U.S. patent application number 10/252881 was filed with the patent office on 2003-05-15 for hybrid inorganic/organic color effect materials and production thereof.
This patent application is currently assigned to Engelhard Corporation. Invention is credited to Fuller, Daniel S., Zimmermann, Curtis N..
Application Number | 20030091813 10/252881 |
Document ID | / |
Family ID | 25521085 |
Filed Date | 2003-05-15 |
United States Patent
Application |
20030091813 |
Kind Code |
A1 |
Fuller, Daniel S. ; et
al. |
May 15, 2003 |
Hybrid inorganic/organic color effect materials and production
thereof
Abstract
A color effect material is composed of a plurality of
encapsulated substrate platelets in which each platelet is
encapsulated with a first layer which acts as a reflector to light
directed thereon, a visibly transparent second organic layer
encapsulating the first layer in which the second layer provides an
optically variable reflection of light impinging thereon and a
third layer encapsulating the second layer and being selectively
transparent to light directed thereon.
Inventors: |
Fuller, Daniel S.; (Beacon,
NY) ; Zimmermann, Curtis N.; (Cold Spring,
NY) |
Correspondence
Address: |
DICKSTEIN SHAPIRO MORIN & OSHINSKY, LLP
1177 Avenue of the Americas
New York
NY
10036
US
|
Assignee: |
Engelhard Corporation
|
Family ID: |
25521085 |
Appl. No.: |
10/252881 |
Filed: |
September 24, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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10252881 |
Sep 24, 2002 |
|
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09973632 |
Oct 9, 2001 |
|
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Current U.S.
Class: |
428/323 ;
428/623; 428/624 |
Current CPC
Class: |
C09C 2220/20 20130101;
C09C 2200/1054 20130101; C09C 2200/1025 20130101; C09C 1/0078
20130101; Y10T 428/12549 20150115; Y10T 428/25 20150115; C09C
2200/304 20130101; C01P 2006/64 20130101; C01P 2006/63 20130101;
C09C 2200/303 20130101; C09C 1/0015 20130101; C01P 2006/62
20130101; Y10T 428/12556 20150115; C09C 2200/1008 20130101 |
Class at
Publication: |
428/323 ;
428/623; 428/624 |
International
Class: |
B32B 005/16 |
Claims
What is claimed is:
1. A hybrid inorganic/organic color effect material comprising a
platelet-shaped substrate encapsulated with: (a) a first layer
highly reflective to light directed thereon; and (b) a visibly
transparent second organic layer encapsulating the first layer and
providing a variable pathlength for light dependent on the angle of
incidence of light impinging thereon; and (c) a selectively
transparent third layer to light directed thereon.
2. The hybrid inorganic/organic color effect material of claim 1,
wherein the substrate is selected from the group consisting of
mica, aluminum oxide, bismuth oxychloride, boron nitride, glass
flake, iron oxide-coated mica, iron oxide coated glass, silicon
dioxide, titanium dioxide coated mica, titanium dioxide coated
glass, copper flakes, zinc flakes, alloy of copper flakes, and
alloy of zinc flakes.
3. The hybrid inorganic/organic color effect material of claim 1,
wherein the first layer is selected from the group consisting of
silver, gold, platinum, palladium, rhodium, ruthenium, osmium,
iridium and alloys thereof.
4. The hybrid inorganic/organic color effect material of claim 1,
wherein the first layer is selected from the group consisting of
aluminum, copper, gold, palladium, platinum, silver, zinc, an alloy
of aluminum, an alloy of copper, and an alloy of zinc.
5. The hybrid inorganic/organic color effect material of claim 4,
wherein the first layer is silver.
6. The hybrid inorganic/organic color effect material of claim 4,
wherein the first layer is gold.
7. The hybrid inorganic/organic color effect material of claim 4,
wherein the first layer is platinum.
8. The hybrid inorganic/organic color effect material of claim 4,
wherein the first layer is palladium.
