome. The potential of using TiO.sub.2 to functionalize hard
surfaces (1) is limited to surfaces exposed to outdoor levels of UV
and (2) requires special surface safety precautions to protect
against photoactivated damage mechanisms. In addition, TiO.sub.2 is
difficult to apply to said surfaces and often requires professional
treatment of the surface.
[0008] In the case of TiO.sub.2 thin films, an approach taken in
JP. Pat. No. 11181339 A2, titled "Hydrophilic Coating Composition",
discloses a room-temperature-settable coating composition
comprising an aqueous fluid containing photocatalytic titanium
oxide particles having a particle diameter of 1-100 nm and tin
oxide particles having a particle diameter of 1-100 nm and having a
pH of 8-12 or a pH of 0-5, and a coating film which exhibits
hydrophilicity when it is formed on a substrate and irradiated with
ultraviolet rays at a wavelength of 200-400 nm and, and the
photocatalytic titanium oxide is photoexcited. Other related
patents disclosing methods and articles of use for the
abovementioned titanium oxide coating composition include JP. Pat.
No. 11172239 A2, titled "Hydrophilic Member, Method For
Hydrophilization/Hydrophilicity Retention Of Surface Of Member, And
Hydrophilic Coating Composition"; JP. Pat. No. 10297436 A2, titled
"Manufacture Of Mirror For Vehicle With Improved Rainy Weather
Visibility"; JP. Pat. No. 10046759 A2, titled "Roof Material Having
Ice-Snow Sticking Preventive Performance, JP. Pat. No. 09056549 A2,
titled "Anti-Fogging Mirror"; JP. Pat. No. 00128672 A2, titled
"Ceramic Ware And Its Production"; JP. Pat. No. 00096800 A2, titled
"Antifouling Building Material And Manufacture Thereof; JP. Pat.
No. 11300303 A2, titled "Cleaning Method Of Composite Material And
Self-Cleaning Composite Material Mechanism"; JP. Pat. No. 10237431
A2, titled "Member With Ultrawater-Repellent Surface"; JP. Pat. No.
10212809 A2, titled "Building Material For External Wall"; JP. Pat.
No. 09230107 A2, titled "Anti-Fogging Glass Lens And Its
Anti-Fogging Method"; and JP. Pat. No. 09228072 A2, titled "Outdoor
Member". In the abovementioned patents, the hydrophilic TiO.sub.2
film can cause photo- and chemical-degradation of organic
undercoats, and any rubber or plastic it comes into contact with,
and requires professional means of application and treatment.
[0009] U.S. Pat. No. 4,164,509, titled " Process For Preparing
Finely Divided Hydrophobic Oxide Particles" discloses a process for
preparing hydrophobic finely divided particles of oxides of metals
and/or oxides of silicon by chemically bonding hydrocarbon radicals
to the surface of the oxide particles.
[0010] It is apparent that there is a continuing need in order to
improve the various properties of all hard surfaces, including but
not limited to fiberglass, plastics, metals, glass, ceramic, wood,
stone, concrete, asphalt, mineral, and painted surfaces, via a
coating composition, method of use and article of manufacture which
would result in hard surfaces having one or more of the following
highly desirable modified surface properties such as improved
surface wetting and sheeting, quick drying, uniform drying, soil
removal, self-cleaning, anti-spotting, anti-soil deposition,
cleaner appearance, enhanced gloss, enhanced color, minor surface
defect repair, improved smoothness, anti-hazing properties,
modification of surface friction, release of actives, reduced
damage to abrasion and improved transparency. There is also a
continuing need that these modified surface benefits be made longer
lasting than the approach made by the polymer patents or
semi-permanent to be more responsive to consumer applications than
the approach that utilizes photoactivated coatings alone (e.g.
TiO.sub.2).
[0011] Nanoparticles have been used for a number of purposes in
general coatings, but not for the abovementioned benefits. One
example is disclosed in U.S. Pat. No. 4,173,480, titled
"Photographic Sheet With Synthetic Hectorite Antistatic Additive As
Sizing Or Backcoat", wherein a polymer film base is coated with a
synthetic hectorite clay, specifically Laponite S.TM.. The binder
is gelatin, starch or carboxy methylcellulose. The primary benefit
here is to impart antistatic properties to the surface. In the
present invention, the binder is not required to apply the
nanoparticle to the surface.
[0012] Another example is disclosed in U.S. Pat. No. 4,868,048,
titled "Conductive Sheet Material Having An Aqueous Conductive
Composition, wherein certain fractions (i.e., neighborite) are
removed from synthetic hectorite before use thereof as a coating
with a non-epoxy binder. The primary benefit here is to impart
conduction of electric charge to the surface. In the present
invention, the binder is not required to apply the nanoparticle to
the surface.
[0013] Another example is disclosed in JP. Pat. No. 8053558 A2,
titled "Anti-Fog Synthetic Resin Film For Agriculture", wherein
colloidal alumina, colloidal silica, anionic surfactant, organic
electrolyte and an inorganic layered compound form a film that
exhibits sustained anti-fog properties at low- and
high-temperatures. Another example is disclosed in JP. Pat. No.
04353438 A2, titled "Transparent Plastic Films With Good Dew And
Blocking Preventing Effects", discloses Li-Mg-Na silicate layers on
1 side of the films useful for greenhouses, book covers, card
holders, etc.. See also, EP 0732387 titled, "Antifogging agent
composition and agricultural film coated therewith".
[0014] Another example is disclosed in U.S. Pat. No. 4,786,558,
titled "Composite Film And Antistatic Composite Film Comprising A
Swellable Inorganic Silicate", where the inorganic nanoparticle is
modified by treating it with various ions to provide a composite
film with antistatic benefits comprising a swellable inorganic
silicate.
[0015] Another example is disclosed in W.O. Pat. 99/00457 A1,
titled "Coating Agent For Reducing The Soiling Process Of Facades",
wherein the invention relates to the preparation of a system used
for reducing the soiling process of building facades. Here the
layered silicate is disclosed for its use as a gellant and is not
responsible for the reduction of surface soiling benefits
alone.
[0016] Another approach is disclosed in U.S. Pat. No. 5,853,809,
entitled "Scratch Resistant Clearcoats Containing Surface Reactive
Microparticles and Method Therefor" issued to Campbell, et al. This
patent is directed to clearcoat coating compositions that, after
application, comprise the outermost layer on automotive body
panels. Reactive inorganic microparticles are added to the coating
composition to improve scratch resistance.
[0017] Another approach taken is disclosed in U.S. Pat. No.
6,020,419, titled "Transparent Coating Compositions Containing
Nanoscale Particles And Having Improved Scratch Resistance",
wherein specific combinations of properties in coatings, such as
transparency and wear resistance, may be obtained by using
nanoparticles.
[0018] The present invention relates to materials, coatings,
compositions, methods, and articles of manufacture that provide
some important hard surface multi-use benefits that can be made
long lasting or semi-permanent. These multi-use benefits include at
least one of the following: improved surface wetting and sheeting,
quick drying, uniform drying, soil removal, self-cleaning,
anti-spotting, anti-soil deposition, cleaner appearance, enhanced
gloss, enhanced color, minor surface defect repair, improved
smoothness, anti-hazing properties, modification of surface
friction, release of actives, reduced damage to abrasion, and
improved transparency (the latter in the case of surfaces such as
glass and the like, particularly after such surfaces are soiled or
contacted with water) relative to transparent surfaces that are not
treated with the materials, coatings, or coating composition, and
anti-fogging in the case of surfaces (such as mirrors) that are
designed to reflect.
SUMMARY OF THE INVENTION
[0019] In one embodiment of the present invention there is provided
a material for coating a hard surface. The material for coating a
hard surface can comprise a plurality of non-photoactive
nanoparticles, or it can comprise a hard surface coating
composition. Such a coating composition may comprise: (a) an
effective amount of non-photoactive nanoparticles; (b) optionally a
surfactant; (c) optionally having associated to said nanoparticle
surface a quantity of one or more functionalized surface molecules
exhibiting properties selected from the group consisting of
hydrophilic, hydrophobic and mixtures thereof, (d) optionally one
or more adjunct ingredients; and (e) optionally a suitable carrier
medium.
[0020] In another embodiment of the present invention, there is
provided a method of applying a substantially clear coating to a
hard surface comprising: applying a material comprising an
effective amount of non-photoactive nanoparticles to the hard
surface; and, actively curing the material to form a coating on the
hard surface.
[0021] In another embodiment of the present invention there is
provided a method of using a coating composition by (a) mixing said
nanoparticles in suitable carrier medium to form said coating
composition; (b) optionally mixing said nanoparticles dispersed in
suitable carrier medium with adjunct ingredients to form said
coating composition; (c) optionally mixing said nanoparticles
dispersed in suitable carrier medium with surfactant to form said
coating composition; (d) optionally mixing said nanoparticles
dispersed in suitable carrier medium with adjunct ingredients and
surfactant to form said coating composition; (e) applying said
coating composition to a hard surface; (f) allowing said coating
composition to dry, or drying the coating composition; and (g)
optionally repeating any of steps (a) through (f) as needed.
[0022] The drying step can comprise air drying in ambient
conditions, or it can comprise actively drying the coating
composition by utilizing any technology known for accelerating the
drying process. It has been found the heat drying the hard surface
coating composition can greatly increase the durability of the hard
surface coating.
[0023] In another embodiment of the present invention there is
provided an article of manufacture comprising an applicator, such
as a spray dispenser, an immersion container, a hose spray
dispenser attachment, a fabric or a sponge; further comprising (a)
a coating composition, wherein said coating composition is in the
physical form selected from the group consisting of liquid, liquid
concentrate, gel, powder, tablet, granule and mixtures thereof; (b)
optionally a source of water or deionized water; and (c) optionally
a set of instructions in association with said spray dispenser
comprising an instruction to dispense said coating composition from
said spray dispenser onto said hard surface.
[0024] In another embodiment of the present invention there is
provided a treated hard surface coated with the coating
composition. Substrates treated with the benefit agent materials of
the present invention exhibit a greater improvement in wetting and
sheeting, quick drying, uniform drying, soil removal,
self-cleaning, anti-spotting, anti-soil deposition, cleaner
appearance, enhanced gloss, enhanced color, minor surface defect
repair, improved smoothness, anti-hazing properties, modification
of surface friction, release of actives, reduced damage to abrasion
and improved transparency than substrates treated without such
benefit agent materials.
[0025] In another embodiment of the invention there is provided a
treated hard surface coated with a coating composition, where the
coating composition is strippable. Substrates treated with the
benefit agent materials of the present invention exhibit a greater
improvement in soil removal, self-cleaning, anti-spotting,
anti-soil deposition, cleaner appearance after at least one
effective nanoparticle layer has been stripped than substrates
treated without such benefit agent materials.
[0026] These and other objects, features and advantages will be
clear from the following detailed description, examples and
appended claims.
[0027] All percentages, ratios and proportions herein are on a
weight basis based on a neat product unless otherwise indicated.
All documents cited herein are hereby incorporated by
reference.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] While the specification concludes with claims particularly
pointing out and distinctly claiming the subject matter which is
regarded as forming the present invention, it is believed that the
invention will be better understood from the following description
taken in conjunction with the accompanying drawings, in which:
[0029] FIG. 1 is a schematic side view of a hard surface with
several layers of nanoparticles that form a coating thereon, and
soil on a portion of the nanoparticle coating.
[0030] FIG. 2 is a schematic side view similar to FIG. 1, only
showing how the removal of the top layer of nanoparticles may
remove the soil deposited on the coating.
[0031] FIG. 3 is a schematic side view similar to FIGS. 1, 2
showing a further step in the removal process.
[0032] FIG. 4 is a flow diagram showing the steps in one embodiment
of a clear coat application process for use in the automotive
industry.
DETAILED DESCRIPTION OF THE INVENTION
[0033] Inanimate Hard Surfaces
[0034] Fiberglass surfaces comprise resins, polymers, reinforcing
fabric and fibers. Hard surfaces made from fiberglass include but
are not limited to bathtubs, boats, motorcycles, car bodies,
canoes, airplanes, model aircraft, jet skis, sculptures, as well as
traditional industrial molding and model-making articles.
[0035] There are seven basic types of hard surface plastics which
include polyethylene terephthalate (PET), high density polyethylene
(HDPE), polyvinyl chloride (PVC), low density polyethylene (LDPE),
polypropylene (PP), polystyrene (PS), polymers and mixtures
thereof. Manufacturers are unlimited in the number and types of
articles that can be made from plastic. Carbon and graphite fibers
are high-strength materials that are used as reinforcing agents in
plastic composites. Examples of plastic articles include bottles,
jars, jugs, bags, covers, pipes, furniture, containers, caps, cups,
trays, aircraft fuselages and wings, spacecraft structures, and
sports equipment.
[0036] Both ferrous and nonferrous metal surfaces are available for
use with this invention. These include aluminum, brass, bronze,
chrome, copper, tin, zinc, iron, stainless steel and steel.
Examples of metal surfaces include (e.g. buildings, doors, window
frames, automobiles, boats, structures, and many more too numerous
to mention).
[0037] There are three basic types of glass-sheet, plate, and
float. These basic glass types can be changed to meet modern
requirements for comfort, security, safety, and architectural needs
by adding chemicals or other ingredients during fabrication and
processing.
[0038] There are a number of distinct dishware surface types
available. Dishware can include glassware, ceramic ware, plastic
ware, wood ware and metal ware. Examples of dishware include
agateware, basalt, bisque, bone china, cauliflower ware, cream
ware, delft, earthenware, flambe, hard paste porcelain, ironstone,
jackfield, jasper, lusterware, majolica, marbled, parian,
pate-sur-pate, pearl ware, porcelain, redware, salt glaze,
slipware, snowman-porcelain, soft paste porcelain, spatter ware,
staffordshire figures, stoneware, tortoiseshell, and transfer ware.
Utensils can also be made from any of the above materials.
[0039] Ceramic surfaces include glazed tile, mosaic tile, and
quarry tile. Applications of ceramic tiles include countertops,
walls, floors, ceilings and appliances.
[0040] Other types of surfaces, such as sinks, bath tubs, and
toilets may be made of porcelain, ceramic, or other materials.
[0041] There are many types of wood surfaces available. Examples of
some types of wood include wood surface is selected from the group
consisting of alder, ash, aspen, beech, birch, bocote, bubinga,
butternut, cedar, cherry, cocobolo, canarywood, cypress, ebony,
hickory, holly, kingwood, lacewood, locust, mahogany, maple, oak,
osage, parawood, padauk, pecan, persimmon, poplar, purpleheart,
redheart, rosewood, spanish cedar, sycamore, teak, tulipwood,
walnut, wenge, zebrawood, ziricote. Articles made from wood can
include furniture, baseball bats, chairs, stools, furniture,
handles, motor-vehicle parts, barrels and crates, sporting and
athletic goods, railroad ties, veneer, flooring, treated lumber,
such as that used for decks, siding, crates, and interior
finishing.
[0042] There are three basic types of stone surfaces available-
igneous, metamorphic and sedimentary. Some of these surfaces
include granite, marble, slate, sandstone, serpentinite, schistose
gneiss, quartzite, sandstone, limestone and fieldstone. Stone is
often used in construction of buildings, roads, walls, fireplaces
and monuments. There are a number of types of concrete surfaces
available as well. These surfaces include unreinforced concrete,
reinforced concrete, cast-in-place concrete, precast concrete,
post-tensioned concrete, and prestressed concrete. Examples of
concrete surfaces include building components, bridge components,
walls, streets, curbs and gutters. Asphalt comes in four types -
hot-mix asphalt, cold-mix asphalt, glassphalt and rubberized
asphalt. Asphalt is used on road surfaces, walls, roofing and
sporting tracks. There are a multitude of mineral surfaces
available. Minerals comprise ores of metal and other natural
substances that can be mined. Examples of mineral surfaces may
include jewelry, furniture, building components and many more.
Finally coated and painted surfaces are also examples of hard
surfaces that can be modified by the present invention to derive
the desired benefits.
[0043] Nanoparticle System
[0044] The nanoparticle system can comprise materials,
compositions, devices, appliances, procedures, methods, conditions,
etc. serving a common purpose of modification of hard surfaces to
bring about the desired multi-use benefits of improved wetting and
sheeting, quick drying, uniform drying, soil removal,
self-cleaning, anti-spotting, anti-soil deposition, cleaner
appearance, enhanced gloss, enhanced color, minor surface defect
repair, improved smoothness, anti-hazing properties, modification
of surface friction, release of actives, reduced damage to abrasion
and improved transparency.
[0045] Nanoparticles, defined as particles with diameters of about
400 nm or less, are technologically significant, since they are
utilized to fabricate structures, coatings, and devices that have
novel and useful properties due to the very small dimensions of
their particulate constituents. Nanoparticles with particle sizes
ranging from about 2 nm to about 400 nm can be economically
produced. Particle size distributions of the nanoparticles in the
present invention may fall anywhere within the range from about 1
nm, or less, to less than about 400 nm, alternatively from about 2
nm to less than about 100 nm, and alternatively from about 2 nm to
less than about 50 nm. For example, a layer synthetic silicate can
have a mean particle size of about 25 nanometers while its particle
size distribution can generally vary between about 10 nm to about
40 nm. Alternatively, nanoparticles can also include crystalline or
amorphous particles with a particle size from about 1, or less, to
about 100 nanometers, alternatively from about 2 to about 50
nanometers. Nanotubes can include structures up to 1 centimeter
long, alternatively with a particle size from about 1, or less, to
about 50 nanometers.
[0046] The coating composition comprises nanoparticles; optionally
a surfactant; optionally having associated to said nanoparticle
surface a quantity of one or more functionalized surface molecules
exhibiting properties selected from the group consisting of
hydrophilic, hydrophobic and mixtures thereof; optionally one or
more adjunct ingredients; and a suitable carrier medium to form a
transparent coating on a hard surface.
[0047] Inorganic nanoparticles generally exist as oxides,
silicates, carbonates and hydroxides. Some layered clay minerals
and inorganic metal oxides can be examples of nanoparticles. The
layered clay minerals suitable for use in the present invention
include those in the geological classes of the smectites, the
kaolins, the illites, the chlorites, the attapulgites and the mixed
layer clays. Typical examples of specific clays belonging to these
classes are the smectites, kaolins, illites, chlorites,
attapulgites and mixed layer clays. Smectites, for example, include
montmorillonite, bentonite, pyrophyllite, hectorite, saponite,
sauconite, nontronite, talc, beidellite, volchonskoite and
vermiculite. Kaolins include kaolinite, dickite, nacrite,
antigorite, anauxite, halloysite, indellite and chrysotile. Illites
include bravaisite, muscovite, paragonite, phlogopite and biotite.
Chlorites include corrensite, penninite, donbassite, sudoite,
pennine and clinochlore. Attapulgites include sepiolite and
polygorskyte. Mixed layer clays include allevardite and
vermiculitebiotite. Variants and isomorphic substitutions of these
layered clay minerals offer unique applications.
[0048] The layered clay minerals of the present invention may be
either naturally occurring or synthetic. An example of one
embodiment of the present invention uses natural or synthetic
hectorites, montmorillonites and bentonites. Another embodiment
uses the hectorites clays commercially available, and typical
sources of commercial hectorites are the Laponites from Southern
Clay Products, Inc., U.S.A; Veegum Pro and Veegum F from R. T.
Vanderbilt, U.S.A.; and the Barasyms, Macaloids and Propaloids from
Baroid Division, National Read Comp., U.S.A.
[0049] The inorganic metal oxides of the present invention may be
silica- or alumina- based nanoparticles that are naturally
occurring or synthetic. Aluminum can be found in many naturally
occurring sources, such as kaolinite and bauxite. The naturally
occurring sources of alumina are processed by the Hall process or
the Bayer process to yield the desired alumina type required.
Various forms of alumina are commercially available in the form of
Gibbsite, Diaspore, and Boehmite from manufactures such as
Condea.
[0050] Natural Clays--Natural clay minerals typically exist as
layered silicate minerals and less frequently as amorphous
minerals. A layered silicate mineral has SiO.sub.4 tetrahedral
sheets arranged into a two-dimensional network structure. A 2:1
type layered silicate mineral has a laminated structure of several
to several tens of silicate sheets having a three layered structure
in which a magnesium octahedral sheet or an aluminum octahedral
sheet is sandwiched between two sheets of silica tetrahedral
sheets.