9. The hybrid inorganic/organic color effect material of claim 4,
wherein the first layer is said alloy.
10. The hybrid inorganic/organic color effect material of claim 1,
wherein the third encapsulating layer is selected from the group
consisting of silver, gold, platinum, palladium, rhodium,
ruthenium, osmium, iridium and alloys thereof.
11. The hybrid inorganic/organic color effect material of claim 10,
wherein the third encapsulating layer is silver.
12. The hybrid inorganic/organic color effect material of claim 10,
wherein the third encapsulating layer is gold.
13. The hybrid inorganic/organic color effect material of claim 10,
wherein the third encapsulating layer is platinum.
14. The hybrid inorganic/organic color effect material of claim 10,
wherein the third encapsulating layer is palladium.
15. The hybrid inorganic/organic color effect material of claim 10,
wherein the third encapsulating layer is said alloy.
16. The hybrid inorganic/organic color effect material of claim 1,
wherein the third layer is selected from the group consisting of
aluminum, copper, silicon, titanium dioxide, iron oxide, chromium
oxide, a mixed metal oxide, aluminum, and alloys thereof.
17. The hybrid inorganic/organic color effect material of claim 1,
wherein the first layer is a sputter deposited layer.
18. The hybrid inorganic/organic color effect material of claim 1,
wherein the first layer is an electroless deposition layer.
19. A cosmetic preparation comprising the color effect material of
claim 1.
20. A paint formulation comprising the color effect material of
claim 1.
21. An ink formulation comprising the color effect material of
claim 1.
22. A nail enamel formulation comprising the color effect material
of claim 1.
23. A plastic formulation comprising the color effect material of
claim 1.
24. A toiletry preparation comprising the color effect material of
claim 1.
Description
[0001] This is a continuation of U.S. patent application Ser. No.
09/973,632, filed Oct. 9, 2001.
BACKGROUND OF THE INVENTION
[0002] Optically variable pigments have been described in the
patent literature since the 1960s. Hanke in U.S. Pat. No. 3,438,796
describes the pigment as being "thin, adherent, translucent, light
transmitting films or layers of metallic aluminum, each separated
by a thin, translucent film of silica, which are successively
deposited under controlled conditions in controlled, selective
thickness on central aluminum film or substrate." These materials
are recognized as providing unique color travel and optical color
effects.
[0003] The prior art approaches to optically variable pigments have
generally adopted one of two techniques. In the first, a stack of
layers is provided on a temporary substrate which is often a
flexible web. The layers are generally made up of aluminum and
MgF.sub.2. The stack of film is separated from the substrate and
subdivided through powder processing into appropriately dimensioned
particles. The pigments are produced by physical techniques such as
physical vapor deposition onto the substrate, separation from the
substrate and subsequent comminution. In the pigments obtained in
this way, the central layer and all other layers in the stack are
not completely enclosed by the other layers. The layered structure
is visible at the faces formed by the process of comminution.
[0004] In the other approach, a platelet shaped opaque metallic
substrate is coated or encapsulated with successive layers of
selectively absorbing metal oxides and non-selectively absorbing
layers of carbon, metal and/or metal oxide. To obtain satisfactory
materials using this approach, the layers are typically applied by
chemical vapor deposition techniques in a fluidized bed. A major
shortcoming of this technique is that fluidized bed processes are
cumbersome and require substantial technical infrastructure for
production. An additional limitation related to the substrates
utilized is that traditional metal flakes usually have structural
integrity problems, hydrogen outgassing problems and other
pyrophoric concerns.
[0005] The prior art approaches suffer from additional
disadvantages. For instance, certain metals or metal flake such as
chromium and aluminum, specifically when they are used as outer
layers may have perceived health and environmental impacts
associated with their use. The minimization of their use in optical
effect materials should be advantageous due to their perceived
impact.