[0051] A sheet of an expandable layer silicate has a negative
electric charge, and the electric charge is neutralized by the
existence of alkali metal cations and/or alkaline earth metal
cations. Smectite or expandable mica can be dispersed in water to
form a sol with thixotropic properties. Further, a complex variant
of the smectite type clay can be formed by the reaction with
various cationic organic or inorganic compounds. As an example of
such an organic complex, an organophilic clay in which a
dimethyldioctadecyl ammonium ion(a quaternary ammonium ion) is
introduced by cation exchange and has been industrially produced
and used as a gellant of a coating.
[0052] Synthetic Clays--With appropriate process control, the
processes for the production of synthetic nanoscale powders (i.e.
synthetic clays) does indeed yield primary particles, which are
nanoscale. However, the particles are not usually present in the
form of discrete particles, but instead predominantly assume the
form of agglomerates due to consolidation of the primary particles.
Such agglomerates may reach diameters of several thousand
nanometers, such that the desired characteristics associated with
the nanoscale nature of the particles cannot be achieved. The
particles may be deagglomerated, for example, by grinding as
described in EP-A 637,616 or by dispersion in a suitable carrier
medium, such as water or water/alcohol and mixtures thereof.
[0053] The production of nanoscale powders such as layered hydrous
silicate, layered hydrous aluminum silicate, fluorosilicate,
mica-montmorillonite, hydrotalcite, lithium magnesium silicate and
lithium magnesium fluorosilicate are common. An example of a
substituted variant of lithium magnesium silicate is where the
hydroxyl group is partially substituted with fluorine. Lithium and
magnesium may also be partially substituted by aluminum. In fact,
the lithium magnesium silicate may be isomorphically substituted by
any member selected from the group consisting of magnesium,
aluminum, lithium, iron, chromium, zinc and mixtures thereof.
[0054] Synthetic hectorite was first synthesized in the early
1960's and is now commercially marketed under the trade name
LaponiteTm by Southern Clay Products, Inc. There are many grades or
variants and isomorphous substitutions of LaponiteTM marketed.
Examples of commercial hectorites are Lucentite SWNTM, Laponite
STM, Laponite XLSTM, Laponite RDTM and Laponite RDSTM. One
embodiment of this invention uses Laponite XLSTM having the
following characteristics: analysis (dry basis) SiO.sub.2 59.8%,
MgO 27.2%, Na.sub.2 0 4.4%, Li.sub.2 0 0.8%, structural H.sub.2O
7.8%, with the addition of tetrasodium pyrophosphate (6%); specific
gravity 2.53; bulk density 1.0.
[0055] Synthetic hectorites, such as Laponite RDTM, do not contain
any fluorine. An isomorphous substitution of the hydroxyl group
with fluorine will produce synthetic clays referred to as sodium
magnesium lithium fluorosilicates. These sodium magnesium lithium
fluorosilicates, marketed as Laponite.TM. and Laponite S.TM.,
contain fluoride ions of approximately 5% by weight. Laponite B.TM.
has a mean particle size of about 25 nanometers in length and about
1 nanometer in thickness. Another variant, called Laponite S.TM.,
contains about 6% of tetrasodium polyphosphate as an additive.
[0056] LaponiteTm has the formula:
[Mg.sub.wLi.sub.xSi.sub.8O.sub.20OH.sub.4-yF.sub.y]
[0057] wherein w=3 to 6, x=0 to 3, y=0 to 4, z=12-2w-x, and the
overall negative lattice charge is balanced by counter-ions; and
wherein the counter-ions are selected from the group consisting of
selected Na.sup.+, K.sup.+, NH.sub.4.sup.+, Cs.sup.+, Li.sup.+,
Mg.sup.++, Ca.sup.++, Ba.sup.++, N(CH.sub.3).sub.4.sup.+ and
mixtures thereof.
[0058] Depending upon the application, the use of variants and
isomorphous substitutions of Laponite.TM. provides great
flexibility in engineering the desired properties of the coating
composition of the present invention. The individual platelets of
LaponiteTm are negatively charged on their faces and possess a high
concentration of surface bound water. When applied to a hard
surface, the hard surface is hydrophilically modified and exhibits
surprising and significantly improved wetting and sheeting, quick
drying, uniform drying, anti-spotting, anti-soil deposition,
cleaner appearance, enhanced gloss, enhanced color, minor surface
defect repair, improved smoothness, anti-hazing properties,
modification of surface friction, release of actives, reduced
damage to abrasion and improved transparency properties. In
addition, the Laponite.TM. modified surface exhibits short lived
"self-cleaning" properties (dirt removal via water rinsing, e.g.
from rainwater) and/or soil release benefits (top layers are
strippable via mild mechanical action).
[0059] In contrast to hydrophilic modification with organic
polymers, benefits provided by Laponite.TM. , either alone or in
combination with a charged modifier, are longer lived. For example,
sheeting/anti-spotting benefits are maintained on an automobile
body and glass window after multiple rinses versus one rinse with
tap water or rainwater versus on a surface coated with current
hydrophilic polymer technology.
[0060] Inorganic Metal Oxides--Inorganic metal oxides generally
fall within two groups--photoactive and non-photoactive
nanoparticles. General examples of photoactive metal oxide
nanoparticles include zinc oxide and titanium oxide. Photoactive
metal oxide nanoparticles require photoactivation from either
visible light (e.g. zinc oxide) or from UV light (TiO.sub.2). Zinc
oxide coatings have generally been used as anti-microbial agents or
as anti-fouling agents.
[0061] Titanium dioxide is taken to be rutiles, anatases and
amorphous titanium dioxide having a particle size of 1 to 100 nm,
alternatively of 1 to 10 nm, or titanium dioxide having the
above-stated particle size in dispersed form. A range of
interesting industrial applications for such titanium dioxide
particles is beginning to emerge: as a photoactive UV screening
agent in cosmetics, plastics, silicone resins and lacquers, wherein
the transparency due to the small particle size is a particularly
desirable characteristic of the particles; as a flame retardant and
to increase the refractive index of silicones and plastics, as
described in FR 2 682 369; in protection to degrade organic
pollutants, including halogenated pollutants, in waste waters by
photocatalysis; to accelerate the decomposition of (bio)degradable
polymers; as a support material for novel dye solar cells, as are
described, for example, in PCT-WO 93/20569; together with SiO.sub.2
produced using the same method, as a component in special glasses
(JP. Pat. No. 10,297,436 A2).
[0062] Non-photoactive metal oxide nanoparticles do not use UV or
visible light to produce the desired effects. Examples of
non-photoactive metal oxide nanoparticles include silica and
alumina.
[0063] It is possible using the sol/gel process, starting from
metal alkoxides, to produce particles having an average diameter of
below 50 nm by a controlled increase in molecular weight. Such
systems are used, for example, as coating compositions or active
substance precursors as described, e.g., in The Polymeric Materials
Encyclopedia1996, volume 6, 4782-4792 et seq.).
[0064] Nanoscale metal oxide sols are usually 10 to 50% colloidal
solutions of metal oxides (Si, Al, Ti, Zr, Ta, Sn, Zn) having
average particle sizes of 2 to about 50 nm in aqueous or organic
media. Organophilic particles of a metal oxide chosen from alumina
(A1.sub.2O.sub.3), silica (SiO.sub.3), titanium (TiO.sub.2) in
which process an aqueous-alcoholic suspension of metal oxide
particles have no pores less than 5 nm in diameter at their
surface. It is possible to prevent such metal oxide sols from
agglomerating by electric and/or steric stabilization of the
particle surfaces. Aqueous silica sols may in particular be
mentioned, which may be produced, for example, from alkaline
solutions by ion exchange processes (for example Ullmann's
Encyclopedia of Industrial Chemistry, 5.sup.th edition, volume A23,
VCH-Verlag, Weinheim, 1993, pp. 614-629). Such products are
commercially available, for example under trade names such as
Levasil (Bayer AG).
[0065] Boehmite alumina is a water dispersible, inorganic metal
oxide having a mean particle size of about 25 nanometers in length
and about 2-4 nanometers in thickness. Such product is commercially
available, for example, under the trade name Disperal P2.TM..
[0066] Prior art disclosures have shown it is possible to coat
cellulosic materials with colloidal silica sols. In the past,
generally dilute aqueous solutions of colloidal silica and urea for
non-skid surface compositions for paper products, especially
paperboard containing recycled paper fibers, are disclosed in U.S.
Pat. Nos. 4,418,111 and 4,452,723 Carstens (assigned to Key Tech
Corporation). The use of colloidal silica sols to coat paper in
order to provide slip resistance is disclosed in U.S. Pat. Nos.
2,643,048 and 2,872,094.
[0067] Inorganic metal oxide nanoparticle provide an additional
benefit above those of the layered clays where concentrated sols of
inorganic metal oxides can be prepared without gelling. This is
particularly advantageous for applications that utilize a dilution
step prior to application of the coating composition. Additionally,
inorganic metal oxide nanoparticles can provide tolerance to hard
water used in making nanoparticle dispersions, diluting
nanoparticles dispersion compositions, and the application of
nanoparticle compositions wherein the surface contains hard water
ions.
[0068] Colloidal silica sols have also been employed to impart
stiffness to paper and generally for the treatment of paper as
disclosed in U.S. Pat. Nos. 2,883,661; 2,801,938; 2,980,558 and
other patents.
[0069] Charged Functionalized Molecules
[0070] In the present invention, one or more charged functionalized
surface molecules may comprise at least two different types of
functionalized surface molecules. Furthermore, charged
functionalized surface molecules are selected from the group
consisting of polymers, copolymers, surfactants and mixtures
thereof. Functionalized surface molecules can also be selected from
the group consisting of multi-valent inorganic salts consisting of
Ca.sup.+2, Mg.sup.+2, Ba.sup.+2, Al.sup.+3, Fe.sup.+2, Fe.sup.+3,
Cu.sup.+2 and mixtures thereof, where an appropriate anion is used
to balance the charge.
[0071] In application, hydrophilic modification can be augmented
via use of Laponite.TM. as a basecoat or primer and then treating
the negatively charged surface with functionalized charged
molecules as a two-step process. Specifically, sequential layering
of Laponite.TM. and ethoxylated, quatemized oligoamines results in
a reduction in the contact angles, and enhanced sheeting/wetting of
the treated surface. Moreover, if the charged functionalized
molecule species possess a lipophilic component, the Laponite
treated surface can be hydrophobically modified. Net, the
combination of nanoclay plus charge functionalized molecules
provides a novel technique for tailoring the hydrophilic/lipophilic
character of a hard surface.
[0072] Similarly, hydrophilic modification can be augmented via use
of alumina as a basecoat or primer and then treating the positively
charged surface with functionalized charged molecules as a two-step
process. Specifically, sequential layering of alumina and
hydrophilic anionic polymers results in enhanced sheeting/wetting
of the treated surface. Moreover, if the charged functionalized
molecule species possess a lipophilic component, the alumina
treated surface can be hydrophobically modified. Net, the
combination of inorganic metal oxides plus charge functionalized
molecules provides a novel technique for tailoring the
hydrophilic/lipophilic character of a hard surface.
I. COMPOSITION
[0073] If the coating is in the form of a composition, the coating
composition may be in any form, such as liquids (aqueous or
non-aqueous), granules, pastes, powders, spray, foam, tablets,
gels, and the like. Granular compositions can be in "compact" form
and the liquid compositions can also be in a "concentrated" form.
The coating compositions of the present invention encompass
compositions that are used on any suitable hard surface including,
but not limited to: fiberglass, plastics, metals, glass, ceramic,
wood, stone, concrete, asphalt, mineral, coated surfaces, painted
surfaces and mixtures thereof.
[0074] In one embodiment, the hard surface coating composition
comprises: (a) an effective amount of non-photoactive
nanoparticles; (b) optionally one or more adjunct ingredients; and
(c) optionally a suitable carrier medium.
[0075] In another embodiment, the hard surface coating composition
comprises: (a) an effective amount of non-photoactive
nanoparticles; (b) a surfactant; (c) optionally one or more adjunct
ingredients; and (d) a suitable carrier medium.
[0076] In another embodiment, the hard surface coating composition
comprises: (a) an effective amount of non-photoactive
nanoparticles; (b) a surfactant; (c) having associated to said
nanoparticle surface a quantity of one or more functionalized
surface molecules exhibiting properties selected from the group
consisting of hydrophilic, hydrophobic and mixtures thereof; (d)
optionally one or more adjunct ingredients; and (e) a suitable
carrier medium.
[0077] In another embodiment, the hard surface coating composition
comprises: (a) an effective amount of non-photoactive
nanoparticles; (b) a surfactant; (c) having associated to said
nanoparticle surface a quantity of one or more functionalized
surface molecules exhibiting properties selected from the group
consisting of hydrophilic, hydrophobic and mixtures thereof; (d) an
effective amount of photoactive nanoparticles; (e) optionally one
or more adjunct ingredients; and (f) a suitable carrier medium.
[0078] Alternatively an effective amount of one or more
nanoparticles described above are included in compositions useful
for coating a variety of hard surfaces in need of treatment. As
used herein, "effective amount of one or more nanoparticles" refers
to the quantity of nanoparticles of the present invention described
hereinbefore necessary to impart the desired hard surface coating
benefit in the specific composition. Such effective amounts are
readily ascertained by one of ordinary skill in the art and is
based on many factors, such as the particular nanoparticle used,
the hard surface coating application, the specific composition of
the hard surface coating composition, and whether a liquid or dry
(e.g., granular, powder) composition is required, and the like.
[0079] An effective amount of a non-photoactive nanoparticle in the
present invention, such as a natural clay, synthetic clay or an
inorganic metal oxide, requires that at least 10% of the target
surface is modified to effect the desired benefits.
[0080] The concentration of nanoparticles in the material or the
compositions described herein can range all the way up to 100%. A
non-limiting example of the use of nanoparticles in such a high
concentration would be if the nanoparticles alone were applied in
the form of a powder to the surface to be treated.
[0081] In one non-limiting aspect of the present invention, the
concentration of nanoparticles in the coating composition prior to
application to a hard surface is less than or equal to about 50% by
weight of the coating composition, or any number less than 50% of
the weight of the coating composition (e.g., less than or equal to
about 20%, for example when the coating composition is a liquid
that is to be sprayed onto the hard surface; alternatively, less
than or equal to about 0.5%, alternatively less than or equal to
about 0.1%).
[0082] In one aspect of the present invention, the coating
composition is prepared by dispersing the dry nanoparticle powder
into deionized water to form a 1% concentrated mixture. This
mixture is then applied to said surface by either spraying,
dipping, painting, wiping, or other manner in order to deliver a
coating, especially a transparent coating that covers at least 10%
and/or alternatively at least 30% and/or alternatively at least 50%
and/or alternatively at least 80% and/or alternatively at least
100% of said surface.
[0083] In another embodiment of the present invention, the coating
composition is prepared by diluting a nanoparticle gel with
deionized water to form a 1% concentrated mixture. This mixture is
then applied to said surface by either spraying, dipping, painting,
wiping, or other manner in order to deliver a transparent coating
that covers at least 10% and/or alternatively at least 30% and/or
alternatively at least 50% and/or alternatively at least 80% and/or
alternatively at least 100% of said surface.
[0084] In another embodiment of the present invention, the coating
composition is prepared by diluting a 10% concentrated boehmite
alumina (e.g. Disperal P2TM from Condea, Inc.) coating composition
with deionized water to form a 0.1% concentrated mixture. This
mixture is then applied to said surface by either spraying,
dipping, painting, wiping, or other manner in order to deliver a
coating especially a transparent coating that covers at least 10%
and/or alternatively at least 30% and/or alternatively at least 50%
and/or alternatively at least 80% and/or alternatively at least
100% of said surface.
[0085] In another embodiment of the present invention, the coating
composition is prepared by diluting a 1% concentrated sodium
magnesium lithium fluorosilicate (e.g. Laponite BTM from Southern
Clay Products, Inc.) coating composition with deionized water to
form a 0.1% concentrated mixture. This mixture is then applied to
said surface by either spraying, dipping, painting, wiping, or
other manner in order to deliver a coating especially a transparent
coating that covers at least 10% and/or alternatively at least 30%
and/or alternatively at least 50% and/or alternatively at least 80%
and/or alternatively at least 100% of said surface.
[0086] In another embodiment of the present invention, the coating
composition is prepared by diluting a 1% concentrated lithium
magnesium sodium silicate (e.g. Lucentite SWNTM from Kobo Products,
Inc.) coating composition with deionized water to form a 0. 1%
concentrated mixture. This mixture is then applied to said surface
by either spraying, dipping, painting, wiping, or other manner in
order to deliver a coating especially a transparent coating that
covers at least 10% and/or alternatively at least 30% and/or
alternatively at least 50% and/or alternatively at least 80% and/or
alternatively at least 100% of said surface.
[0087] In another embodiment of the present invention, the coating
composition is prepared by dispersing the dry nanoparticle powder
into deionized water to form a 0.1% concentrated mixture. This
mixture is then applied to said surface by either spraying,
dipping, painting, wiping, or other manner in order to deliver a
coating especially a transparent coating that covers at least 10%
and/or alternatively at least 30% and/or alternatively at least 50%
and/or alternatively at least 80% and/or alternatively at least
100% of said surface.
[0088] In other embodiments, the coating composition is prepared by
dispersing the dry nanoparticle powder with a surfactant and a
dispersant into tap water, so that the use of deionized water is
not necessary. Two non-limiting examples of such a coating
composition are provided in the Examples section at the end of this
description. Examples of other suitable dispersants include, but
are not limited to: poly (acrylic/allyl alcohol), poly
(acrylic/maleic), poly (a-hydroxyacrylic acid), poly
(tetramathylene-1,2-dicarbocylic acid), poly
(4-methocy-tetramethylene-1,- 2-dicarbocylic acid) -sodium
tripolyphosphate, pyrophosphate, and the other dispersants and
builders described herein. This mixture is then applied to said
surface by either spraying, dipping, painting, wiping, or other
manner in order to deliver a coating especially a transparent
coating that covers at least 10% and/or alternatively at least 30%
and/or alternatively at least 50% and/or alternatively at least 80%
and/or alternatively at least 100% of said surface.
[0089] In one non-limiting aspect, an effective amount of charged
functionalized surface molecules that provide hydrophobic
properties to the nanoparticle surface, generally modifies from
about 1% to about 100% of the nanoparticle surface or from about
0.01 to about 5% by weight of the coating composition.
[0090] In other embodiments, rather than modifying the
characteristic of the surface to be coated, the charged
functionalized molecules can be used to aid in the delivery of the
nanoparticles to the surface to be coated. For instance, in one
non-limiting embodiment, a surfactant could be mixed with the
nanoparticles in order to aid in the delivery of the nanoparticles
to the surface to be coated in cases in which it is difficult to
combine the nanoparticle coating with another carrier medium, or in
which it is difficult to apply the nanoparticles to a particular
surface. For example, if the nanoparticles are to be used with an
organic clearcoat composition, it may be difficult to suspend the
nanoparticles in the clearcoat composition, or to spread the
nanoparticle coating on the surface of such a clearcoat
composition. In such a case, the addition of a relatively small
amount of surfactant (e.g., virtually any amount of surfactant or
functionalized molecules, for example a stoichiometric amount) to
the nanoparticles, will aid in overcoming these difficulties. In
such a case, the amount of charged functionalized molecules can be
less than about 0.01% of the coating composition.
[0091] Several non-limiting examples of various coatings and
coating compositions wherein the nanoparticles of the present
invention may be employed are discussed in further detail below.
Also, the coating compositions may include from about 0.001% to
about 99.999%, alternatively from about 0.01% to about 99.99% by
weight of the coating composition of the adjunct materials.
[0092] As used herein, the coatings and "coating compositions"
include hand and machine applied coatings, compositions, including
additive coatings, additive compositions, and compositions suitable
for use in the soaking and/or pretreatment of unclean or stained
hard surfaces. The coatings, coating compositions and/or methods
and/or articles of manufacture of the present invention are for all
uses including manufacturing, commercial, industrial,
institutional, agricultural and/or for domestic use.
[0093] When the coating compositions are formulated as compositions
suitable for use in an enumerated method or article of manufacture,
the coating compositions of the present invention alternatively
contain both an effective amount of nanoparticles and a suitable
carrier medium to form the nanoparticle system and may optionally
include one or more of the following: a surfactant, a quantity of
one or more charged functionalized surface molecules, photoactive
nanoparticles, and one or more adjunct ingredients.