SUMMARY OF THE INVENTION
[0006] The present invention provides a color effect material
comprising a platelet-shaped substrate encapsulated with(a) a first
layer highly reflective to light directed thereon; (b) a visibly
transparent second organic layer encapsulating the first layer and
providing a variable pathlength for light dependent on the angle of
incidence of light impinging thereon in accordance with Snell=s
Law; and (c) a selectively transparent third layer to light
directed thereon.
BRIEF DESCRIPTION OF THE DRAWING
[0007] FIG. 1 represents a modified plow type mixer under vacuum
and at elevated temperature. The reactor consists of refractory
tube 1 containing a ceramic boat 2 filled with polymer precursor
dichlorodipara-xylylene. The precursor is volatilized in the tube
and enters the pyrolysis furnace 3 operating at a temperature
greater than about 600.degree. C. Under elevated temperature, the
precursor is converted into a highly reactive monomeric vapor. The
reactive monomer is transported to the main chamber of the
evacuated mixer while being maintained at about 0.1 torr by vacuum
pump 10. The reactive monomer enters the mixing chamber through the
tapered ceramic tube 5 where it immediately comes in contact with
particles 11 which are mechanically aerosolized by mixing blades 6.
The mixing blades are driven by motor 8 having a shaft 7 extending
into the mixer 4 through vacuum seal 9.
DESCRIPTION OF THE INVENTION
[0008] It is an object of the present invention to provide novel
hybrid inorganic/organic color effect materials (HIO-CEMs) which
can also be prepared in a reliable, reproducible and technically
efficient manner. This object is achieved by a HIO-CEM comprising a
platelet-shaped substrate coated with: (a)a first layer highly
reflective to light directed thereon; and (b) a visibly transparent
second organic layer encapsulating the first layer in which the
second layer consists of a low index of refraction material,
typically a refractive index from 1.3 to 2.5 and more specifically
between 1.4 and 2.0, that provides a variable path length for light
dependent on the angle of incidence of light impinging thereon; and
(c) a selectively transparent third layer to light directed
thereon.
[0009] The degree of reflectivity for the first encapsulating layer
should be from 100% to 5% reflectivity, whereas the selective
transparency of the third encapsulating layer should be from 5% to
95% transmission. More specifically, one would prefer to have
50-100% reflectivity and 50-95% transparency for the first and
third encapsulating layers, respectively. The degree of
reflectivity and transparency for different layers can be
determined by a variety of methods such as ASTM method E1347-97,
E1348-90 (1996) or F1252-89 (1996).
[0010] The substrate can be mica, aluminum oxide, bismuth
oxychloride, boron nitride, glass flake, iron oxide-coated mica
(ICM), silicon dioxide, titanium dioxide-coated mica (TCM), copper
flake, zinc flake, alloy of copper flake, alloy of zinc flake, or
any encapsulatable smooth platelet.
[0011] The first and third layers can be the same or different such
as precious metals (i.e., silver, gold, platinum, palladium,
rhodium, ruthenium, osmium and/or iridium or alloys thereof),
copper, zinc, an alloy of copper or an alloy of zinc, silicon,
titanium dioxide, iron oxide, chromium oxide, a mixed metal oxide,
and aluminum. Of course, when the substrate is copper flake, zinc
flake, alloy of copper flake or alloy of zinc flake, there is no
need for such a first layer since it would be part of the
substrate.
[0012] The second encapsulating layer can be any organic material
such as polymer, for example and preferably para-xylylene polymers
and polydivinylbenzene.
[0013] An advantage of the present invention is the wide variety of
visibly transparent polymers that can be easily processed and
economically employed. Of particular advantage is the use of
para-xylylene polymers, the monomers of which can be produced in
quantitative yields via thermal cleavage of cyclic dimmers without
the production of gaseous by products. Additional advantages of
these polymers would include their superior dimensional stability
with respect to changes in relative humidity and unique optical,
chemical and mechanical properties. The above advantages are
imperative when being utilized as an optical encapsulation for
controlling light and applications involving a variety of
environments. Prior art has always focused on established, however
limiting, inorganic materials. The historical view of polymer
technology is their poor thermal and mechanical stability and thus
were ignored prior to the present invention.