[0094] The coating compositions of the present invention can also
be used as detergent additive products in solid or liquid form.
Such additive products are intended to supplement or boost the
performance of conventional coating compositions used to clean hard
surfaces and can be added at any stage of the cleaning process,
however addition of the transparent hard surface coating
composition to a clean surface is more effective.
[0095] Aqueous liquid, coating compositions according to the
present invention can also be in a "concentrated form", in such
case, the concentrated liquid, coating compositions according the
present invention will contain a lower amount of a suitable carrier
medium, compared to conventional liquid, coating compositions.
Typically the suitable carrier medium content of the concentrated
system, hard surface coating composition is alternatively 99.99 to
50% by weight of the coating composition.
[0096] Aqueous liquid, coating compositions according to the
present invention can also be in a "concentrated form" that is
compatible with "tap water", in such case, the concentrated liquid,
coating compositions according the present invention will contain a
lower amount of a suitable carrier medium, compared to conventional
liquid, coating compositions and a dispersant. Typically the
suitable carrier medium content of the concentrated system, hard
surface coating composition is alternatively 99.99 to 50% by weight
of the coating composition. Typically the dispersant content of the
concentrated system, hard surface coating composition is
alternatively 0.001 to 10%.
[0097] The present invention comprises liquid (a compatible
carrier), coating compositions, alternatively aqueous liquid (a
compatible carrier), coating compositions. Aqueous liquid, coating
compositions alternatively comprise in addition to the nanoparticle
system described hereinabove, about 50% to about 99.99%,
alternatively from about 80% to about 99.99%, by weight of liquid
carrier or suitable carrier medium, such as an alcohol and/or
water.
[0098] The aqueous liquid, coating compositions of the present
invention also alternatively comprise one or more adjunct
materials. The term "adjunct materials", as used herein, means any
liquid, solid or gaseous material selected for aqueous liquid,
coating compositions, alternatively compatible with the other
ingredients present in the aqueous liquid, coating compositions of
the present invention.
[0099] The specific selection of adjunct materials is readily made
by considering the surface or to be cleaned. Examples of suitable
adjunct materials include, but are not limited to, surfactants,
builders, bleaches, bleach activators, bleach catalysts, enzymes,
enzyme stabilizing systems, chelants, optical brighteners, soil
release polymers, dye transfer agents, dispersants, suds
suppressors, dyes, perfumes, colorants, filler salts, hydrotropes,
photoactivators, fluorescers, conditioners, hardening agents,
hydrolyzable surfactants, preservatives, anti-oxidants,
anti-wrinkle agents, germicides, fungicides, color speckles,
silvercare, anti-tarnish and/or anti-corrosion agents, alkalinity
sources, solubilizing agents, carriers, processing aids, pigments
and pH control agents as described in U.S. Pat. Nos. 5,705,464;
5,710,115; 5,698,504; 5,695,679; 5,686,014 and 5,646,101. Specific
adjunct materials are exemplified in detail hereinafter.
[0100] If the adjunct materials are not compatible with the other
ingredients present in the aqueous liquid, coating compositions of
the present invention, then suitable methods of keeping the
incompatible adjunct materials and the other ingredients separate
(not in contact with each other) until combination of the two
components is appropriate can be used. Suitable methods can be any
method known in the art, such as gelcaps, encapsulation, tablets,
physical separation, etc.
[0101] The coating compositions of the present invention can
comprise: (a) an effective amount of non-photoactive nanoparticles;
(b) optionally a surfactant; (c) optionally having associated to
said nanoparticle surface a quantity of one or more functionalized
surface molecules exhibiting properties selected from the group
consisting of hydrophilic, hydrophobic and mixtures thereof; (d)
optionally an effective amount of photoactive nanoparticles; (e)
optionally one or more adjunct ingredients; and (f) a suitable
carrier medium.
[0102] The coating compositions of the present invention can also
be used as detergent additive products in liquid form for automatic
dishwashing machines. Such additive products are intended to
supplement or boost the performance of conventional coating
compositions and can be added at any stage of the dishwashing
process, however, best results are achieved in the rinsing
cycle.
[0103] Further, the coating compositions according to the present
invention may be isotropic liquids, aqueous gels, phase-separated
liquid compositions and/or colored liquid compositions.
[0104] The coating compositions according to the present invention
may be of any suitable viscosity. The viscosity of the coating
compositions should be such that they are able to be effectively
applied to the surface to be coated. Thus, for instance, if the
coating compositions are to be applied to a hard surface that has
portions that are sloped (their slope has a vertical component),
the hard surface coating composition should not have such a low
viscosity that the coating composition runs off the surface to be
coated. Non-limiting examples of suitable viscosities are less than
or equal to about 1,000 Cps at 100 rpm, or any increment of 10 less
than 1,000 (including, but not limited to 100 Cps, 40 Cps, and 1
Cps (the latter being the viscosity of water)). The method for
determining the viscosity of the coating compositions is set forth
in the Test Methods section.
[0105] The dry coating compositions of the present invention can
comprise: (a) an effective amount of non-photoactive nanoparticles;
(b) optionally a surfactant; (c) optionally having associated to
said nanoparticle surface a quantity of one or more functionalized
surface molecules exhibiting properties selected from the group
consisting of hydrophilic, hydrophobic and mixtures thereof; (d)
optionally one or more adjunct ingredients; and (e) an optionally,
a suitable carrier medium.
[0106] The dry coating compositions of the present invention can
also be used as detergent additive products in powder, granule or
tablet form for automatic dishwashing machines. Such additive
products are intended to supplement or boost the performance of
conventional coating compositions and can be added at any stage of
the dishwashing process, however, best results are achieved in the
rinsing cycle.
[0107] Further, the dry coating compositions according to the
present invention may be in powder, granule, tablet or encapsulated
complex form.
[0108] Suitable Carrier Medium
[0109] Suitable carrier mediums include liquids, solids and gases.
One suitable carrier medium is water, which can be distilled,
deionized, or tap water. Water is valuable due to its low cost,
availability, safety, and compatibility. Though aqueous carrier
mediums are more common than dry, nonaqueous mediums, the present
invention can exist as a dry powder, granule or tablet or
encapsulated complex form.
[0110] Optionally, in addition to water, the carrier can contain a
low molecular weight organic solvent that is highly soluble in
water, e.g., ethanol, methanol, propanol, isopropanol and the like,
and mixtures thereof. Low molecular weight alcohols can allow the
treated hard surface to dry faster. The optional water soluble low
molecular weight solvent can be used at a level of up to about 50%,
typically from about 0.1% to about 25%, alternatively from about 2%
to about 15%, alternatively from about 5% to about 10%, by weight
of the suitable carrier medium. Factors that need to consider when
a high level of solvent is combined with the suitable carrier
medium are odor, flammability, dispersancy of the nanoparticle and
environment impact.
[0111] In one non-limiting embodiment, the carrier can comprise any
known clearcoat composition. U.S. Pat. No. 5,853,809 describes one
non-limiting example of a clearcoat composition.
[0112] In other embodiments, the carrier can be an airstream. For
instance, the material, or the composition can be added into a
stream of moving air, and the air can convey the non-photoactive
nanoparticles to the surface to be treated.
[0113] In other embodiments, the coating material or composition
can simply be dropped through the air by gravity onto the surface
to be treated (one example of which would be by sifting a solid
material onto the surface).
[0114] Classes of Functionalized Surface Molecules
[0115] Polymer Classes and Examples
[0116] Polymers and copolymers in which at least one segment or
group of the polymer comprises functionality that serves to anchor
or enhance adsorption on nanoparticle surfaces. These polymers also
comprise at least one segment or group that serves to provide
either hydrophilic or hydrophobic character to the polymer when
adsorbed on a nanoparticle. Note that in some cases, the anchoring
segment may also serve as the hydrophilizing segment.
[0117] Examples of the anchoring segments or groups include:
polyamines, quaternized polyamines, amino groups, quatemized amino
groups, and corresponding amine oxides; zwitterionic polymers;
polycarboxylates; polyethers; polyhydroxylated polymers;
polyphosphonates and polyphosphates; and polymeric chelants.
[0118] Examples of the hydrophilizing segments or groups include:
water soluble polyethers; water soluble polyhydroxylated groups or
polymers, including saccharides and polysaccharides; water soluble
carboxylates and polycarboxylates; water soluble anionic groups
such as carboxylates, sulfonates, sulfates, phosphates,
phosphonates and polymers thereof; water soluble amines,
quaternaries, amine oxides and polymers thereof; water soluble
zwitterionic groups and polymers thereof; water soluble amides and
polyamides; and water soluble polymers and copolymers of
vinylimidazole and vinylpyrrolidone.
[0119] Examples of the hydrophobizing segments or groups include:
alkyl, alkylene, and aryl groups, and polymeric aliphatic or
aromatic hydrocarbons; fluorocarbons and polymers comprising
fluorocarbons; silicones; hydrophobic polyethers such as
poly(styrene oxide), poly(propylene oxide), poly(butene oxide),
poly(tetramethylene oxide), and poly(dodecyl glycidyl ether); and
hydrophobic polyesters such as polycaprolactone and
poly(3-hydroxycarboxylic acids).
[0120] Hydrophilic Surface Polymers
[0121] Ethoxylated or alkoxylated polyamines including:
hexamethylenediamine, ethoxylated to a degree of 3-100 on each NH
site; bis(hexamethylenetriamine), ethoxylated to a degree of 3-100
on each NH site; tetraethylenepentamine, ethoxylated to a degree of
3-100 on each NH site; polyethyleneimine of MW 300-25,000
ethoxylated to a degree of 3-100 per NH or alkoxylated with
propylene or butylene oxide and ethoxylated sufficiently to confer
hydrophilicity; polyvinylamine of MW 200-25,000, ethoxylated to a
degree of 2-100 per NH; polyallylamine of MW 200-25,000,
ethoxylated to a degree of 2-100 per NH; quaternized analogs of the
above with at least one nitrogen quaternized by an alkylating agent
such as methyl chloride, dimethyl sulfate, benzyl chloride, and
ethylene or propylene oxide and mixtures thereof. In addition,
quaternization may be with hydrophobic materials such as dodecyl
bromide with the provision that the level of hydrophobic group so
introduced is not sufficient to make the nanoparticle surface on
which the polymer is adsorbed hydrophobic; sulfated, carboxylated,
or phosphated analogs of the above with at least one of the
terminal OH groups derivatized to introduce the anionic
functionality; amine oxide analogs of the ethoxylated or
alkoxylated polyamines in which at least one amine group is
oxidized to the amine oxide; betaine and sulfobetaine analogs of
the ethoxylated or alkoxylated polyamines in which at least one
amine group is quaternized by an agent such as chloroacetate
propanesultone, or allyl chloride which is subsequently sulfonated;
and combinations of the above.
[0122] Polycarboxylated polyamines include: reaction products of
polyethyleneimine with maleic acid, fumaric acid or chloroacetate.
These may also comprise ethoxylated segments. See US Pat. No.
5,747,440 which is incorporated by reference.
[0123] Polycarboxylates include: polyacrylic and polymethacrylic
acid and copolymers with maleic acid; polymaleic acid and
copolymers comprising maleic acid, fumaric acid, or maleic
anhydride with another monomer such as methyl vinyl ether or a
lower alkene; and graft copolymers of the above polycarboxylates
which further comprise ethoxyated segments such as derived from the
monomethyl ether of polyethylene glycol. The above polycarboxylate
polymers may also comprise hydrophobic groups such as esters of
butanol or 2-ethylhexanol, provided that their level is not
sufficient to render the nanoparticle surface on which the polymer
is adsorbed hydrophobic.
[0124] Polyethers include: block copolymers of ethylene oxide with
propylene oxide, butylene oxide, tetramethylene oxide, styrene
oxide, phenyl glycidyl ether, or fatty glycidyl ethers; block
silicone copolyols comprising polydimethylsiloxane segments and
polyoxyethylene segments, particularly those with small siloxane
segments.
[0125] Polyhydroxyl materials include: methyl cellulose,
hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl
cellulose and hydrophobically modified analogs, provided that the
level of hydrophobic substitution is not sufficient to make the
nanoparticle on which the polymer is adsorbed hydrophobic;
polyvinyl acetate with sufficient hydrolysis to provide
hydrophilicity; and polyvinyl alcohol and hydrophobically modified
polyvinyl alcohol, provided that the level of hydrophobe is not
sufficient to render the nanoparticle on which the polymer is
adsorbed hydrophobic.
[0126] Also included are polyphosphates and phosphonates, such as,
polyphosphoric acid salts.
[0127] Hydrophobic Surface Polymers
[0128] Alkylated polyamines include: polyethyleneimine alkylated
with fatty alkylating agents such as dodecyl bromide, octadecyl
bromide, oleyl chloride, dodecyl glycidyl ether and benzyl chloride
or mixtures thereof, and polyethyleneimine acylated with fatty
acylating agents such as methyl dodecanoate and oleyl chloride.
[0129] Silicones include: polydimethylsiloxane having pendant
aminopropyl or aminoethylaminopropyl groups.
[0130] Fluorinated polymers include: polymers including as monomers
(meth)acrylate esters of perfluorinated or highly fluorinated alkyl
groups.
[0131] Non-Polymeric Materials
[0132] Molecules with at least one segment or group which comprises
functionality that serves to anchor or enhance adsorption on
nanoparticle surfaces. These molecules also comprise at least one
segment or group that serves to provide either hydrophilic or
hydrophobic character to the molecule when adsorbed on a
nanoparticle. Note that in some cases, the anchoring segment may
also serve as the hydrophilizing segment.
[0133] Examples of the anchoring segments or groups that may also
serve as the hydrophilizing segment include amino groups,
quaternized amino groups, and corresponding amine oxides groups;
and zwitterionic groups.
[0134] Examples of the hydrophobizing segments or groups include
alkyl, aryl, alkaryl, and fluoroalkyl surfactants.with cationic,
zwitterionic, semi-polar, nonionic, or anionic head groups.
[0135] Examples of Non-Polymeric Surface Modifying Materials
[0136] Fatty amines and quats including: ditallowdimethylammonium
chloride; octadecyltrimethylammonium bromide; dioleyl amine; and
Benzyltetradecyldimethylammonium chloride.
[0137] Examples of fluorocarbon-based surfactants include:
1-propanaminium,
3-[[(heptadecafluorooctyl)sulfonyl]amino]-N,N,N-trimethy- l-,
iodide (9CI) 1
[0138] 1-propanaminium,
3-[(8-chloro-2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradeca-
fluoro-1-oxooctyl)amino]-N,N,N-trimethyl-, methyl sulfate (9CI)
2
[0139] Silicone-based surfactants include: 1-propanaminium,
N,N,N-trimethyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl-
]-, bromide (9CI) 3
[0140] Fatty zwitterionic surfactants include: 1-dodecanaminium,
N-(2-hydroxy-3-sulfopropyl)-N,N-dimethyl-, inner salt (9CI) 4
[0141] Fatty amine oxides such as hexadecyldimethylamine oxide are
included. Fatty anionic surfactants including: Sodium oleyl
sulfate; potassium oleate; sodium dodecylbenzenesulfonate; xodium
tetradecyl sulfate; and disodium 2-hexadecenylbutanedioate.
[0142] Surfactant
[0143] Surfactant is an optional ingredient of the present
invention. Surfactant is especially useful in the coating
composition to facilitate the dispersion of nanoparticles onto a
hard surface. Such surfactant is alternatively included when the
coating composition is used to treat a hydrophobic hard surface or
when the coating composition is applied with a spray dispenser in
order to enhance the spray characteristics of the coating
composition and allow the coating composition, including the
nanoparticles, to distribute more evenly. The spreading of the
coating composition can also allow it to dry faster, so that the
treated material is ready to use sooner. For concentrated
compositions, the surfactant facilitates the dispersion of many
adjunct ingredients such as antimicrobial actives and perfumes in
the concentrated aqueous compositions. Suitable surfactant useful
in the present invention is surfactant selected from the group
consisting of anionic surfactants, cationic surfactants, nonionic
surfactants, amphoteric surfactants, zwitterionic surfactants and
mixtures thereof.
[0144] When a surfactant is used in the coating composition of the
present invention, it is added at an effective amount to provide
one, or more of the benefits described herein, typically from about
0.01% to about 5%, alternatively from about 0.01% to about 3%,
alternatively from about 0.01% to about 0.5%, by weight of the
usage composition.
[0145] An alternative type of surfactant is ethoxylated surfactant,
such as addition products of ethylene oxide with fatty alcohols,
fatty acids, fatty amines, etc. Optionally, addition products of
mixtures of ethylene oxide and propylene oxide with fatty alcohols,
fatty acids, and fatty amines can be used. The ethoxylated
surfactant includes compounds having the general formula:
R.sup.8-Z--(CH.sub.2CH.sub.2O).sub.sB
[0146] wherein R.sup.8 is an alkyl group or an alkyl aryl group,
selected from the group consisting of primary, secondary and
branched chain alkyl hydrocarbyl groups, primary, secondary and
branched chain alkenyl hydrocarbyl groups, and/or primary,
secondary and branched chain alkyl- and alkenyl-substituted
phenolic hydrocarbyl groups having from about 6 to about 20 carbon
atoms, alternatively from about 8 to about 18, alternatively from
about 10 to about 15 carbon atoms; s is an integer from about 2 to
about 45, alternatively from about 2 to about 20, alternatively
from about 2 to about 15; B is a hydrogen, a carboxylate group, or
a sulfate group; and linking group Z is --O--, --C(O)O--, or
--C(O)N(R)--, and mixtures thereof, in which R, when present, is
R.sup.8 or hydrogen.
[0147] The nonionic surfactants herein are characterized by an HLB
(hydrophilic-lipophilic balance) of from 5 to 20, alternatively
from 6 to 15.
[0148] Nonlimiting examples of alternative ethoxylated surfactant
are:
[0149] straight-chain, primary alcohol ethoxylates, with R being
C.sub.8-C.sub.18 alkyl and/or alkenyl group, alternatively
CIO-C.sub.14, and s being from about 2 to about 8;
[0150] straight-chain, secondary alcohol ethoxylates, with R being
C.sub.8-C.sub.18 alkyl and/or alkenyl, e.g., 3-hexadecyl,
2-octadecyl, 4-eicosanyl, and 5-eicosanyl, and s being from about 2
to about 10;
[0151] alkyl phenol ethoxylates wherein the alkyl phenols having an
alkyl or alkenyl group containing from 3 to 20 carbon atoms in a
primary, secondary or branched chain configuration, alternatively
from 6 to 12 carbon atoms, and s is from about 2 to about 12;
[0152] branched chain alcohol ethoxylates, wherein branched chain
primary and secondary alcohols (or Guerbet alcohols), which are
available, e.g., from the well-known "OXO" process or modification
thereof, are ethoxylated.
[0153] Other examples of alternative ethoxylated surfactants
include carboxylated alcohol ethoxylate, also known as ether
carboxylate, with R.sup.8 having from about 12 to about 16 carbon
atoms and s being from about 5 to about 13; ethoxylated quaternary
ammonium surfactants, such as PEG-5 cocomonium methosulfate, PEG-15
cocomonium chloride, PEG-15 oleammonium chloride and
bis(polyethoxyethanol)tallow ammonium chloride.
[0154] Other suitable nonionic ethoxylated surfactants are
ethoxylated alkyl amines derived from the condensation of ethylene
oxide with hydrophobic alkyl amines, with R.sup.8 having from about
8 to about 22 carbon atoms and s being from about 3 to about
30.
[0155] Also suitable nonionic ethoxylated surfactants for use
herein include alkylpolysaccharides, which are disclosed in U.S.
Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986, having a
hydrophobic group containing from about 8 to about 30 carbon atoms,
alternatively from about 10 to about 16 carbon atoms and a
polysaccharide, e.g., a polyglycoside, hydrophilic group containing
from about 1.3 to about 10, alternatively from about 1.3 to about
3. Any reducing saccharide containing 5 or 6 carbon atoms can be
used, e.g., glucose, galactose and galactosyl moieties can be
substituted for the glucosyl moieties. The intersaccharide bonds
can be, e.g., between the one position of the additional saccharide
units and the 2-, 3-, 4-, and/or 6-positions on the preceding
saccharide units. The alternative alkylpolyglycosides have the
formula:
R.sup.2O(C.sub.nH.sub.2nO)t(glYcosyl).sub.x
[0156] wherein R.sup.2 is selected from the group consisting of
alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures
thereof in which the alkyl groups contain from 10 to 18,
alternatively from 12 to 14, carbon atoms; n is 2 or 3, t is from 0
to about 10; and x is from about 1.3 to about 10 alternatively. The
glycosyl is alternatively derived from glucose.