[0014] Another advantage of the present invention is that one does
not have to start with a traditional particulate metal flake which
may have structural integrity problems, hydrogen outgassing
problems and a host of other perceived issues (pyrophoric and
environmental concerns) typically associated with metal flakes. The
precious metals when used in this invention are much more
chemically stable than traditional particulate metal flakes such as
aluminum and generally prefer to be in their non-oxidized metallic
ground state. Furthermore, silver is preferred when employed as one
of the reflecting layers, as it can maximize the chromaticity of
the reflected color(s) of the HIO-CEM. In addition, when silver is
used as the final (outer) layer of the particle, it imparts
electrical conductivity to the HIO-CEM which may be desirable in
some applications such as powder coatings. Advantages can also be
realized when utilizing alloys as the first and/or third
encapsulating layer. For instance, brass alloy when used in this
invention is much more chemically stable than aluminum and is known
to have long term weather stability. Brass is nearly chemically
inert which allows great flexibility in the chemical systems
employed in the manufacture of such effect materials and in their
applications in end uses such as in paint, ink and polymer systems.
Another advantage over the prior art is that brass when used as one
of the reflecting layers in this invention, is a good reflector of
white light and at the same time provides an attractive bulk color.
The same would be true for an aluminum-copper alloy. Such an alloy
is advantageous due to its attractive bulk color effect, while
maintaining high reflectivity. Additionally, both brass and copper
coated substrates provide the decorative/functional attributes of
brass and copper, however under more environmentally favorable
terms due to the reduced metal concentration since the HIO-CEMs of
the present invention are not pure brass or copper, rather brass or
copper coated inorganic substrates. In addition, one can produce
the HIO-CEMs where the outer encapsulating layers are not made of
brass, or other alloys.
[0015] A surprising aspect of the present invention is that cost
effective composite materials are created with desirable optical
effect and conductive properties.
[0016] Organic polymer layers can be deposited by aqueous
polymerization/precipitation, solvent polymerization/deposition or
chemical vapor deposition. For aqueous deposition, the polymer is
deposited from aqueous monomers and initiators. For solvent
deposition, the polymer is solubilized in an appropriate solvent
and deposited on the substrate during solvent evaporation, or
alternatively monomers added to the solvent would be initiated and
polymerized on the surface of the coated substrate. For chemical
vapor deposition, the polymer is deposited from gaseous monomers
such as hexamethylene diisocyanate, toluene diisocyanate or
isophorone diisocyanate and polymerized on the coated substrate
surface with hexamethylene diamine or hydrazine. In addition,
parylene can be directly deposited in the gas phase from the
thermal cleavage of cyclic dimmers.
[0017] Inorganic metal layers are preferably deposited by
electroless deposition and the non-metal layers preferably by
sol-gel deposition. An advantage of electroless deposition (Egypt.
J. Anal. Chem., Vol. 3, 118-123 (1994)) is that it is a world wide
established chemical technique, not requiring cumbersome and
expensive infrastructure compared to other techniques. The
electroless deposition technique also allows one to control the
degree of reflectivity of light quite accurately and easily by
varying the metal film thickness. Additionally, the known
procedures are generalized procedures capable of being utilized for
coating a variety of surfaces. Furthermore, an encapsulating layer
of a metal or metal oxide can also be deposited onto any of the
substrates by chemical vapor deposition from an appropriate
precursor (The Chemistry of Metal CVD, edited by Toivo T. Kodas and
Mark J. Hampden-Smith; VCH Verlagsgesellschaft GmbH, D-69451
Weinheim, 1994, ISBN 3-527-29071-0).
[0018] For deposition of alloys, a unique method has been developed
as described in U.S. Pat. No. 4,940,523 which outlines a "process
and apparatus for coating fine particles." In addition, the
technique can be used to deposit pure metals such as chromium,
platinum, gold and aluminum, or ceramics.