[0157] Another class of alternative surfactants that are useful in
the formulation of the coating compositions of the present
invention, to solubilize and/or disperse silicone lubricants and/or
silicone-containing adjunct shape retention copolymers, are
silicone surfactants. Also known as silicone superwetting agents.
They can be used alone and/or alternatively in combination with the
alternative alkyl ethoxylate surfactants described herein above.
Nonlimiting examples of silicone surfactants are the polyalkylene
oxide polysiloxanes having a dimethyl polysiloxane hydrophobic
moiety and one or more hydrophilic polyalkylene side chains, and
having the general formula:
R.sup.1--CH.sub.3).sub.2SiO--[(CH.sub.3)(R.sup.1)Sio].sub.b--Si(CH.sub.3).-
sub.2--R.sup.1
[0158] wherein a+b are from about 1 to about 50alternatively, and
each R.sup.1 is the same or different and is selected from the
group consisting of methyl and a poly(ethyleneoxide/propyleneoxide)
copolymer group having the general formula:
[0159]
--(CH.sub.2).sub.nO(C.sub.2H.sub.4O).sub.c(C.sub.3H.sub.6O).sub.dR.-
sup.2
[0160] wherein n is 3 or 4; total c (for all polyalkyleneoxy side
groups) has a value of from 1 to about 100, alternatively from
about 6 to about 100; total d is from 0 to about 14; alternatively
d is 0; total c+d has a value of from about 5 to about 150,
alternatively from about 9 to about 100 and each R.sup.2 is the
same or different and is selected from the group consisting of
hydrogen, an alkyl having 1 to 4 carbon atoms, and an acetyl group,
alternatively hydrogen and methyl group. Each polyalkylene oxide
polysiloxane has at least one R.sup.1 group being a
poly(ethyleneoxide/propyleneoxide) copolymer group.
[0161] Nonlimiting examples of this type of surfactants are the
Silwet.RTM. surfactants, which are available OSi Specialties, Inc.,
Danbury, Connecticut. Representative Silwet surfactants which
contain only ethyleneoxy (C.sub.2H.sub.4O) groups are as
follows.
1 Name Average MW Average a + b Average total c L-7608 600 1 9
L-7607 1,000 2 17 L-77 600 1 9 L-7605 6,000 20 99 L-7604 4,000 21
53 L-7600 4,000 11 68 L-7657 5,000 20 76 L-7602 3,000 20 29 L-7622
10,000 88 75
[0162] The molecular weight of the polyalkyleneoxy group (R.sup.1)
is less than or equal to about 10,000. A1ternatively, the molecular
weight of the polyalkyleneoxy group is less than or equal to about
8,000, and most alternatively ranges from about 300 to about 5,000.
Thus, the values of c and d can be those numbers which provide
molecular weights within these ranges. However, the number of
ethyleneoxy units (--C.sub.2H.sub.4O) in the polyether chain
(R.sup.1) must be sufficient to render the polyalkylene oxide
polysiloxane water dispersible or water soluble. If propyleneoxy
groups are present in the polyalkylenoxy chain, they can be
distributed randomly in the chain or exist as blocks. Surfactants
which contain only propyleneoxy groups without ethyleneoxy groups
are not preferred. Alternative Silwet surfactants are L-77, L-7280,
L-5550, L-7280, L7608, L7607, and mixtures thereof.
[0163] Another nonlimiting example of this type of surfactant are
silicone superwetting agents available from Dow Corning and sold as
silicone superwetting agents such as silicone glycol copolymers
(e.g. Q2-5211 and Q2-5212).
[0164] Other useful silicone surfactants are those having a
hydrophobic moiety and hydrophilic ionic groups, including, e.g.,
anionic, cationic, and amphoteric groups. Nonlimiting examples of
anionic silicone surfactants are silicone sulfosuccinates, silicone
sulfates, silicone phosphates, silicone carboxylates, and mixtures
thereof, as disclosed respectively in U.S. Pat. Nos, 4,717,498;
4,960,845; 5,149,765 and 5,296,434. Nonlimiting examples of
cationic silicone surfactants are silicone alkyl quats (quaternary
ammoniums), silicone amido quats, silicone imidazoline quats, and
mixtures thereof, as disclosed respectively in U.S. Pat. Nos.
5,098,979; 5,135,294 and 5,196,499. Nonlimiting examples of
amphoteric silicone surfactants are silicone betaines, silicone
amino proprionates, silicone phosphobetaines, and mixtures thereof,
as disclosed respectively in U.S. Pat. Nos. 4,654,161; 5,073,619
and 5,237,035. A1l of these patents are incorporated herein by
reference.
[0165] The coating composition of the present invention to be used
in the automatic dishwashing cycle can be either used along with a
general detergent or actually as a rinse aid in the rinsing or
drying cycle. The coating compositions according to the present
invention comprise a nanoparticle system and optionally a
surfactant or surfactant system wherein the surfactant can be
selected from nonionic and/or anionic and/or cationic and/or
ampholytic and/or zwitterionic and/or semi-polar nonionic
surfactants.
[0166] The surfactant is typically present at a level of from about
0.01% to about 5% by weight. More alternative levels of
incorporation are about 0.01% to about 3% by weight, most
alternatively from 0.01% to 0.5% by weight of coating compositions
in accord with the invention.
[0167] The surfactant is alternatively formulated to be compatible
with the nanoparticle system, suitable carrier medium and optional
adjunct ingredients present in the coating composition.
[0168] Examples of suitable nonionic, anionic, cationic,
ampholytic, zwitterionic and semi-polar nonionic surfactants are
disclosed in U.S. Pat. Nos. 5,707,950 and 5,576,282, incorporated
herein by reference.
[0169] Other nonlimiting examples of nonionic surfactants are
polyhydroxy fatty acid amide surfactants of the formula:
R.sup.2--C(O)--N(R.sup.1)--Z,
[0170] wherein R.sup.1 is H, or R.sup.1 is C.sub.1-4 hydrocarbyl,
2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R.sup.2 is
C.sub.5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a
linear hydrocarbyl chain with at least 3 hydroxyls directly
connected to the chain, or an alkoxylated derivative thereof.
Alternatively, R.sup.1 is methyl, R.sup.2 is a straight C.sub.1-15
alkyl or C.sub.16-18 alkyl or alkenyl chain such as coconut alkyl
or mixtures thereof, and Z is derived from a reducing sugar such as
glucose, fructose, maltose, lactose, in a reductive amination
reaction.
[0171] Alternative anionic surfactants include alkyl alkoxylated
sulfate surfactants hereof are water soluble salts or acids of the
formula RO(A).sub.mSO.sub.3M wherein R is an unsubstituted
C.sub.10-C.sub.24 alkyl or hydroxyalkyl group having a
C.sub.10-C.sub.24 alkyl component, alternatively a
C.sub.12-C.sub.20 alkyl or hydroxyalkyl, alternatively
C.sub.12-C.sub.18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy
unit, m is greater than zero, typically between about 0.5 and about
6, alternatively between about 0.5 and about 3, and M is H or a
cation which can be, for example, a metal cation (e.g., sodium,
potassium, lithium, calcium, magnesium, etc.), ammonium or
substituted-ammonium cation. Alkyl ethoxylated sulfates as well as
alkyl propoxylated sulfates are contemplated herein.
[0172] When included therein, the coating compositions of the
present invention typically comprise from about 0.01% to about 5%,
alternatively from about 0.01% to about 3% by weight of such
anionic surfactants.
[0173] Alternative cationic surfactants are the water-soluble
quaternary ammonium compounds useful in the present composition
having the formula:
R.sub.1R.sub.2R.sub.3R.sub.4N+X--
[0174] wherein R.sub.1 is C.sub.8-C.sub.16 alkyl, each of R.sub.2,
R.sub.3 and R.sub.4 is independently C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 hydroxy alkyl, benzyl, and
--(C.sub.2H.sub.4O).sub.xH where x has a value from 2 to 5, and X
is an anion. Not more than one of R.sub.2, R.sub.3 or R.sub.4
should be benzyl.
[0175] When included therein, the coating compositions of the
present invention typically comprise from 0.01% to about 15%,
alternatively from about 0.01% to about 3% by weight of such
cationic surfactants.
[0176] When included therein, the coating compositions of the
present invention typically comprise from 0.01% to about 15%,
alternatively from about 0.01% to about 3% by weight of such
ampholytic surfactants.
[0177] When included therein, the coating compositions of the
present invention typically comprise from 0.01% to about 15%,
alternatively from about 0.01% to about 5% by weight of such
zwitterionic surfactants.
[0178] When included therein, the coating compositions of the
present invention typically comprise from 0.01% to about 15%,
alternatively from about 0.01% to about 5% by weight of such
semi-polar nonionic surfactants.
[0179] The detergent composition of the present invention can
further comprise a cosurfactant selected from the group of primary
or tertiary amines.
[0180] Suitable primary amines for use herein include amines
according to the formula R.sub.1NH.sub.2 wherein R.sup.1 is a
C.sub.6-C.sub.12, alternatively C.sub.6-C.sub.1o alkyl chain or
R.sub.4X(CH.sub.2).sub.n, X is --O--, --C(O)NH-- or --NH-- R.sub.4
is a C.sub.6-C.sub.12 alkyl chain n is between 1 to 5,
alternatively 3. R.sub.1 alkyl chains can be straight or branched
and can be interrupted with up to 12, alternatively less than 5
ethylene oxide moieties.
[0181] Alternative amines according to the formula herein above are
n-alkyl amines. Suitable amines for use herein can be selected from
1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other
alternative primary amines include C.sub.8-C.sub.10 oxypropylamine,
octyloxypropylamine, 2-ethylhexyl-oxypropylamine, lauryl amido
propylamine and amido propylamine.
[0182] Suitable tertiary amines for use herein include tertiary
amines having the formula R.sub.1R.sub.2R.sub.3N wherein R.sub.1
and R.sub.2 are C.sub.1-C.sub.8 alkyl chains or 5
[0183] R.sub.3 is either a C.sub.6-C.sub.12, alternatively
C.sub.6-C.sub.1o alkyl chain, or R.sub.3 is
R.sub.4X(CH.sub.2).sub.n, whereby X is --O--, -C(O)NH- or --NH--
R.sub.4 is a C.sub.4-C.sub.12, n is between 1 to 5, alternatively
2-3, R.sub.5 is H or C.sub.1-C.sub.2 alkyl and x is between 1 to
6.
[0184] R.sub.3 and R.sub.4 can be linear or branched; R.sub.3 alkyl
chains can be interrupted with up to 12, alternatively less than 5,
ethylene oxide moieties.
[0185] Alternative tertiary amines are R.sub.1R.sub.2R.sub.3N where
R.sub.1 is a C.sub.6-C.sub.12 alkyl chain, R.sub.2 and R.sub.3 are
C.sub.1-C.sub.3 alkyl or 6
[0186] where R.sub.5 is H or CH.sub.3 and x=1-2.
[0187] Alternatives are the amidoamines of the formula: 7
[0188] wherein R.sub.1 is C.sub.6-C.sub.12 alkyl; n is 2-4,
alternatively n is 3; R.sub.2 and R.sub.3 is C.sub.1-C.sub.4
Alternative amines of the present invention include 1-octylamine,
1-hexylamine, 1-decylamine, 1-dodecylamine,C8-10oxypropylamine, N
coco 1-3diaminopropane, coconutalkyldimethylamine,
lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco
bis(hydroxyethyl)amine, lauryl amine 2 moles propoxylated, octyl
amine 2 moles propoxylated, lauryl amidopropyldimethylamine, C8-10
amidopropyldimethylamine and C10 amidopropyldimethylamine.
[0189] Alternative amines for use in the coating compositions
herein are 1-hexylamine, 1-octylamine, 1-decylamine,
1-dodecylamine. Especially desirable are n-dodecyldimethylamine and
bishydroxyethylcoconutalkylamine and oleylamine 7 times
ethoxylated, lauryl amido propylamine and cocoamido
propylamine.
ALTERNATIVE ADJUNCT MATERIALS
[0190] Aminocarboxylate Chelators
[0191] Chelators, e.g., ethylenediaminetetraacetic acid (EDTA),
hydroxyethylene-diaminetriacetic acid,
diethylenetriaminepentaacetic acid, and other aminocarboxylate
chelators, and mixtures thereof, and their salts, and mixtures
thereof, can optionally be used to increase antimicrobial and
preservative effectiveness against Gram-negative bacteria,
especially Pseudomonas species. Although sensitivity to EDTA and
other aminocarboxylate chelators is mainly a characteristic of
Pseudomonas species, other bacterial species highly susceptible to
chelators include Achromobacter, Alcaligenes, Azotobacter,
Escherichia, Salmonella, Spirillum, and Vibrio. Other groups of
organisms also show increased sensitivities to these chelators,
including fungi and yeasts. Furthermore, aminocarboxylate chelators
can help, e.g., maintaining product clarity, protecting fragrance
and perfume components, and preventing rancidity and off odors.
[0192] Although these aminocarboxylate chelators may not be potent
biocides in their own right, they function as potentiators for
improving the performance of other antimicrobials/preservatives in
the coating compositions of the present invention. Aminocarboxylate
chelators can potentiate the performance of many of the cationic,
anionic, and nonionic antimicrobials/preservatives, phenolic
compounds, and isothiazolinones, that are used as
antimicrobials/preservatives in the coating composition of the
present invention. Nonlimiting examples of cationic
antimicrobials/preservatives potentiated by aminocarboxylate
chelators in solutions are chlorhexidine salts (including
digluconate, diacetate, and dihydrochloride salts), and
Quaternium-15, also known as Dowicil 200, Dowicide Q, Preventol D1,
benzalkonium chloride, cetrimonium, myristalkonium chloride,
cetylpyridinium chloride, lauryl pyridinium chloride, and the like.
Nonlimiting examples of useful anionic antimicrobials/preservatives
which are enhanced by aminocarboxylate chelators are sorbic acid
and potassium sorbate. Nonlimiting examples of useful nonionic
antimicrobials/preservatives which are potentiated by
aminocarboxylate chelators are DMDM hydantoin, phenethyl alcohol,
monolaurin, imidazolidinyl urea, and Bronopol
(2-bromo-2-nitropropane-1,3- -diol).
[0193] Examples of useful phenolic antimicrobials/preservatives
potentiated by these chelators are chloroxylenol, phenol,
tert-butyl hydroxyanisole, salicylic acid, resorcinol, and sodium
o-phenyl phenate. Nonlimiting examples of isothiazolinone
antimicrobials/preservatives which are enhanced by aminocarboxylate
chelators are Kathon, Proxel and Promexal.
[0194] The optional chelators are present in the coating
compositions of this invention at levels of, typically, from about
0.01% to about 0.3%, alternatively from about 0.02% to about 0.1%
by weight of the usage compositions to provide antimicrobial
efficacy in this invention.
[0195] Free, uncomplexed aminocarboxylate chelators are required to
potentiate the efficacy of the antimicrobials. Thus, when excess
alkaline earth (especially calcium and magnesium) and transitional
metals (iron, manganese, copper, and others) are present, free
chelators are not available and antimicrobial potentiation is not
observed. In the case where significant water hardness or
transitional metals are available or where product esthetics
require a specified chelator level, higher levels may be required
to allow for the availability of free, uncomplexed aminocarboxylate
chelators to function as antimicrobial/preservative
potentiators.
[0196] Other Optional Ingredients
[0197] The coating composition of the present invention can
optionally contain adjunct odor-controlling materials, chelating
agents, antistatic agents, insect and moth repelling agents,
colorants, bluing agents, antioxidants, and mixtures thereof in
addition to the cyclic silicone molecules. These optional
ingredients exclude the other ingredients specifically mentioned
hereinbefore. Incorporating adjunct odor-controlling materials can
enhance the capacity of the cyclodextrin to control odors as well
as broaden the range of odor types and molecule sizes which can be
controlled. Such materials include but are not limited to for
example, metallic salts, zeolites, water-soluble bicarbonate salts,
antimicrobial preservatives, UV absorbers, and mixtures
thereof.
[0198] Antimicrobial Preservative
[0199] Optionally, but alternatively, an antimicrobial preservative
can be added to the coating composition of the present invention,
alternatively solubilized, water-soluble, antimicrobial
preservative, to protect the composition. Growth of microorgamisms
in the coating composition can lead to the problem of storage
stability of hard surface coating solutions for any significant
length of time. Contamination by certain microorganisms with
subsequent microbial growth can result in an unsightly and/or
malodorous solution. Because microbial growth in the hard surfaces
is highly objectionable when it occurs, it is highly preferable to
include an antimicrobial preservative, alternatively solubilized,
water-soluble, antimicrobial preservative, which is effective for
inhibiting and/or regulating microbial growth in order to increase
storage stability of the alternatively clear, aqueous containing
the hard surface coating composition.
[0200] It is preferable to use a broad spectrum preservative, e.g.,
one that is effective on both bacteria (both gram positive and gram
negative) and fungi. A limited spectrum preservative, e.g., one
that is only effective on a single group of microorganisms, e.g.,
fungi, can be used in combination with a broad spectrum
preservative or other limited spectrum preservatives with
complimentary and/or supplementary activity. A mixture of
broad-spectrum preservatives can also be used. In some cases where
a specific group of microbial contaminants is problematic (such as
Gram negatives), aminocarboxylate chelators can be used alone or as
potentiators in conjunction with other preservatives. These
chelators which include, e.g., ethylenediaminetetraacetic acid
(EDTA), hydroxyethylenediaminetriacetic acid,
diethylenetriaminepentaacetic acid, and other aminocarboxylate
chelators, and mixtures thereof, and their salts, and mixtures
thereof, can increase preservative effectiveness against
Gram-negative bacteria, especially Pseudomonas species.
[0201] Antimicrobial preservatives useful in the present invention
include biocidal compounds, i.e., substances that kill
microorganisms, or biostatic compounds, i.e., substances that
inhibit and/or regulate the growth of microorganisms. Suitable
preservatives are disclosed in U.S. Pat. Nos. 5,534,165; 5,578,563;
5,663,134; 5,668,097; 5,670,475; and 5,714,137, Trinh et al. issued
Jul. 9, 1996; Nov. 26, 1996; Sep. 2, 1997; Sep. 16, 1997; Sep. 23,
1997; and Feb. 3, 1998 respectively, all of said patents being
incorporated hereinbefore by reference. Many antimicrobial
preservatives are given under the section on Antimicrobial Active
given herein above. Water insoluble antimicrobial preservatives
such as paraben and triclosan are useful in the coating
compositions of the present invention, but they require the use of
a solubilizer, an emulsifier, a dispersing agent, or the like, such
as a surfactant and/or cyclodextrin to effectively distribute said
preservative in the liquid composition. Alternative antimicrobial
preservatives are those that are water-soluble and are effective at
low levels. Water-soluble preservatives useful in the present
invention are those that have a solubility in water of at least
about 0.3 g per 100 ml of water, i.e., greater than about 0.3% at
room temperature, alternatively greater than about 0.5% at room
temperature.
[0202] The water-soluble antimicrobial preservative in the present
invention is included at an effective amount. The term "effective
amount" as herein defined means a level sufficient to prevent
spoilage, or prevent growth of inadvertently added microorganisms,
for a specific period of time. In other words, the preservative is
not being used to kill microorganisms on the surface onto which the
coating composition is deposited in order to eliminate odors
produced by microorganisms. Instead, it is alternatively being used
to prevent spoilage of the hard surface coating composition in
order to increase the shelf life of the coating composition.
Alternative levels of preservative are from about 0.0001% to about
0.5%, alternatively from about 0.0002% to about 0.2%, alternatively
from about 0.0003% to about 0.1%, by weight of the usage
composition.
[0203] The preservative can be any organic preservative material
which will not cause damage to hard surface appearance, e.g.,
discoloration, coloration, bleaching. Alternative water-soluble
preservatives include organic sulfur compounds, halogenated
compounds, cyclic organic nitrogen compounds, low molecular weight
aldehydes, quaternary ammonium compounds, dehydroacetic acid,
phenyl and phenolic compounds, and mixtures thereof.
[0204] The preservatives of the present invention can be used in
mixtures in order to control a broad range of microorganisms.
[0205] Bacteriostatic effects can sometimes be obtained for aqueous
compositions by adjusting the coating composition pH to an acid pH,
e.g., less than about pH 4, alternatively less than about pH 3, or
a basic pH, e.g., greater than about 10, alternatively greater than
about 11.
[0206] UV Absorbers
[0207] Not to be bound by theory, but UV absorbers can operate by
protecting the coating deposited on the hard surface from UV
exposure. UW light is know to initiate auto-oxidation processes and
UV absorbers can be deposited on hard surface in such a way that UV
light is blocked from the hard surface and unsaturated fatty
materials, thus preventing the initiation of auto-oxidation.
[0208] Oxidative Stabilizers
[0209] Oxidative stabilizers can be present in the coating
compositions of the present invention and these prevent yellowing
by acting as a scavenger for the oxidative processes, thus
preventing and/or terminating auto-oxidation, or by reversing
oxidation and thus reversing yellowing. The term "oxidative
stabilizer," as used herein, includes antioxidants and reductive
agents. These agents are present at a level of from O% to about 2%,
alternatively from about 0.01% to about 0.2%, alternatively from
about 0.035% to about 0.1% for antioxidants, and, alternatively,
from about 0.01% to about 0.2% for reductive agents.
[0210] Examples of antioxidants that can be added to the coating
compositions and in the processing of this invention include a
mixture of ascorbic acid, ascorbic palmitate, propyl gallate,
available from Eastman Chemical Products, Inc., under the trade
names Tenox.RTM. PG and Tenox.RTM. S-1; a mixture of BHT (butylated
hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate,
and citric acid, available from Eastman Chemical Products, Inc.,
under the trade name Tenox.RTM.-6; butylated hydroxytoluene,
available from UOP Process Division under the trade name
Sustane.RTM. BHT; tertiary butylhydroquinone, Eastman Chemical
Products, Inc., as Tenox.RTM. TBHQ; natural tocopherols, Eastman
Chemical Products, Inc., as Tenox.RTM. GT-1/GT-2; and butylated
hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chain
esters (C.sub.8-C.sub.22) of gallic acid, e.g., dodecyl gallate;
Irganoxo 1010; Irganox.RTM. 1035; Irganox.RTM. B 1171; Irganoxo
1425; Irganoxo 3114; Irganox.RTM. 3125; and mixtures thereof;
alternatively Irganox.RTM. 3125, Irganox.RTM. 1425, Irganox.RTM.
3114, and mixtures thereof; alternatively Irganox.RTM. 3125 alone
or mixed with citric acid and/or other chelators such as isopropyl
citrate, Dequest.RTM. 2010, available from Monsanto with a chemical
name of 1-hydroxyethylidene-1, 1-diphosphonic acid (etidronic
acid), and Tiron.RTM., available from Kodak with a chemical name of
4,5-dihydroxy-m-benzene-sulfonic acid/sodium salt, and DTPA.RTM.,
available from Aldrich with a chemical name of
diethylenetriaminepentaace- tic acid.
[0211] Oxidative stabilizers can also be added at any point during
the process. These assure good odor stability under long-term
storage conditions.
[0212] Colorant
[0213] Colorants, dyes, and bluing agents can be optionally added
to the coating compositions for visual appeal and performance
impression. When colorants are used, they are used at extremely low
levels to avoid hard surface staining. Alternative colorants for
use in the present compositions are highly water-soluble dyes,
e.g., Liquitint(.RTM. dyes available from Milliken Chemical Co.
Non-limiting examples of suitable dyes are, Liquitint Blue HP.RTM.,
Liquitint Blue 65.RTM., Liquitint Pat. Blue.RTM., Liquitint Royal
Blue(, Liquitint Experimental Yellow 8949-43.RTM., Liquitint Green
HMC.RTM., Liquitint Yellow II.RTM., and mixtures thereof,
alternatively Liquitint Blue HP.RTM., Liquitint Blue 65.RTM.,
Liquitint Pat. Blue.RTM., Liquitint Royal Blue.RTM., Liquitint
Experimental Yellow 8949-43.RTM., and mixtures thereof.
[0214] Builders
[0215] The coating compositions according to the present invention
can further comprise a builder or builder system, especially for
coating compositions. Any conventional builder system is suitable
for use herein including aluminosilicate materials, silicates,
polycarboxylates, alkyl- or alkenyl-succinic acid and fatty acids,
materials such as ethylenediamine tetraacetate, diethylene triamine
pentamethyleneacetate, metal ion sequestrants such as
aminopolyphosphonates, particularly ethylenediamine tetramethylene
phosphonic acid and diethylene triamine pentamethylenephosphonic
acid. Phosphate builders can also be used herein.
[0216] The present invention can include a suitable builder or
detergency salt. The level of detergent salt/builder can vary
widely depending upon the end use of the coating composition and
its desired physical form. When present, the coating compositions
will typically comprise at least about 1% builder and more
typically from about 10% to about 80%, even more typically from
about 15% to about 50% by weight, of the builder. Lower or higher
levels, however, are not meant to be excluded.
[0217] Inorganic or P-containing detergent salts include, but are
not limited to, the alkali metal, ammonium and alkanolammonium
salts of polyphosphates (exemplified by the tripolyphosphates,
pyrophosphates, and glassy polymeric meta-phosphates),
phosphonates, phytic acid, silicates, carbonates (including
bicarbonates and sesquicarbonates), sulphates, and
aluminosilicates. However, non-phosphate salts are required in some
locales. Importantly, the coating compositions herein function
surprisingly well even in the presence of the so-called "weak"
builders (as compared with phosphates) such as citrate, or in the
so-called "underbuilt" situation that may occur with zeolite or
layered silicate builders.
[0218] Organic detergent builders suitable for the purposes of the
present invention include, but are not restricted to, a wide
variety of polycarboxylate compounds. As used herein,
"poly-carboxylate" refers to compounds having a plurality of
carboxylate groups, alternatively at least 3 carboxylates.
Polycarboxylate builder can generally be added to the coating
composition in acid form, but can also be added in the form of a
neutralized salt. When utilized in salt form, alkali metals, such
as sodium, potassium, and lithium, or alkanolammonium salts are
alternatives.
[0219] Examples of suitable silicate builders, carbonate salts,
aluminosilicate builders, polycarboxylate builders, citrate
builders, 3,3-dicarboxy-4-oxa-1,6-hexanedioate builders and related
compounds disclosed in U.S. Pat. No. 4,566,984, to Bush, succinic
acid builders, phosphorous-based builders and fatty acids, is
disclosed in U.S. Pat. Nos. 5,576,282, 5,728,671 and 5,707,950.
[0220] Additional suitable builders can be an inorganic ion
exchange material, commonly an inorganic hydrated aluminosilicate
material, more particularly a hydrated synthetic zeolite such as
hydrated zeolite A, X, B, HS or MAP.
[0221] Specific polycarboxylates suitable for the present invention
are polycarboxylates containing one carboxy group include lactic
acid, glycolic acid and ether derivatives thereof as disclosed in
Belgian Pat. Nos. 831,368, 821,369 and 821,370. Polycarboxylates
containing two carboxy groups include the water-soluble salts of
succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic
acid, diglycollic acid, tartaric acid, tartronic acid and fumaric
acid, as well as the ether carboxylates described in German
Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Pat. No.
3,935,257 and the sulfinyl carboxylates described in Belgian Pat.
No. 840,623. Polycarboxylates containing three carboxy groups
include, in particular, water-soluble citrates, aconitrates and
citraconates as well as succinate derivatives such as the
carboxymethyloxysuccinates described in British Pat. No. 1,379,241,
lactoxysuccinates described in Netherlands Application 7205873, and
the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane
tricarboxylates described in British Pat. No. 1,387,447.
[0222] Polycarboxylates containing four carboxy groups include
oxydisuccinates disclosed in British Pat. No. 1,261,829,
1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates
and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing
sulfo substituents include the sulfosuccinate derivatives disclosed
in British Pat. Nos. 1,398,421 and 1,398,422 and in U.S. Pat. No.
3,936,448, and the sulfonated pyrolysed citrates described in
British Pat. No. 1,082,179, while polycarboxylates containing
phosphone substituents is disclosed in British Pat. No.
1,439,000.
[0223] Alicyclic and heterocyclic polycarboxylates include
cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide
pentacarboxylates, 2,3,4,5-tetrahydro-furan-cis, cis,
cis-tetracarboxylates, 2,5-tetrahydro-furan -cis-dicarboxylates,
2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane
-hexacarboxylates and carboxymethyl derivatives of polyhydric
alcohols such as sorbitol, mannitol and xylitol. Aromatic
poly-carboxylates include mellitic acid, pyromellitic acid and the
phthalic acid derivatives disclosed in British Pat. No.
1,425,343.
[0224] Of the above, the alternative polycarboxylates are
hydroxycarboxylates containing up to three carboxy groups per
molecule, more particularly citrates.
[0225] Builder systems for use in the present compositions include
a mixture of a water-insoluble aluminosilicate builder such as
zeolite A or of a layered silicate (SKS-6), and a water-soluble
carboxylate-chelating agent such as citric acid.
[0226] Builder systems include a mixture of a water-insoluble
aluminosilicate builder such as zeolite A, and a water-soluble
carboxylate chelating agent such as citric acid. Builder systems
for use in liquid, coating compositions of the present invention
are soaps and polycarboxylates.
[0227] Other suitable water-soluble organic salts are the homo- or
copolymeric acids or their salts, in which the polycarboxylic acid
comprises at least two carboxyl radicals separated from each other
by not more than two carbon atoms. Polymers of this type are
disclosed in GB-A-1,596,756. Examples of such salts are
polyacrylates of MW 2000-5000 and their copolymers with maleic
anhydride, such copolymers having a molecular weight of from 20,000
to 70,000, especially about 40,000.
[0228] Detergency builder salts are normally included in amounts of
from 5% to 80% by weight of the coating composition alternatively
from 10% to 70% and most usually from 30% to 60% by weight.
[0229] Suds Suppressor
[0230] Another optional ingredient is a suds suppressor,
exemplified by silicones, and silica-silicone mixtures. Examples of
suitable suds suppressors are disclosed in U.S. Pat. Nos. 5,707,950
and 5,728,671. These suds suppressors are normally employed at
levels of from 0.001% to 2% by weight of the coating composition,
alternatively from 0.01% to 1% by weight.
[0231] Enzymes
[0232] Enzymes can be included in the present detergent
compositions for a variety of purposes, including removal of
protein-based, carbohydrate-based, or triglyceride-based stains
from surfaces such as textiles or dishes, for the prevention of
refugee dye transfer, for example in laundering, and for fabric
restoration. Suitable enzymes include proteases, amylases, lipases,
cellulases, peroxidases, and mixtures thereof of any suitable
origin, such as vegetable, animal, bacterial, fungal and yeast
origin. Alternative selections are influenced by factors such as
pH-activity and/or stability optima, thermostability, and stability
to active detergents, builders and the like. In this respect
bacterial or fungal enzymes are alternatives, such as bacterial
amylases and proteases, and fungal cellulases.
[0233] "Detersive enzyme", as used herein, means any enzyme having
a cleaning, stain removing or otherwise beneficial effect in a
laundry detergent composition. Alternative detersive enzymes are
hydrolases such as proteases, amylases and lipases. Alternative
enzymes for laundry purposes include, but are not limited to,
proteases, cellulases, lipases and peroxidases.
[0234] Enzymes are normally incorporated into detergent or
detergent additive compositions at levels sufficient to provide a
"cleaning-effective amount". The term "cleaning effective amount"
refers to any amount capable of producing a cleaning, stain
removal, soil removal, whitening, deodorizing, or freshness
improving effect on substrates such as fabrics, dishware and the
like. In practical terms for current commercial preparations,
typical amounts are up to about 5 mg by weight, more typically 0.01
mg to 3 mg, of active enzyme per gram of the detergent composition.
Stated otherwise, the compositions herein will typically comprise
from 0.001% to 5%, alternatively 0.01%-1% by weight of a commercial
enzyme preparation. Protease enzymes are usually present in such
commercial preparations at levels sufficient to provide from 0.005
to 0.1 Anson units (AU) of activity per gram of composition. Higher
active levels may also be desirable in highly concentrated
detergent formulations.
[0235] Examples of suitable enzymes include, but are not limited
to, hemicellulases, peroxidases, proteases, cellulases, xylanases,
lipases, phospholipases, esterases, cutinases, pectinases,
keratanases, reductases, oxidases, phenoloxidases, lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases,
Bglucanases, arabinosidases, hyaluronidase, chondroitinase,
laccase, mannanases, more preferably plant cell wall degrading
enzymes and non-cell wall-degrading enzymes (WO 98/39403 A) and
can, more specifically, include pectinase (WO 98/06808 A,
JP10088472 A, JP10088485 A); pectolyase (WO98/06805 A1); pectin
lyases free from other pectic enzymes (WO9806807 A1);
chondriotinase ( EP 747,469 A); xylanase ( EP 709,452 A, WO
98/39404 A, WO98/39402 A) including those derived from
microtetraspora flexuosa (U.S. Pat. No. 5683911); isopeptidase (WO
98/16604 A); keratinase (EP 747,470 A, WO 98/40473 A); lipase ( GB
2,297,979 A; WO 96/16153 A; WO 96/12004 A; EP 698,659 A; WO
96/16154 A); cellulase or endoglucanase (GB 2,294,269 A; WO
96/27649 A; GB 2,303,147 A; WO98/03640 A; see also neutral or
alkaline cellulases derived from chrysosporium lucknowense strain
VKM F-3500D as disclosed in WO9815633 A); polygalacturonase (WO
98/06809 A); mycodextranase (WO 98/13457 A); thermitase (WO
96/28558 A); cholesterol esterase (WO 98 28394 A); or any
combination thereof; and known amylases; oxidoreductases; oxidases
or combination systems including same (DE19523389 A1); mutant blue
copper oxidases (WO9709431 A1), peroxidases (see for example U.S.
Pat. No. 5,605,832, WO97/31090 A1), mannanases (WO.sub.9711164, WO
99/09126, PCT/USOO/00839); xyloglucanases (WO 98/50513,
PCT/US/00/00839, WO 99/02663); laccases, see WO9838287 A1or
WO9838286 A1or for example, those laccase variants having amino
acid changes in myceliophthora or scytalidium laccase(s) as
described in WO.sub.9827197 A1or mediated laccase systems as
described in DE19612193 A1), or those derived from coprinus strains
(see, for example WO9810060 A1or WO9827198 A1), phenol oxidase or
polyphenol oxidase (JP10174583 A) or mediated phenol oxidase
systems (WO.sub.9711217 A); enhanced phenol oxidase systems (WO
9725468 A WO9725469 A); phenol oxidases fused to an amino acid
sequence having a cellulose binding domain (WO.sub.9740127 A1,
WO9740229 A1) or other phenol oxidases (WO9708325 A, WO9728257 A1)
or superoxide dismutases. Oxidoreductases and/or their associated
antibodies can be used, for example with H.sub.2O.sub.2, as taught
in WO 98/07816 A. Depending on the type of composition, other
redox-active enzymes can be used, even, for example, catalases
(see, for example JP09316490 A).
[0236] Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B. subtilis and B.
licheniformis. One suitable protease is obtained from a strain of
Bacillus, having maximum activity throughout the pH range of 8-12,
developed and sold as ESPERASE(I by Novo Industries A/S of Denmark,
hereinafter "Novo". The preparation of this enzyme and analogous
enzymes is described in GB 1,243,784 to Novo. Other suitable
proteases include ALCALASE.RTM. and SAVINASE.RTM. from Novo and
MAXATASE.RTM. from International Bio-Synthetics, Inc., The
Netherlands; as well as Protease A as disclosed in EP 130,756 A,
Jan. 9, 1985 and Protease B as disclosed in EP 303,761 A, Apr.28,
1987 and EP 130,756 A, Jan. 9, 1985. See also a high pH protease
from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo.
Enzymatic detergents comprising protease, one or more other
enzymes, and a reversible protease inhibitor are described in WO
9203529 A to Novo. Other alternative proteases include those of WO
9510591 A to Procter & Gamble . When desired, a protease having
decreased adsorption and increased hydrolysis is available as
described in WO 9507791 to Procter & Gamble. A recombinant
trypsin-like protease for detergents suitable herein is described
in WO 9425583 to Novo.
[0237] In more detail, an alternative protease, referred to as
"Protease D" is a carbonyl hydrolase variant having an amino acid
sequence not found in nature, which is derived from a precursor
carbonyl hydrolase by substituting a different amino acid for a
plurality of amino acid residues at a position in said carbonyl
hydrolase equivalent to position +76, alternatively also in
combination with one or more amino acid residue positions
equivalent to those selected from the group consisting of +99,
+101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135,
+156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222,
+260, +265, and/or +274 according to the numbering of Bacillus
amyloliquefaciens subtilisin, as described in the patent
applications of A. Baeck, et al, entitled "Protease-Containing
Cleaning Compositions" having U.S. Ser. No. 8/322,676, and C.
Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes"
having US Serial No. 8/322,677, both filed Oct. 13, 1994.
[0238] An alternative protease, "Protease E", is a carbonyl
hydrolase variant having an amino acid sequence not found in
nature, which is derived from a precursor carbonyl hydrolase by
substituting a different amino acid for a plurality of amino acid
residues at a position in said carbonyl hydrolase equivalent to
position 103 of Bacillus amyloliquefaciens subtilisin in
combination with a substitution of an amino acid residue with
another naturally occurring amino acid residue at one or more amino
acid residue positions corresponding to positions 1, 3, 4, 8, 9,
10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43,
48, 55, 57,58, 61, 62, 68, 72, 75, 76,77,78,79,86,87,
89,97,98,99,101,102, 104,106,107,109,111, 114,116,117,119,121, 123,
126, 128, 130, 131, 133, 134, 137, 140, 141, 142, 146, 147, 158,
159, 160, 166, 167, 170, 173,174,177,181,182, 183,184,185,188,192,
194, 198,203,204,205,206,209,210,211, 212, 213, 214, 215, 216, 217,
218, 222, 224, 227, 228, 230, 232, 236, 237, 238, 240, 242, 243,
244, 245, 246, 247, 248, 249, 251, 252, 253, 254, 255, 256, 257,
258, 259, 260, 261, 262, 263, 265, 268, 269, 270, 271, 272, 274 and
275 of Bacillus amyloliquefaciens subtilisin; wherein when said
protease variant includes a substitution of amino acid residues at
positions corresponding to positions 103 and 76, there is also a
subtitution of an amino acid residue at one or more amino acid
residue positions other than amino acid residue positions
corresponding to positions 27, 99, 101, 104, 107, 109, 123, 128,
166, 204, 206, 210, 216, 217, 218, 222, 260, 265 or 274 of Bacillus
amyloliquefaciens subtilisin; and one or more cleaning adjunct
materials.
[0239] While any combination of the above listed amino acid
substitutions may be employed, the preferred protease variant
enzymes useful for the present invention comprise the substitution,
deletion or insertion of amino acid residues in the following
combinations:
[0240] (1) a protease variant including substitutions of the amino
acid residues at position 103 and at one or more of the following
positions 236 and 245;
[0241] (2) a protease variant including substitutions of the amino
acid residues at positions 103 and 236 and at one or more of the
following positions: 12, 61, 62, 68, 76, 97, 98, 101, 102, 104,
109, 130, 131, 159, 183, 185, 205, 209, 210, 211, 212, 213, 215,
217, 230, 232, 248, 252, 257, 260, 270 and 275;
[0242] (3) a protease variant including substitutions of the amino
acid residues at positions 103 and 245 and at one or more ofthe
following positions: 12, 61, 62, 68, 76, 97, 98, 101, 102, 104,
109, 130, 131, 159, 170, 183, 185, 205, 209, 210, 211, 212, 213,
215, 217, 222, 230, 232, 248, 252, 257, 260, 261, 270 and 275;
and
[0243] (4) a protease variant including substitutions of the amino
acid residues at positions 103, 236 and 245 and at one or more of
the following positions: 12, 61, 62, 68, 76, 97, 98, 101, 102, 104,
109, 130, 131, 159, 183, 185, 205, 209, 210, 211, 212, 213, 215,
217, 230, 232, 243, 248, 252, 257, 260, 270 and 275 , as described
in the patent applications of C. Ghosh, et al, entitled"Cleaning
Compositions Containing Multiply-Substituted Protease Variants"
having U.S. Ser. No. 9/529905, filed Oct. 23, 1998.