[0019] The products of the present invention are useful in
automotive, cosmetic, industrial or any other application where
metal flake, iridescent materials, pearlescent or absorption
pigments are traditionally used.
[0020] The size of the platelet-shaped substrate is not critical
per se and can be adapted to the particular use. In general, the
particles have average largest major dimensions of about 5-250
.mu.m, in particular 5-100 .mu.m. Their specific free surface area
(BET) is in general from 0.2 to 25 m.sup.2/g. Of course similar
size substrates can be made in which their surface area has been
engineered to a much higher or lower value.
[0021] The HIO-CEMs of the invention are notable for multiple
encapsulation of the platelet-shaped substrate.
[0022] The first metallic encapsulating layer is highly reflective
to light directed thereon. The thickness of the first layer is not
critical so long as it is sufficient to make the layer highly
reflective. If desirable, the thickness of the first layer can be
varied to allow for selective transmission of light. The thickness
of the first metallic layer may be 5 nm to 500 nm and preferably 25
nm to 100 nm for copper, zinc, silver, aluminum or alloys thereof.
A metallic layer thickness out of the above-mentioned ranges will
typically be either completely opaque or allow for substantial
transmission of light. In addition to its reflective properties,
the metallic encapsulating layer may exhibit unique bulk color
effects depending on the film thickness. For example, a brass
coating thickness of >50 nm will begin to exhibit a metallic
gold bulk color, while maintaining good reflectivity. The mass
percent of the coating will be directly related to the surface area
of the particulate substrate being utilized.
[0023] The second organic encapsulating layer must provide a
variable pathlength for light dependent on the angle of incidence
of light impinging thereon and therefore, any low index of
refraction material that is visibly transparent may be utilized.
Preferably, the second layer is selected from the group consisting
of parylene, polytetrafluoroethylene, polyvinylacetate,
polydivinylbenzene, ethylcellulose, polymethylmethacrylate,
polyvinylalcohol, polyurethanes and polyureas. More preferably, the
second layer is a parylene or polydivinylbenzene.
[0024] The thickness of the second layer varies depending on the
degree of color travel desired. In addition, the second layer will
have a variable thickness depending on a variety of factors,
especially refractive index. Materials having a refractive index
around 1.5 tend to require a film thickness of a few hundred
nanometers for generation of unique color travel. For instance, a
second layer has a preferable thickness of about 75 to 500 nm for
parylene, polytetrafluoroethylene, polyvinylacetate,
polydivinylbenzene, ethylcellulose, polymethylmethacrylate,
polyvinylalcohol, polyurethanes and polyureas.
[0025] In one embodiment, the second layer is encapsulated by a
selectively-transparent third layer that allows for partial
reflection of light directed thereon. Preferably, the third
encapsulating layer is selected from the group consisting of
copper, silicon, titanium dioxide, iron oxide, chromium oxide, a
mixed metal oxide, aluminum or alloys thereof. More preferably, the
third encapsulating layer is one or more of the precious metals
selected from the group consisting of silver, gold, platinum,
palladium, rhodium, ruthenium, osmium and/or iridium or alloys
thereof.
[0026] Of course, the third layer can also contribute to the
interference color of the pigment. Its thickness can vary but must
always allow for partial transparency. For instance, a third layer
has a preferable thickness of about 5 to 45 nm for silicon; about 2
to 25 nm for aluminum; about 2 to 25 nm for copper; about 2 to 20
nm for zinc; about 1 to 25 nm for titanium nitride; about 10 to 60
nm for iron oxide; about 10 to 60 nm for chromium oxide; about 10
to 120 nm for titanium dioxide; about 5 to 100 nm for a mixed metal
oxide, about 5 to 50 nm for silver; about 3 to 30 nm for gold;
about 3 to 30 nm for platinum; and about 5 to 30 nm for palladium.
The precious metal and base metal alloys generally have a similar
film thickness requirement compared to the pure metal. It is
recognized that a film thickness out of the above range may be
applicable depending on the desired effect.