[0244] Amylases suitable herein, especially for, but not limited to
automatic dishwashing purposes, include, for example, x-amylases
described in GB 1,296,839 to Novo; RAPIDASE(, International
Bio-Synthetics, Inc. and TERMAMYL.RTM., Novo. FUNGAMYL.RTM. from
Novo is especially useful. Engineering of enzymes for improved
stability, e.g., oxidative stability, is known. See, for example J.
Biological Chem., Vol. 260, No. 11, June 1985, pp 6518-6521. These
alternative amylases herein share the characteristic of being
"stability-enhanced" amylases, characterized, at a minimum, by a
measurable improvement in one or more of: oxidative stability,
e.g., to hydrogen peroxide/tetraacetylethylenedi- amine in buffered
solution at pH 9-10; thermal stability, e.g., at common wash
temperatures such as about 60.degree. C.; or alkaline stability,
e.g., at a pH from about 8 to about 11, measured versus the
above-identified reference-point amylase. Stability can be measured
using any of the art-disclosed technical tests. See, for example,
references disclosed in WO 9402597. Stability-enhanced amylases can
be obtained from Novo or from Genencor International. One class of
alternative amylases herein have the commonality of being derived
using site-directed mutagenesis from one or more of the Baccillus
amylases, especialy the Bacillus xc-amylases, regardless of whether
one, two or multiple amylase strains are the immediate precursors.
Oxidative stability-enhanced amylases vs. the above-identified
reference amylase are alternative for use, especially in bleaching,
alternatively oxygen bleaching, as distinct from chlorine
bleaching, detergent compositions herein. Such alternative amylases
include (a) an amylase according to the hereinbefore incorporated
WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant
in which substitution is made, using alanine or threonine,
alternatively threonine, of the methionine residue located in
position 197 of the B. licheniformis alpha-amylase, known as
TERMAMYL.RTM., or the homologous position variation of a similar
parent amylase, such as B. amyloliquefaciens, B.subtilis, or
B.stearothermophilus; (b) stability-enhanced amylases as described
by Genencor International in a paper entitled "Oxidatively
Resistant alpha-Amylases" presented at the 207th American Chemical
Society National Meeting, March 13-17 1994, by C. Mitchinson.
Methionine (Met) was identified as the most likely residue to be
modified. Met was substituted, one at a time, in positions 8, 15,
197, 256, 304, 366 and 438 leading to specific mutants,
particularly important being M197L and M197T with the M197T variant
being the most stable expressed variant. Other alternative
oxidative stability enhanced amylase include those described in WO
9418314 to Genencor International and WO 9402597 to Novo. Any other
oxidative stability-enhanced amylase can be used, for example as
derived by site-directed mutagenesis from known chimeric, hybrid or
simple mutant parent forms of available amylases. Other alternative
enzyme modifications are accessible. See WO 9509909 A to Novo.
[0245] Cellulases usable herein include both bacterial and fungal
types, alternatively having a pH optimum between 5 and 9.5. U.S.
4,435,307, Barbesgoard et al, March 6, 1984, discloses suitable
fungal cellulases from Humicola insolens or Humicola strain DSM
1800 or a cellulase 212-producing fungus belonging to the genus
Aeromonas, and cellulase extracted from the hepatopancreas of a
marine mollusk, Dolabella Auricula Solander. Suitable cellulases
are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and
DE-OS-2.247.832. CAREZYME.RTM. (Novo) is especially useful. See
also WO 9117243 to Novo.
[0246] Suitable lipase enzymes for detergent usage include those
produced by microorganisms of the Pseudomonas group, such as
Pseudomonas stutzeri ATCC19.154, as disclosed in GB 1,372,034. See
also lipases in Japanese Patent Application 53,20487, laid open
Feb. 24, 1978. This lipase is available from Amano Pharmaceutical
Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or
"Amano-P." Other suitable commercial lipases include Amano-CES,
lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;
CHromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A.
and Disoynth Co., The Netherlands, and lipases ex Pseudomonas
gladioli. LIPOLASE.RTM. enzyme derived from Humicola lanuginosa and
commercially available from Novo, see also EP 341,947, is a
alternative lipase for use herein. Lipase and amylase variants
stabilized against peroxidase enzymes are described in WO 9414951 A
to Novo. See also WO 9205249 and RD 94359044.
[0247] Cutinase enzymes suitable for use herein are described in WO
8809367 A to Genencor.
[0248] Peroxidase enzymes may be used in combination with oxygen
sources, e.g., percarbonate, perborate, hydrogen peroxide, etc.,
for "solution bleaching" or prevention of transfer of dyes or
pigments removed from substrates during the wash to other
substrates present in the wash solution. Known peroxidases include
horseradish peroxidase, ligninase, and haloperoxidases such as
chloro- or bromo-peroxidase. Peroxidase-containing detergent
compositions are disclosed in WO 89099813 A, Oct. 19, 1989 to Novo
and WO 8909813 A to Novo.
[0249] A range of enzyme materials and means for their
incorporation into synthetic detergent compositions is also
disclosed in WO 9307263 A and WO 9307260 A to Genencor
International, WO 8908694 A to Novo, and U.S. Pat. No. 3,553,139,
Jan. 5, 1971 to McCarty et al. Enzymes are further disclosed in
U.S. Pat. No. 4,101,457, Place et al, Jul. 18, 1978, and in U.S.
Pat. No. 4,507,219, Hughes, Mar. 26, 1985. Enzyme materials useful
for liquid detergent formulations, and their incorporation into
such formulations, are disclosed in U.S. Pat. No. 4,261,868, Hora
et al, Apr. 14, 1981. Enzymes for use in detergents can be
stabilized by various techniques. Enzyme stabilization techniques
are disclosed and exemplified in U.S. Pat. No. 3,600,319, Aug. 17,
1971, Gedge et al, EP 199,405 and EP 200,586, Oct. 29, 1986,
Venegas. Enzyme stabilization systems are also described, for
example, in U.S. Pat. No. 3,519,570. A useful Bacillus, sp. AC13
giving proteases, xylanases and cellulases, is described in WO
9401532 A to Novo.
[0250] Other Materials
[0251] Detersive ingredients or adjuncts optionally included in the
instant compositions can include one or more materials for
assisting or enhancing the performance of the treating
compositions, treatment of the substrate to be cleaned, or designed
to improve the aesthetics of the compositions. Adjuncts which can
also be included in compositions of the present invention, at their
conventional art-established levels for use (generally, adjunct
materials comprise, in total, from about 30% to about 99.9%,
alternatively from about 70% to about 95%, by weight of the
compositions), include other active ingredients such as photoactive
inorganic metal oxides, color speckles, anti-tarnish agents,
anti-corrosion agents, alkalinity sources, hydrotropes,
anti-oxidants, organic solvents, surfactants, polymers, builders,
bleaches, bleach activators, bleach catalysts, non-activated
enzymes, enzyme stabilizing systems, chelants, optical brighteners,
soil release polymers, wetting agents, dye transfer agents,
dispersants, suds suppressors, dyes, perfumes, colorants, filler
salts, photoactivators, fluorescers, conditioners, hydrolyzable
cosurfactants, perservatives, anti-shrinkage agents, germicides,
fungicides, silvercare, solubilizing agents, carriers, processing
aids, pigments,and pH control agents as described in U.S. Pat. Nos.
5,705,464; 5,710,115; 5,698,504; 5,695,679; 5,686,014;
5,576,282.and 5,646,101.
II. METHODS OF USE
[0252] The coating composition, which contains a nanoparticle
system with an effective amount of non-photoactive nanoparticles in
and aqueous suitable carrier medium, and optionally a surfactant,
one or more charged functionalized surface molecules, an effective
amount of photoactive nanoparticles, and optionally, e.g., adjunct
organic solvents, surfactants, polymers, chelants, builders,
bleaches, bleach activators, bleach catalysts, non-activated
enzymes, enzyme stabilizing systems, optical brighteners, soil
release polymers, wetting agents, dye transfer agents, dispersants,
suds suppressors, dyes, perfumes, colorants, filler salts,
hydrotropes, photoactivators, fluorescers, conditioners,
hydrolyzable cosurfactants, preservatives, anti-oxidants,
anti-shrinkage agents, germicides, fungicides, color speckles,
silvercare, anti-tarnish and/or anti-corrosion agents, alkalinity
sources, solubilizing agents, carriers, processing aids, pigments,
and pH control agents, etc. and mixtures thereof, can be used by
(a) mixing said nanoparticles in suitable carrier medium to form
said coating composition; (b) optionally mixing said nanoparticles
dispersed in suitable carrier medium with adjunct ingredients to
form said coating composition; (c) optionally mixing said
nanoparticles dispersed in suitable carrier medium with surfactant
to form said coating composition; (d) optionally mixing said
nanoparticles dispersed in suitable carrier medium with adjunct
ingredients and surfactant to form said coating composition; (e)
applying said coating composition to said hard surface; (f)
allowing said coating composition to dry, or actively drying the
coating composition, or otherwise curing the coating composition;
and (g) optionally repeating any of steps (a) through (f) as
needed.
[0253] Distribution of the coating composition can be achieved by
using a spray device, an immersion container, a spray hose
attachment, or an applicator, such as a fabric, sponge, roller, a
pad, etc., alternatively a spray dispenser. The coating
compositions and articles of the present invention which contain
the nanoparticle system can be used to treat all hard surfaces to
provide at least one of the following improved durable benefits:
improved hard surface wetting and sheeting, quick drying, uniform
drying, soil removal, self-cleaning, anti-spotting, anti-soil
deposition, cleaner appearance, enhanced gloss, enhanced color,
minor surface defect repair, improved smoothness, anti-hazing
properties, modification of surface friction, release of actives,
reduced damage to abrasion and improved transparency.
[0254] In one aspect of the present invention, an effective amount
of the liquid coating composition of the present invention is
alternatively sprayed onto hard surfaces and/or hard surface
articles include, but are not limited to: interior and exterior
glass windows, walls and doors; exterior vehicle bodies, including
but not limited to auto bodies, trucks, trains, boats and planes;
ceramic tile, floors and walls; bathroom and kitchen countertops;
appliances; metal fixtures, siding and roofing; dishware; wood
furniture, flooring and wall treatments; stone tiles and walls;
asphalt roofing, siding and driveways; jewelry; exterior building
surfaces; painted and coated surfaces, etc. When the coating
composition is sprayed onto a hard surface, an effective amount of
the nanoparticle system should be deposited onto the hard surface,
with the hard surface becoming damp or totally saturated with the
coating composition. The hard surface coating composition can also
be applied to a hard surface via roll coating, curtain coating, a
dipping and/or soaking process in an immersion container. Any of
the application steps can be followed by a drying, or curing
step.
[0255] In one non-limiting aspect of the present invention, the
coating composition is used to apply a durable coating on the
surface of a vehicle, such as an automobile. The steps in applying
the coating composition can involve one or more of the following
steps, in addition to a step of applying the coating composition: a
pre-wash step; a washing step, such as with soap and a sponge to
produce lather; a rinse step; an activated rinse step; a step for
applying the coating composition described herein; and a drying
step. These steps can be performed by consumers at home, such as if
they are provided with the components needed to carry out the steps
in the form of a kit, such as a car care kit. Instructions can be
provided. Alternatively, the steps can be performed in a commercial
operation, such as at a car wash, which may be of the automatic
type, or the "self serve" type where customers use a wash bay to
spray their car clean.
[0256] The hard surface coating composition can be applied to the
hard surface at any suitable air temperature. It has been found
that the hard surface coating composition can be applied at any
temperature above freezing. For instance, the coating composition
can be applied at temperatures as low as 1.degree., 5.degree.,
10.degree., or 15.degree. C.
[0257] The hard surface can then be subjected to conditions so as
to cure or dry the coating composition. The drying step can
comprise air drying in ambient conditions. Alternatively, the
drying step can comprise actively drying or curing the coating
composition by utilizing any technology known for accelerating a
drying or curing process. The term "actively curing", as used
herein, refers to any technique used to accelerate the curing
process beyond merely allowing the coating composition to dry under
ambient conditions. For instance, known cross-linking agents can be
incorporated into the composition to cure the same. Although
various methods of curing may be used, thermal or heat curing, or
heat drying is preferred. The hard surface coating composition can
be heat dried at any air temperature which is above the ambient
temperature (which air temperature of drying may, for example, be
greater than or equal to about any five degree increment above
0.degree. C.). Generally, heat curing is effected by exposing the
coated surface to elevated temperatures, such as those provided by
radiative heat sources. Such technology may include moving (or
forced) air drying such as drying by fans, blow drying, etc., or
the application of heat (such as by radiative heat sources, such as
drying in ovens, etc.), or both moving or forced air drying and the
application of heat (such as heated blow drying).
[0258] It has been found that heat drying the hard surface coating
composition can greatly increase the durability of the hard surface
coating. The amount of increase in the durability of the hard
surface coating composition can, in fact, be quite unexpectedly
high.
[0259] For instance, in some embodiments, it has been found that
when the hard surface coating composition is applied to a hard
surface and air dried at ambient temperature, the hard surface
coating is able to provide the benefits described herein (or at
least some of such benefits) after it has been subjected to one or
two routines/cycles of the mechanical Scrub method described in the
Test Methods section below. This is believed to translate into
about two to four weeks of surface protection and modification in
an outside environment, including washing the surface about once a
week.
[0260] However, if the hard surface coating composition is heat
dried above ambient temperature (which may be about 20-22 .degree.
C. in the case of a moderate outside temperature, or interior air
temperature in a building), the hard surface coating formed on the
surface has been found to have increased durability, so that it
provides more lasting benefits. The term "long lasting", as used
herein, refers to a coating that is able to provide at least some
of the benefits described herein after more than one cycle of the
Scrub Method described in the Test Methods section. The hard
surface coating composition can be heat dried at any air
temperature of greater than or equal to about 50.degree. C. and any
five degree increment above 50.degree. C. (e.g., 80.degree. C.) to
provide long lasting benefits. However, this could be influenced by
accelerants, i.e., solvents and cross-linking agents. The hard
surface coating composition can be air dried at temperatures that
approach, but preferably do not exceed a temperature that would
cause the hard surface being coated to be altered, such as by
melting, buckling, or the like. In one non-limiting embodiment, the
hard surface coating composition can be applied to an automobile
body panel, and then heat dried at an air temperature of about
145.degree. C. to about 160.degree. C., or any five degree
increment therebetween. It has been found that a coating dried with
such a heat drying process can withstand 500 or more cycles of the
mechanical scrubbing test. In another non-limiting embodiment, the
hard surface coating composition can be applied to an automobile
body panel, and then heat dried at an air temperature of about
135.degree. C. It has been found that a coating dried with such a
heat drying process can withstand 50 or more cycles of the
mechanical scrubbing test.
[0261] In another non-limiting embodiment, the hard surface coating
composition can be applied to automobile glass, and then heat dried
at an air temperature of about 135.degree. C. It has been found
that a coating dried with such a heat drying process can withstand
50 or more cycles of the mechanical scrubbing test.
[0262] The dried hard surface coating is preferably substantially
hydrophilic. The dried hard surface, in some embodiments may have a
contact angle with water of: less than or equal to about 60; or
alternatively, less than or equal to about any increment of five
less than 60 (e.g., less than or equal to about 50, 45, 40, . . . ,
20, . . . , 10, etc.). In some embodiments, higher temperatures of
application or drying result in higher initial contact angles, and
lower temperatures of application or drying result in lower initial
contact angles. However, the contact angle can change over the
duration of the coating. The visual appearance of the dried hard
surface coating, in some embodiments, can be improved after the
surface is hydrated for 500 seconds. The visual improvement is
characterized as improved sheeting or improved curtaining of water
on the surface coating.
[0263] The application of the hard surface coating composition can
be performed by large-scale processes on hard surfaces and/or
finished articles in an industrial application, or in the
consumer's home by the use of an article of manufacture.
[0264] In one aspect, the method of the present invention can be
used in an automobile manufacturing and/or painting operation to
provide a durable finish on the exterior of an automobile. FIG. 4
is a flow chart which shows one non-limiting example of the steps
in painting and applying a clear coat finish to the exterior body
panels of an automobile. One clear coat composition comprises a
polyurethane produced from polymerization of carbamate and melamin
composition, such as that available under the tradename URECLEARO
from BASF, Southfield, Michigan, USA.
[0265] In the example shown in FIG. 4, the first step in painting
the automobile body panels is the application of two coats of
primer without flash time (elapsed time for organic solvent
evaporation) between coats. Following this, the primer is flashed
(dried at lower temperatures at first to drive off much of the
solvent(s), then heated to a higher temperature to cure the same;
this prevents bubbling) for 10 minutes. The panels are then baked
at 129.degree. C. for 30 minutes. After this, two coats of basecoat
(paint) are applied with a 60 second flash in between coats. Then,
two coats of clear coat are applied with a 60 second flash in
between coats. The panels are then heated for 10 minutes at
82.degree. C. This heating process is ramped up to 132.degree. C.,
and held at that temperature for 25 minutes. The final step is to
place the panels in an oven at 160.degree. C. for five minutes. Of
course, in other processes the temperatures and times can be varied
in any suitable manner. For example, a process used by ACT
Laboratories, Inc. (Hillsdale, MI, USA) that is used in the
automotive industry to test automobile body panels is described in
the Test Methods section.
[0266] As shown in FIG. 4, the hard surface coating composition
described herein can be applied at many different steps in the
process of applying the clear coat finish to the automobile body
panels. The hard surface coating composition described herein can
be applied after said one or more coats of paint are applied to
said automobile body parts; during the step of applying one or more
coats of clear coat to said automobile body parts; or, after said
one or more coats of clear coat are applied to said automobile body
parts.
[0267] In other embodiments, it may be desired to use nanoparticles
in the form of a powder. The nanoparticles can be used alone, or
they can be combined with some other substance to form a
composition. The clear coat composition, in such embodiments can be
provided in any suitable form, including, but not limited to
liquids, and powders. In embodiments in which it is desired to use
a powder hard surface coating comprising nanoclay with a powder
clear coat, it may be desirable to modify the application
procedure. The application procedure can be modified in many
different ways. In any embodiments desired, the surface onto which
the powder coating is to be deposited can also be charged to
facilitate attraction and adherence of the nanoparticles
thereto.
[0268] For instance, the clear coat powder composition can first be
applied by electrostatic deposition techniques or fluidized bed
techniques or other such techniques that are commonly practiced,
followed by application of the nanoclay coating composition by
electrostatic deposition or fluidized bed or other such techniques
that are commonly practiced. The surface can then be heated to
provide adequate curing.
[0269] In another embodiment, the clear coat powder composition can
first be coated with the powdered hard surface coating comprising
nanoclay. This can be followed by application of the clear coat
powder composition coated with the powder hard surface coating
comprising nanoclay to the desired surface by electrostatic
deposition techniques or fluidized bed techniques or other such
techniques that are commonly practiced. The surface can then be
heated to provide adequate curing.
[0270] In another embodiments, the clear coat powder composition
and the powder hard surface coating comprising nanoclay can be
applied simultaneously to the desired surface by electrostatic
deposition techniques or fluidized bed techniques or other such
techniques that are commonly practiced. The surface can then be
heated to provide adequate curing.
[0271] In other embodiments, such as in the auto body repair
business, where in some cases it is not possible to heat the body
panels to the temperatures described in the preceding paragraphs
without damaging other portions of the automobile, the hard surface
coating composition can be applied at much lower temperatures, such
as temperatures above 60.degree. C. (the temperature the surface of
a car can reach on a hot day). In such embodiments, accelerants can
be used, if desired.
[0272] In embodiments in which it is desired to use an aqueous hard
surface coating composition comprising nanoclay with an organic
clearcoat, it may be desirable to modify the application procedure.