[0027] All the encapsulating layers of the CEM of the invention are
altogether notable for a uniform, homogeneous, film-like structure
that results from the manner of preparation according to the
invention.
[0028] In the novel process for preparing the coated platelet-like
substrates, the individual coating steps are each effected by
sputter deposition, electroless deposition, complex coacervation,
vapor deposition or hydrolysis/condensation of suitable starting
compounds in the presence of the substrate particles to be coated.
Alloys, such as brass, can be deposited by a sputtering technique
as described in U.S. Pat. No. 4,940,523. In addition, pure metals
such as aluminum, copper and zinc, as well as others, can be
sputter deposited. Electroless deposition of metals is an
established technique for coating particulate materials. For
instance, metals can be deposited by electroless techniques from
reduction of aqueous salts of the metals, such as HAuCl.sub.4,
AgNO.sub.3, CuSO.sub.4, H.sub.2PtCl.sub.6, PdCl.sub.2. Polymers
such as parylene can readily be deposited in the vapor phase
according to well established techniques. Detailed parylene
chemistry, along with vapor deposition techniques, is taught to us
in U.S. Pat. No. 3,342,754 by Gorham, this disclosure of which is
hereby incorporated by reference. It is understood that one can
control and vary the refractive index by the multitude of polymer
structures prepared by the teachings of Gorham, as well as other
polymer synthesis techniques. Titanium dioxide can be deposited
from tetraalkoxides such as titanium tetraethoxide, halide
compounds such as titanium tetrachloride and sulfate compounds such
as titanium sulfate, titanium nitride from titanium tetrachloride,
tetrakis(diethylamido)titanium (TDEAT) and
tetrakis(dimethylamido)titaniu- m (TDMAT); iron oxide from iron
carbonyl, iron sulfate and iron chloride; and chromium oxide from
chromium carbonyl and chromium chloride.
[0029] In general, the synthesis of a hybrid inorganic/organic
color effect material can be as follows: a platelet material such
as mica is suspended while stirring in an aqueous medium. To the
suspension is added a metal precursor capable of depositing metal
on the substrate by electroless deposition, along with a suitable
reducing agent. The highly reflective metal coated substrate is
filtered, washed and dried. An aqueous deposition process can be
employed for the deposition of an organic polymer on the metal
coated mica or other substrate. The polymer is deposited from
aqueous monomers and initiators. The organic material encapsulated
metal coated platelet is filtered, washed and re-suspended in a
stirred aqueous medium. To the aqueous medium is added a metal
precursor capable of depositing metal on the substrate by
electroless deposition, along with a suitable reducing agent. The
metal solution for electroless deposition is added as described
above allowing for the deposition of a selectively transparent
metal coating. The final particulate product is washed, dried and
exhibits optical color effects as a function of viewing angle.
[0030] Depending on the thickness of the low refractive index
second encapsulating layer, the final HIO-CEM will display multiple
different color effects as a function of viewing angle (red,
orange, green, violet). The platelet substrate acts as a carrier
substrate. It may, or may not, have a contribution or effect on the
final optical properties of the particulate.
[0031] The hybrid inorganic/organic color effect materials
(HIO-CEMs) of the invention are advantageous for many purposes,
such as the coloring of paints, printing inks, plastics, glasses,
ceramic products and decorative cosmetic preparations. Their
special functional properties make them suitable for many other
purposes. The CEMs, for example, could be used in electrically
conductive or electromagnetically screening plastics, paints or
coatings or in conductive polymers. The conductive functionality of
the CEMs makes them of great utility for powder coating
applications.
[0032] The above-mentioned compositions in which the compositions
of this invention are useful are well known to those of ordinary
skill in the art. Examples include printing inks, nail enamels,
lacquers, thermoplastic and thermosetting materials, natural resins
and synthetic resins. Some non-limiting examples would include
polystyrene and its mixed polymers, polyolefins, in particular
polyethylene and polypropylene, polyacrylic compounds, polyvinyl
compounds, for example polyvinyl chloride and polyvinyl acetate,
polyesters and rubber, and also filaments made of viscose and
cellulose ethers, cellulose esters, polyamides, polyurethanes,
polyesters, for example polyglycol terephthalates, and
polyacrylonitrile.