For instance, the clearcoat composition could first be applied, and
then a "skim" or film could be formed on the top of the wet clear
coat using techniques known to those of skill in the art (clearcoat
compositions generally dry from the top portion thereof to the
bottom, and become slightly tacky when drying). The hard surface
coating composition could be placed on top of the skim, and then
the clearcoat with the hard surface coating composition thereon
could be heated together.
[0273] In any of the embodiments described in this specification,
multiple layers of the hard surface coating composition can be
applied to any of the hard surfaces described herein. These
multiple layers of hard surface coating composition can all have
the same chemical composition, or they can have different chemical
compositions.
[0274] In addition to applying the hard surface coating composition
described herein to automotive body panels, the hard surface
coating composition can be applied to glass, plastic, or rubber.
The hard surface coating composition can, for example, be applied
to automotive window glass. The hard surface coating composition
can be applied to automotive window glass at any stage in the
manufacture of the window glass, or in the manufacture of the
automobile.
[0275] In other embodiments, the method of applying the hard
surface coating composition described herein can be applied to the
components of aircraft, water craft, buildings, etc. to provide a
more durable surface coating.
[0276] The present invention also comprises a method of using
concentrated liquid or solid coating compositions, which are
diluted to form compositions with the usage concentrations, as
given hereinabove, for use in the "usage conditions". Concentrated
compositions comprise a higher level of nanoparticle concentration,
typically from about 0.1% to about 50%, alternatively from about
0.5% to about 40%, alternatively from about 1% to about 30%, by
weight of the concentrated coating composition.
[0277] Concentrated compositions are used in order to provide a
less expensive product. The concentrated product is alternatively
diluted with 1,000 parts suitable carrier medium, alternatively 100
parts suitable carrier medium, and alternatively 10 parts suitable
carrier medium of the coating composition.
[0278] In another embodiment of the present invention there is a
provided a method of using a liquid, coating composition comprising
(a) an effective amount of non-photoactive nanoparticles; (b)
optionally a surfactant; (c) optionally having associated to said
nanoparticle surface a quantity of one or more functionalized
surface molecules exhibiting properties selected from the group
consisting of hydrophilic, hydrophobic and mixtures thereof; (d)
optionally an effective amount of photoactive nanoparticles; (e)
optionally one or more adjunct ingredients; and (f) a suitable
carrier medium, alternatively concentrated liquid, for treating
dishware in the rinse step of an automatic dishwashing machine. The
rinse water should contain typically from about 0.0005% to about
1%, alternatively from about 0.0008% to about 0.1%, alternatively
from about 0.001% to about 0.02% of the nanoparticle.
[0279] Another alternative method comprises the treatment of
dishware with a coating composition dispensed from a sprayer at the
beginning and/or during the drying cycle. It is preferable that the
treatment is performed in accordance with the instructions for use,
to ensure that the consumer knows what benefits can be achieved,
and how best to obtain these benefits.
[0280] Another alternative method comprises stripping at least one
layer of nanopaticles from the transparent coating on a treated
hard surface using mechanical or chemical means to remove the layer
of foreign matter (i.e. soil, spotting residues, food etc.) in
accordance with the instructions for use to impart the benefits
desired, wherein mechanical or chemical means does not exclude the
weathering or optionally the normal use of the surface. Not to be
limited by theory, the strippable-film mechanism of this method is
depicted in FIGS. 1-3.
[0281] In FIGS. 1-3, the hard surface is designated by reference
number 20. The individual nanoparticles are designated by reference
number 22, and the layers formed thereby are designated by
reference number 24. The soil deposited on the nanoparticles is
designated by reference number 26. In one embodiment of the present
invention, such as an automotive, exterior building or dishware
surface application, an effective nanoparticle coating is deposited
as an invisible film, preventing soil 26 from adhering to the hard
surface 20 (FIG. 1). The nanoparticle coating consists of multiple
effective layers 24 of nanoparticle sheets that provide the
benefit. During the weathering, washing or stripping treatment
process, at least one top layer 24 of the nanoparticle coating is
removed, taking the soil 26 along with it (FIGS. 2 and 3).
III. ARTICLES OF MANUFACTURE
[0282] The present invention also relates to an article of
manufacture comprising the hard surface coating composition in a
package, in association with instructions for how to use the
coating composition to treat hard surfaces correctly, in order to
obtain the desirable results, viz, improved multi-use benefits
consisting of improved hard surface wetting and sheeting, quick
drying, uniform drying, soil removal, self-cleaning, anti-spotting,
anti-soil deposition, cleaner appearance, enhanced gloss, enhanced
color, minor surface defect repair, improved smoothness,
anti-hazing properties, modification of surface friction, release
of actives, reduced damage to abrasion, improved transparency and
mixtures thereof. An alternative article of manufacture comprises
said composition in a spray dispenser, in association with
instructions for how to use the coating composition to treat hard
surfaces correctly, including, e.g., the manner and/or amount of
composition to spray, and the alternative ways of applying the
coating composition, as will be described with more detailed herein
below. It is important that the instructions be as simple and clear
as possible, so that using pictures and/or icons is desirable.
[0283] Spray Dispenser
[0284] An article of manufacture herein comprises a spray
dispenser. The coating composition is placed into a spray dispenser
in order to be distributed onto the hard surface. Said spray
dispenser for producing a spray of liquid droplets can be any of
the manually activated means as is known in the art, e.g.
trigger-type, pump-type, non-aerosol self-pressurized, and
aerosol-type spray means, for treating the coating composition to
small hard surface areas and/or a small number of substrates, as
well as non-manually operated, powered sprayers for conveniently
treating the coating composition to large hard surface areas and/or
a large number of substrates. The spray dispenser herein does not
normally include those that will substantially form the clear,
aqueous coating composition. It has been found that providing
smaller particle droplets increases the performance. Desirably, the
Sauter mean particle diameter is from about 10 .mu.m to about 120
.mu.m, alternatively, from about 20 .mu.m to about 100 .mu.m.
Coating benefits for example are improved by providing small
particles (droplets), especially when the surfactant is
present.
[0285] The spray dispenser can be an aerosol dispenser. Said
aerosol dispenser comprises a container which can be constructed of
any of the conventional materials employed in fabricating aerosol
containers. The dispenser must be capable of withstanding internal
pressure in the range of from about 20 to about 110 p.s.i.g.,
alternatively from about 20 to about 70 p.s.i.g. The one important
requirement concerning the dispenser is that it be provided with a
valve member which will permit the clear, aqueous coating
composition contained in the dispenser to be dispensed in the form
of a spray of very fine, or finely divided, particles or droplets.
The aerosol dispenser utilizes a pressurized sealed container from
which the clear, aqueous coating composition is dispensed through a
special actuator/valve assembly under pressure. Incorporating
therein a gaseous component generally known as a propellant
pressurizes the aerosol dispenser. Common aerosol propellants,
e.g., gaseous hydrocarbons such as isobutane, and mixed halogenated
hydrocarbons, can be used. Halogenated hydrocarbon propellants such
as chlorofluoro hydrocarbons have been alleged to contribute to
problems, and are not alternatives. When cyclodextrin is present
hydrocarbon propellants are not alternatives, because they can form
complexes with the cyclodextrin molecules thereby reducing the
availability of uncomplexed cyclodextrin molecules for odor
absorption. Alternative propellants are compressed air, nitrogen,
inert gases, carbon dioxide, etc. A more complete description of
commercially available aerosol-spray dispensers appears in U.S.
Pat. Nos.: 3,436,772, Stebbins, issued Apr.8, 1969; and 3,600,325,
Kaufman et al., issued Aug. 17, 1971; both of said references are
incorporated herein by reference.
[0286] Alternatively the spray dispenser can be a self-pressurized
non-aerosol container having a convoluted liner and an elastomeric
sleeve. Said self-pressurized dispenser comprises a liner/sleeve
assembly containing a thin, flexible radially expandable convoluted
plastic liner of from about 0.010 to about 0.020 inch thick, inside
an essentially cylindrical elastomeric sleeve. The liner/sleeve is
capable of holding a substantial quantity of coating composition
and of causing said composition to be dispensed. A more complete
description of self-pressurized spray dispensers can be found in
U.S. Pat. Nos. 5,111,971, Winer, issued May 12, 1992, and
5,232,126, Winer, issued Aug. 3, 1993; both of said references are
herein incorporated by reference. Another type of aerosol spray
dispenser is one wherein a barrier separates the coating
composition from the propellant (alternatively compressed air or
nitrogen), as disclosed in U.S. Pat. No. 4,260,110, issued Apr.7,
1981, and incorporated herein by reference. Such a dispenser is
available from EP Spray Systems, East Hanover, N.J.
[0287] Alternatively, the spray dispenser is a non-aerosol,
manually activated, pump-spray dispenser. Said pump-spray dispenser
comprises a container and a pump mechanism which securely screws or
snaps onto the container. The container comprises a vessel for
containing the aqueous coating composition to be dispensed.
[0288] The pump mechanism comprises a pump chamber of substantially
fixed volume, having an opening at the inner end thereof. Within
the pump chamber is located a pump stem having a piston on the end
thereof disposed for reciprocal motion in the pump chamber. The
pump stem has a passageway there through with a dispensing outlet
at the outer end of the passageway and an axial inlet port located
inwardly thereof.
[0289] The container and the pump mechanism can be constructed of
any conventional material employed in fabricating pump-spray
dispensers, including, but not limited to: polyethylene;
polypropylene; polyethyleneterephthalate; blends of polyethylene,
vinyl acetate, and rubber elastomer. An alternative container is
made of clear, e.g., polyethylene terephthalate. Other materials
can include stainless steel. A more complete disclosure of
commercially available dispensing devices appears in: U.S. Pat.
Nos.: 4,895,279, Schultz, issued Jan. 23, 1990; 4,735,347, Schultz
et al., issued Apr.5, 1988; and 4,274,560, Carter, issued Jun. 23,
1981; all of said references are herein incorporated by
reference.
[0290] Alternatively, the spray dispenser is a manually activated
trigger-spray dispenser. Said trigger-spray dispenser comprises a
container and a trigger both of which can be constructed of any of
the conventional material employed in fabricating trigger-spray
dispensers, including, but not limited to: polyethylene;
polypropylene; polyacetal; polycarbonate;
polyethyleneterephthalate; polyvinyl chloride; polystyrene; blends
of polyethylene, vinyl acetate, and rubber elastomer. Other
materials can include stainless steel and glass. An alternative
container is made of clear, e.g. polyethylene terephthalate. The
trigger-spray dispenser does not incorporate a propellant gas into
the odor-absorbing composition, and alternatively it does not
include those that will form the coating composition. The
trigger-spray dispenser herein is typically one which acts upon a
discrete amount of the coating composition itself, typically by
means of a piston or a collapsing bellows that displaces the
coating composition through a nozzle to create a spray of thin
liquid. Said trigger-spray dispenser typically comprises a pump
chamber having either a piston or bellows which is movable through
a limited stroke response to the trigger for varying the volume of
said pump chamber. This pump chamber or bellows chamber collects
and holds the product for dispensing. The trigger spray dispenser
typically has an outlet check valve for blocking communication and
flow of fluid through the nozzle and is responsive to the pressure
inside the chamber. For the piston type trigger sprayers, as the
trigger is compressed, it acts on the fluid in the chamber and the
spring, increasing the pressure on the fluid. For the bellows spray
dispenser, as the bellows is compressed, the pressure increases on
the fluid. The increase in fluid pressure in either type of trigger
spray dispenser acts to open the top outlet check valve. The top
valve allows the product to be forced through the swirl chamber and
out the nozzle to form a discharge pattern. An adjustable nozzle
cap can be used to vary the pattern of the fluid dispensed.
[0291] For the piston spray dispenser, as the trigger is released,
the spring acts on the piston to return it to its original
position. For the bellows spray dispenser, the bellows acts as the
spring to return to its original position. This action causes a
vacuum in the chamber. The responding fluid acts to close the
outlet valve while opening the inlet valve drawing product up to
the chamber from the reservoir.
[0292] A more complete disclosure of commercially available
dispensing devices appears in U.S. Pat. Nos. 4,082,223, Nozawa,
issued Apr. 4, 1978; 4,161, 288, McKinney, issued Jul. 17, 1985;
4,434,917, Saito et al., issued Mar. 6, 1984; and 4,819,835,
Tasaki, issued Apr. 11, 1989; 5,303,867, Peterson, issued Apr. 19,
1994; all of said references are incorporated herein by
reference.
[0293] A broad array of trigger sprayers or finger pump sprayers is
suitable for use with the coating compositions of this invention.
These are readily available from suppliers such as Calmar, Inc.,
City of Industry, California; CSI (Continental Sprayers, Inc.), St.
Peters, Mo.; Berry Plastics Corp., Evansville, Ind., a distributor
of Guala.RTM. sprayers; or Seaquest Dispensing, Cary, Ill.
[0294] Nonlimiting examples of trigger sprayers are the blue
inserted Guala.RTM. sprayer, available from Berry Plastics Corp.,
or the Calmar TS800-1A.RTM., TS1300.RTM., and TS-800-2.RTM.,
available from Calmar Inc., because of the fine uniform spray
characteristics, spray volume, and pattern size. Alternatives
include sprayers with precompression features and finer spray
characteristics and even distribution, such as Yoshino sprayers
from Japan. Any suitable bottle or container can be used with the
trigger sprayer, an alternative bottle is a 17 fl-oz. bottle (about
500 ml) of good ergonomics similar in shape to the
Cinch.RTM.bottle. It can be made of any materials such as
high-density polyethylene, polypropylene, polyvinyl chloride,
polystyrene, polyethylene terephthalate, glass, or any other
material that forms bottles. Alternatively, it is made of
high-density polyethylene or clear polyethylene terephthalate.
[0295] For smaller fluid ounce sizes ( such as 1 to 8 ounces), a
finger pump can be used with canister or cylindrical bottle. The
alternative pump for this application is the cylindrical Euromist
II.RTM. from Seaquest Dispensing.
[0296] The article of manufacture herein can also comprise a
non-manually operated spray dispenser. By "non-manually operated"
it is meant that the spray dispenser can be manually activated, but
the force required to dispense the coating composition is provided
by another, non-manual means. Non-manually operated sprayers
include, but are not limited to, powered sprayers, air aspirated
sprayers, liquid aspirated sprayers, electrostatic sprayers, and
nebulizer sprayers. The coating composition is placed into a spray
dispenser in order to be distributed onto the hard surface.
[0297] Powered sprayers include self-contained powered pumps that
pressurize the aqueous coating composition and dispense it through
a nozzle to produce a spray of liquid droplets. Powered sprayers
are attached directly or remotely through the use of piping/tubing
to a reservoir (such as a bottle) to hold the aqueous coating
composition. Powered sprayers can include, but are not limited to,
centrifugal or positive displacement designs. It is preferred that
the powered sprayer be powered by a portable DC electrical current
from either disposable batteries (such as commercially available
alkaline batteries) or rechargeable battery units (such as
commercially available nickel cadmium battery units). Powered
sprayers can also be powered by standard AC power supply available
in most buildings. The discharge nozzle design can be varied to
create specific spray characteristics (such as spray diameter and
particle size). It is also possible to have multiple spray nozzles
for different spray characteristics. The nozzle may or may not
contain an adjustable nozzle shroud that would allow the spray
characteristics to be altered.
[0298] Nonlimiting examples of commercially available powered
sprayers are disclosed in U.S. Pat. Nos. 4,865,255, Luvisotto,
issued Sep. 12, 1989 which is incorporated herein by reference.
Alternative powered sprayers are readily available from suppliers
such as Solo, Newport News, Va. (e.g., Solo Spraystar rechargeable
sprayer.TM., listed as manual part #: U.S. Pat. No. 460 395) and
Multi-sprayer Systems, Minneapolis, Minn. (e.g., model: Spray
1).
[0299] Air aspirated sprayers include the classification of
sprayers generically known as "air brushes". A stream of
pressurized air draws up the aqueous coating composition and
dispenses it through a nozzle to create a spray of liquid. The
coating composition can be supplied via separate piping/tubing or
more commonly is contained in ajar to which the aspirating sprayer
is attached.
[0300] Nonlimiting examples of commercially available air aspirated
sprayers appears in U.S. Pat. Nos. 1,536,352, Murray, issued Apr.
22, 1924 and 4,221,339, Yoshikawa, issues Sep. 9, 1980; all of said
references are incorporated herein by reference. Air aspirated
sprayers are readily available from suppliers such as The Badger
Air-Brush Co., Franklin Park, Ill. (e.g., model #: 155) and Wilton
Air Brush Equipment, Woodridge, Ill. (e.g., stock #: 415-4000,
415-4001, 415-4100).
[0301] Liquid aspirated sprayers are typical of the variety in
widespread use to spray garden chemicals. The aqueous coating
composition is drawn into a fluid stream by means of suction
created by a Venturi effect. The high turbulence serves to mix the
aqueous coating composition with the fluid stream (typically water)
in order to provide a uniform mixture/concentration. It is possible
with this method of delivery to dispense the aqueous concentrated
coating composition of the present invention and then dilute it to
a selected concentration with the delivery stream.
[0302] Liquid aspirated sprayers are readily available from
suppliers such as Chapin Manufacturing Works, Batavia, N.Y. (e.g.,
model #: 6006).
[0303] Electrostatic sprayers impart energy to the aqueous coating
composition via a high electrical potential. This energy serves to
atomize and charge the aqueous coating composition, creating a
spray of fine, charged particles. As the charged particles are
carried away from the sprayer, their common charge causes them to
repel one another. This has two effects before the spray reaches
the target. First, it expands the total spray mist. This is
especially important when spraying to fairly distant, large areas.
The second effect is maintenance of original particle size. Because
the particles repel one another, they resist collecting together
into large, heavier particles like uncharged particles do. This
lessens gravity's influence, and increases the charged particle
reaching the target. As the mass of negatively charged particles
approach the target, they push electrons inside the target
inwardly, leaving all the exposed surfaces of the target with a
temporary positive charge. The resulting attraction between the
particles and the target overrides the influences of gravity and
inertia. As each particle deposits on the target, that spot on the
target becomes neutralized and no longer attractive. Therefore, the
next free particle is attracted to the spot immediately adjacent
and the sequence continues until the entire surface of the target
is covered. Hence, charged particles improve distribution and
reduce drippage.
[0304] Nonlimiting examples of commercially available electrostatic
sprayers appears in U.S. Pat. Nos. 5,222,664, Noakes, issued Jun.
29, 1993; 4,962,885, Coffee, issued Oct. 16, 1990; 2,695,002,
Miller, issued Nov. 1954; 5,405,090, Greene, issued Apr. 11, 1995;
4,752,034, Kuhn, issued Jun. 21, 1988; 2,989,241, Badger, issued
June 1961; all of said patents are incorporated herein by
reference. Electrostatic sprayers are readily available from
suppliers such as Tae In Tech Co, South Korea and Spectrum,
Houston, Texas.
[0305] Nebulizer sprayers impart energy to the aqueous coating
composition via ultrasonic energy supplied via a transducer. This
energy results in the aqueous coating composition to be atomized.
Various types of nebulizers include, but are not limited to,
heated, ultrasonic, gas, venturi, and refillable nebulizers.
[0306] Nonlimiting examples of commercially available nebulizer
sprayers appears in U.S. Pat. Nos. 3,901,443, Mitsui, issued Aug.
26, 1975; 2,847,248, Schmitt, issued Aug. 1958; 5,511,726,
Greenspan, issued Apr. 30, 1996; all of said patents are
incorporated herein by reference. Nebulizer sprayers are readily
available from suppliers such as A&D Engineering, Inc.,
Milpitas, Calif. (e.g., model A&D Un-231 ultrasonic handy
nebulizer) and Amici, Inc., Spring City, Pa. (model: swirler
nebulizer).
[0307] The alternative article of manufacture herein comprises a
non-manually operated sprayer, such as a battery-powered sprayer,
containing the aqueous coating composition. Alternatively the
article of manufacture comprises a combination of a non-manually
operated sprayer and a separate container of the aqueous coating
composition, to be added to the sprayer before use and/or to be
separated for filling/refilling. The separate container can contain
a usage composition, or a concentrated composition to be diluted
before use, and/or to be used with a diluting sprayer, such as with
a liquid aspirated sprayer, as described herein above.
[0308] Also, as described hereinbefore, the separate container
should have structure that mates with the rest of the sprayer to
ensure a solid fit without leakage, even after motion, impact, etc.
and when handled by inexperienced consumers. The sprayer desirably
can also have an attachment system that is safe and alternatively
designed to allow for the liquid container to be replaced by
another container that is filled. For example, a filled container
can replace the fluid reservoir. This can minimize problems with
filling, including minimizing leakage, if the proper mating and
sealing means are present on both the sprayer and the container.
Desirably, the sprayer can contain a shroud to ensure proper
alignment and/or to permit the use of thinner walls on the
replacement container. This minimizes the amount of material to be
recycled and/or discarded. The package sealing or mating system can
be a threaded closure (sprayer) which replaces the existing closure
on the filled and threaded container. A gasket is desirably added
to provide additional seal security and minimize leakage. The
gasket can be broken by action of the sprayer closure. These
threaded sealing systems can be based on industry standards.
However, it is highly desirable to use a threaded sealing system
that has non-standard dimensions to ensure that the proper
sprayer/bottle combination is always used. This helps prevent the
use of fluids that are toxic, which could then be dispensed when
the sprayer is used for its intended purpose.
[0309] An alternative sealing system can be based on one or more
interlocking lugs and channels. Such systems are commonly referred
to as "bayonet" systems. Such systems can be made in a variety of
configurations, thus better ensuring that the proper replacement
fluid is used. For convenience, the locking system can also be one
that enables the provision of a "child-proof" cap on the refill
bottle. This "lock-and-key" type of system thus provides highly
desirable safety features. There are a variety of ways to design
such lock and key sealing systems.
[0310] Care must be taken, however, to prevent the system from
making the filling and sealing operation too difficult. If desired,
the lock and key can be integral to the sealing mechanism. However,
for the purpose of ensuring that the correct recharge or refill is
used, the interlocking pieces can be separate from the sealing
system. E.g., the shroud and the container could be designed for
compatibility. In this way, the unique design of the container
alone could provide the requisite assurance that the proper
recharge/refill is used.
[0311] Examples of threaded closures and bayonet systems can be
found in U.S. Pat. No. 4,781,31 1, Nov. 1, 1988 (Angular Positioned
Trigger Sprayer with Selective Snap-Screw Container Connection,
Clorox), U.S. Pat. No. 5,560,505, Oct. 1, 1996 (Container and
Stopper Assembly Locked Together by Relative Rotation and Use
Thereof, Cebal SA), and U.S. Pat. No. 5,725,132, Mar. 10, 1998
(Dispenser with Snap-Fit Container Connection, Centico
International). All of said patents are incorporated herein by
reference.
[0312] The present invention also relates to an article of
manufacture comprising a coating composition for use in spraying
and/or misting an entire hard surface or article in a manner such
that excessive amounts of the coating composition are prevented
from being released to the open environment, provided in
association with instructions for use to ensure that the consumer
applies at least an effective amount of nanoparticle system and/or
coating composition, to provide the desired hard surface multi-use
benefit.
[0313] Other coating compositions of the present invention for use
to treat hard surfaces, such as dishware, in different steps of the
automatic dishwashing process, e.g., pre-wash, wash cycle, rinse
cycle, and drying cycle, can be packaged in association with
instructions for how to use the coating composition to treat
dishware correctly, in order to obtain the desirable hard surface
coating results, viz. improved multi-use hard surface wetting and
sheeting, quick drying, uniform drying, soil removal,
self-cleaning, anti-spotting, anti-soil deposition, cleaner
appearance, enhanced gloss, enhanced color, minor surface defect
repair, improved smoothness, anti-hazing properties, modification
of surface friction, release of actives, reduced damage to abrasion
and improved transparency.
[0314] PRODUCT WITH INSTRUCT10NS FOR USE
[0315] The present invention also encompasses the inclusion of
instructions on the use of the coating compositions of the present
invention with the packages containing the coating compositions
herein or with other forms of advertising associated with the sale
or use of the coating compositions. The instructions may be
included in any manner typically used by consumer product
manufacturing or supply companies. Examples include providing
instructions on a label attached to the container holding the
coating composition; on a sheet either attached to the container or
accompanying it when purchased; or in advertisements,
demonstrations, and/or other written or oral instructions which may
be connected to the purchase or use of the coating
compositions.
[0316] Specifically the instructions will include a description of
the use of the coating composition, for instance, the recommended
amount of composition to use in order to coat the hard surface or
article the recommended amount of composition to apply to the hard
surface; if spraying, soaking or rubbing is appropriate.
[0317] The coating compositions of the present invention are
alternatively included in a product. The product alternatively
comprises a hard surface coating composition in accordance with the
present invention, and further comprises instructions for using the
product to launder hard surfaces by contacting a hard surface in
need of treatment with an effective amount of the coating
composition such that the coating composition imparts one or more
desired hard surface coating benefits to the hard surface.
[0318] The following examples are illustrative of the present
invention, but are not meant to limit or otherwise define its
scope. All parts, percentages and ratios used herein are expressed
as percent weight unless otherwise specified.
[0319] The compositions and methods of the present invention can be
used for industrial modification of hard surfaces, such as in
automotive and building component manufacturing.
EXAMPLE(S)
[0320] The following provides several non-limiting examples of the
present invention.
Example 1
[0321] A composition comprising 68 grams of URECLEAR.RTM. clearcoat
obtained from BASF Corporation of Southfield, Mich., USA is
combined with 0.1 to 25 grams of a nanoclay, such as Laponite.TM.,
a synthetic hectorite clay obtained from Southern Clay Products,
Inc. of Gonzales, Tex. USA. These two components are mixed under
agitation, and 15 grams of methyl isoamylketone methyl-2-hexanone
is added.
[0322] The clearcoat composition is sprayed wet-on-wet over a high
solids basecoat onto electocoated primed automotive body panels.
The panels are flashed at ambient temperatures for 10 minutes and
then cured for 20 minutes at 270.degree. F. (132.20.degree.
C.).
Examples 2-15
[0323] Liquid coating compositions, according to the present
invention, are as follows where the ance is water:
2TABLE 1 Example # Nanoparticle (Wt %) Surfactant (Wt %) 2 Nanoclay
(0.1) Neodol 91-6 (0.075) 3 Nanoclay (0.05) Neodol 91-6 (0.075) 4
Nanoclay (0.05) Silwet L-77 (0.025) 5 Nanoclay (0.1) Q2-5211
(0.025) 6 Nanoclay (0.05) Q2-5211 (0.025) 7 Nanoclay (0.03) Q2-5211
(0.1) 8 Nanoclay (0.1) Tergitol 15-S-9 (0.1) 9 Nanoclay (0.1)
Tergitol NP-9 (0.1) 10 Nanoclay (0.1) Neodol 91-8 (0.075) 11
Nanoclay (0.1) Component A (0.2) 12 Nanoclay (0.2) Component A
(0.2) 13 Nanoclay (0.1) Component B (0.2) 14 Nanoclay (0.1) Neodol
91-6 (0.075) 15 Disperal P2 .TM. (0.1) Neodol 91-6 (0.075) 1.
Nanoclay can be any of the available synthetic hectorite clays,
such as Laponite .TM. available from Southern Clay Products, Inc.
2. Disperal P2 .TM. is boehmite alumina from Condea, Inc.
Examples 16-19
[0324] In the following examples, dispersants were formulated with
the nanoclay and surfactant low the hard surface coating
composition to be made with tap water:
3TABLE 2 Ex- ample Nanoparticle # (Wt %) Surfactant (Wt %)
Dispersant (Wt %) 16 Nanoclay (0.1) Neodol 91-6 (0.075)
Polyacrylate 4500 MW (0.02) 17 Nanoclay (0.1) Neodol 91-6 (0.075)
Poly (acrylic/maleic).sup.2 (0.02) 18 Nanoclay (0.1) Neodol 91-6
(0.075) Polyacrylate 2000 MW (0.02) 19 Nanoclay (0.1) Neodol 91-6
(0.075) STPP (0.02) 1. Nanoclay can be any of the available
synthetic hectorite clays, such as Laponite B .TM. from Southern
Clay Products, Inc. 2. MA:AA = 4:6, MW = 11,000.
Examples 20-27
[0325] Liquid coating compositions, according to the present
invention, where the balance is water, and where said coating
composition can be applied to surface, optionally the said coating
composition is diluted with water to achieve a concentrated coating
composition of 0.1% nanoparticle are as follows:
4TABLE 3 Ex- ample Nanoparticle Surfactant # (Wt %) (Wt %)
Dispersant (Wt %) 20 Nanoclay (1.6) Q2-5211 (0.8) None 21 Nanoclay
(0.8) Q2-5211 (0.4) None 22 Nanoclay (0.8) Neodol 91-6 (0.6) None
23 Disperal P2 .TM. Neodol 91-6 (7.5) None (10) 24 Nanoclay (5.0)
Neodol 91-6 (3.75) Polyacrylate 4500 MW (1.0) 25 Nanoclay (5.0)
Neodol 91-6 (3.75) Poly (acrylic/maleic).sup.3 (1.0) 26 Nanoclay
(1.0) Neodol 91-6 (0.75) Polyacrylate 4500 MW (0.2) 27 Nanoclay
(1.0) Neodol 91-6 (0.75) Polyacrylate 4500 MW (0.1) 1. Nanoclay can
be any of the available synthetic hectorite clays, such as Laponite
.TM. available from Southern Clay Products, Inc. 2. Disperal P2
.TM. is boehmite alumina from Condea, Inc. 3. MA:AA = 4:6, MW =
11,000.
[0326] Panels were treated with 0.1% nanoclay/ 0.075% Neodol 91-6
surfactant using a Solo sprayer and air-dried vertically. Panels
were heated in an oven at the temperatures specified in Table 1 for
25 min., and then allowed to cool. Post-heat performance was
assessed, panels were scrubbed (Sheen Wet Abrasion Scrub Tester,
500 g total wt., sponges saturated with dilute DAWN.RTM.
dishwashing liquid solution), and performance was reassessed.
Contact angle measurements were taken before heating, after
heating, and after scrubbing. A Miniscan XE with C/2.degree.
illuminant (Hunter Associates Laboratory, Inc., Reston, Va., USA)
was used to measure panel color (CIE L*a*b* color scale) after
heating. Some panels were treated with thionin cationic dye (500
ppm) to visually assess the coating compositions' longevity.
[0327] .sup.a black panels, cured 3 days
Results
[0328]
5TABLE 4 Heating Profile - Performance and Removability.sup.a
Sheeting/ Performance Curtaining After Lasts Through: Heating (0,
10, 50, 100 Temperature (.degree. C.) (25 min.) 500 scrubs) 22
Ambient Sheeting <10 scrubs 60 Baking temp used in aftermarket
Sheeting <10 scrubs coating applications 80-110 Low end baking
temp used by Curtaining <50 scrubs Original equipment
manufacturers (OEM's) (80.degree. C.) 135 Curtaining <100 scrubs
148 Curtaining 500 scrubs 160 High end baking temp used by
Curtaining 500 scrubs OEM's
Examples 28-29
[0329] Liquid hard surface coating compositions, according to the
present invention, placed in a spray bottled and delivered as a
spray-on formula for improved tough food soil release benefits on
hard surfaces are as follows:
6 TABLE 5 % by weight Component 28 29 1. Nanoclay 0.005-2 0.005-2
2. Ether capped poly(oxyalkylated) alcohol -- 0.01-1 3. Water
Balance Balance 1. Nanoclay can be any of the available synthetic
hectorite clays, such as Laponite RD .TM. or B .TM. from Southern
Clay Products, Inc. 2. Ether capped poly (oxyalkylated) alcohol
acts as a nonionic wetting agent. 3. Water is used for balance.
[0330] The above coating compositions when applied to a hard
surface, modifies the hard surface to exhibit at least one of the
following multi-use benefits consisting of improved hard surface:
wetting and sheeting, quick drying, uniform drying, soil removal,
self-cleaning, anti-spotting, anti-soil deposition, cleaner
appearance, enhanced gloss, enhanced color, minor surface defect
repair, smoothness, anti-hazing, modification of surface friction,
release of actives, reduced damage to abrasion and transparency; as
compared to a hard surface not treated with said hard surface
coating composition.
[0331] In certain aspects, the hard surface coating has a
transmittance to light of greater than or equal to about 75%
measured according to the Transmittance Test. That is, in such an
aspect, at least 75% of the incident light is transmitted through
the hard surface coating, and 25% of the incident light will not be
transmitted through the hard surface coating. In another aspect,
the hard surface coating has a transparency such that the surface
coated with the hard surface coating appears to the unaided human
eye to be substantially unaltered in comparison to a surface that
has not been coated with the hard surface coating.
[0332] It is also possible that the coatings described herein could
potentially provide other benefits. It is believed, subject to
confirmation, that the coatings described herein could potentially
be useful in reducing drag on moving articles such as skis, and
moving vehicles, such as automobiles, aircraft, watercraft, and the
like, and in preventing the buildup of material on hard surfaces,
such as preventing the buildup of ice on airplane wings and
preventing the buildup of deposits such as scale on the inside of
pipes in order to facilitate transport of fluids. One non-limiting
example of a preventative purpose for the coating would be to
utilize the coating composition in the nature of a drain cleaner.
Such a composition can be poured into drain pipes to prevent the
build up, or further build up, of deposits in the pipes.
[0333] In the case of any of the embodiments described in this
detailed description, unless specified otherwise, the coating can
be applied to the hard surface with or without the active curing
step. It is understood that the active curing step is useful
because it is believed to provide the coating with additional
durability. The coatings described herein can be applied at any
suitable time in the life of the hard surface including during or
after manufacture of the hard surface, if it is a type of hard
surface that is manufactured. The coating can also be applied
during the life of the hard surface for protective purposes,
preventative purposes, or any other purposes.
TEST METHODS
[0334] Unless otherwise stated, all tests are performed under
standard laboratory conditions (50% humidity and at 73OF
(23.degree. C.)).
[0335] Procedure for Measurement of Durability of Coating
[0336] Procedure:
[0337] 1. Clean surface: 4".times.12" auto panels are used as
received with desired coating applied. If X-ray fluorescence (XRF)
analysis is performed, panels are cut into 1".times.1.5"
(2.5.times.3.8 cm) rectangles, and cleaned by an ethanol rinse,
followed by washing with DAWN.RTM. dishwashing liquid available
from The Procter & Gamble Company of Cincinnati, Ohio, USA wash
and deionized water rinse prior to use in the scrub test.
[0338] 2. Apply product with hand pump sprayer until auto panel is
completely wet, allow to air dry (2 hr. minimum).
[0339] 3. Heat in oven for 25 min. (at desired temperature, e.g.,
one of the temperatures listed in Table 4), allow to cool to room
temperature.
[0340] 4. Measure contact angle.
[0341] 5. Assess visual performance.
[0342] 6. Perform scrub test.
[0343] 7. Assess visual performance.
[0344] 8. Measure contact angle once panel has dried.
[0345] 9. Perform dye or XRF analysis.
[0346] Auto Panel Specifications: Test panels, primer and basecoat
compositions are obtained from ACT Laboratories, Inc. (Hillsdale,
MI, USA). Their preparation method is as follows. The primer is
sprayed on in two coats with no flash time between coats. Primer
then flashes for 10 min. Substrates are baked in an oven for 30
min. at 265.degree. F. (129 .degree. C.) (this temperature is the
substrate, or panel, temperature). Film build range=0.9-1.1 mils
(22.9 to 27.9 .mu.m). Once the primer has cooled, the basecoat is
applied in two coats with 60 sec. flash between coats, for a film
build of 0.6-0.8 mils (15.2 to 20.3 .mu.m). Basecoat is flashed for
2 min. before the URECLEAR .RTM. clearcoat is applied in two coats
with 60 sec. flash between coats, to a film build of 1.9-2.1 mils
(48.3 to 53.3 .mu.m). The hard surface coating can be applied to
the panels at any stage of the process as shown in FIG. 4. The
panels are then flashed 20 min. prior to final oven bake: 10 min.
at 180.degree. F. (82 .degree. C.), then temperature is ramped up
to 270.degree. F. (132.degree. C.) for 25 min. (substrate
temperature).
[0347] Visual Performance Assessment
[0348] The substrate is rinsed with water, while the panel is held
at a 90.degree. angle to horizontal, and the panel is judged to
determine whether it exhibits sheeting, curtaining, or beading.
"Sheeting" is when an even film of water covers the substrate, and
slowly dries down without developing breaks in the film.
"Curtaining" occurs when the water slowly pulls into the middle and
drains off the substrate. Performance is judged to be "beading"
when the water shows no affinity for the surface, and quickly runs
off the substrate.
[0349] Scrub Method for Measurement of Durability
[0350] Sheen Wet Abrasion Scrub Tester (Model 903PG, Sheen
Instruments Ltd., Kingston, England) is fitted with
4-3.25".times.1.5".times.1.75" (8.25 cm.times.3.8 cm.times.4.4 cm)
sponges saturated with 30 mL of 0.2% DAWN ( dishwashing liquid in
deionized water with 10 grains per gallon added hardness (3:1 molar
ratio Ca.sup.2+:Mg.sup.2+). The instrument is set to 30 cycles per
minute, with 200 g weights on each of the 300 g carrier arms for a
total of 500 g per carrier arm. Scrub levels: 0, 10, 50, 100, 500
scrubs.
[0351] Contact Angle
[0352] Deionized water (25 .mu.L) is pipetted onto the coated
substrate, and contact angle is measured using a goniometer (NRL
C.A.Model #100-00 115 from Reme-Hart Inc., Mountain Lakes, N.J.,
USA, with Olympus TGHM light source, Olympus Optical Co., Ltd.,
Japan) Three measurements are made and averaged for each sample
tested.
[0353] Dye Analysis
[0354] Only white surfaces can be used for this analysis. The
surface is thoroughly rinsed with a solution of thionin cationic
dye (500 ppm in deionized water), followed by a rinse with water to
remove excess dye. An untreated surface of the same type is used as
a control. The surface coverage of the synthetic hectorite coating
can be assessed qualitatively by visual evaluation or by Hunter
Miniscan XE measurements.
[0355] X-Ray Fluorescence Analysis
[0356] X-Ray Fluorescence (XRF) is a nondestructive and noninvasive
technique that assesses the concentration of elements in a sample
or on the surface of a sample. The analysis is performed using a
Phillips Analytical, 12 Michigan Dr. Natick, Mass. 01760, USA,
PW2404 Sequential "4000W" X-Ray Spectrometer System, Serial No.
DY735. The instrument settings and specifications for XRF analysis
are set out in Table 6 below. Measurement Procedure:
[0357] 1) Calibration curves that relate instrument response to
analyte concentration can be constructed by pipetting known
concentrations of standards on the desired substrate. Standards are
allowed to slowly dry before measurements are performed.
[0358] 2) The standard or sample is assayed by placing the sample
face down in a sample cup, loading the sample cup into the
spectrometer, and initiating the data acquisition sequence. In the
case of synthetic hectorite coatings, the element lines for Mg and
Si are measured whereas the element line for Al is used for
aluminum oxide coating.
[0359] 3) Concentration for samples are determined from the
calibration curve for standards.
7TABLE 6 General conditions used on automobile surfaces Sample
Chamber Environment Vacuum Collimator mask size 16 mm Collimator
size 700 .mu.m Volatage 32 kV Current 125 mA Detector type
Goniometer Analysis time 30 sec. Element line assayed Kal for
desired element Sample Spinner On Tube Type Rhodium
[0360] Transmittance Test
[0361] Transmittance is measured using AS.TM.method D 1003-00.
Transmittance is expressed as a percentage that represents the
amount of incident light that passes through the article that is
tested.
[0362] Viscosity Test
[0363] All measurements were performed with a Brookfield RVDV II+
rotational viscometer available from Brookfield Engineering Labs,
Inc., Stoughton, Mass., USA. The recommended procedure is followed,
with the following exceptions. The recommended procedure is varied
by using a smaller vessel and removing the guard leg. The
calibration is to be determined using a 600 ml low form griffin
type beaker with Glycerin (1400 cp) and olive oil (80 cp) at 100
RPM. All subsequent measurements are performed in 50 ml beakers at
100 RPM with the appropriate spindle.
[0364] While particular embodiments of the subject invention have
been described, it will be obvious to those skilled in the art that
various changes and modifications of the subject invention can be
made without departing from the spirit and scope of the invention.
It is intended to cover, in the appended claims, all such
modifications that are within the scope of the invention.
* * * * *