[0033] For a well-rounded introduction to a variety of pigment
applications, see Temple C. Patton, editor, The Pigment Handbook,
volume II, Applications and Markets, John Wiley and Sons, New York
(1973). In addition, see for example, with regard to ink: R. H.
Leach, editor, The Printing Ink Manual, Fourth Edition, Van
Nostrand Reinhold (International) Co. Ltd., London (1988),
particularly pages 282-591; with regard to paints: C. H. Hare,
Protective Coatings, Technology Publishing Co., Pittsburgh (1994),
particularly pages 63-288. The foregoing references are hereby
incorporated by reference herein for their teachings of ink,
cosmetic, paint and plastic compositions, formulations and vehicles
in which the compositions of this invention may be used including
amounts of colorants. For example, the pigment may be used at a
level of 10 to 15% in an offset lithographic ink, with the
remainder being a vehicle containing gelled and ungelled
hydrocarbon resins, alkyd resins, wax compounds and aliphatic
solvent. The pigment may also be used, for example, at a level of 1
to 10% in an automotive paint formulation along with other pigments
which may include titanium dioxide, acrylic lattices, coalescing
agents, water or solvents. The pigment may also be used, for
example, at a level of 20 to 30% in a plastic color concentrate in
polyethylene.
[0034] In the cosmetic field, these pigments can be used in the eye
area and in all external and rinse-off applications. They are
restricted only for the lip area. Thus, they can be used in hair
sprays, face powder, leg-makeup, insect repellent lotion, mascara
cake/cream, nail enamel, nail enamel remover, perfume lotion, and
shampoos of all types (gel or liquid). In addition, they can be
used in shaving cream (concentrate for aerosol, brushless,
lathering), skin glosser stick, skin makeup, hair groom, eye shadow
(liquid, pomade, powder, stick, pressed or cream), eye liner,
cologne stick, cologne, cologne emollient, bubble bath, body lotion
(moisturizing, cleansing, analgesic, astringent), after shave
lotion, after bath milk and sunscreen lotion.
EXAMPLE 1
Procedure for Evaluation of CEMs According to the Invention
[0035] The luster and color are evaluated using drawdowns on a
hiding chart (Form 2-6 Opacity Charts of the Leneta Company) both
visually and instrumentally. A drawdown on the black portion of the
card displays the reflection color while the white portion displays
the transmission color at non-specular angles.
[0036] The drawdowns are prepared by incorporating 3-12% HIO-CEM in
a nitrocellulose lacquer, with the concentration dependent on the
particle size distribution of the HIO-CEM. For example, a 3%
drawdown would likely be used for an average HIO-CEM particle size
of 20 .mu.m while a 12% drawdown might be used for an average
HIO-CEM particle size of 100 .mu.m. The HIO-CEM-nitrocellulose
suspension is applied to the drawdown card using a Bird film
application bar with a wet film thickness of 3 mil.
[0037] When these drawdowns are observed visually, a variety of
colors can be observed dependent on the viewing angle, such as,
aqua to blue to violet. The degree of color travel observed is
controlled by the thickness of the low index of refraction layer.
Other quantifiable parameters commonly used to describe effect
pigments, such as lightness (L*) and chromaticity (C*), can be
controlled through both: a) the choice of materials used as lower
reflecting and top, selectively transmitting encapsulating layers
and b) the thickness of said lower and top encapsulating
layers.
[0038] The drawdown is further characterized using a
goniospectrophotometer (CMS-1500 from Hunter). The reflectivity vs.
wavelength curve is obtained at various viewing angles. The color
travel for the HIO-CEM is described using the CIELab L*a*b* system.
The data is recorded both numerically and graphically. The
numerical recording for a HIO-CEM representative of that obtained
in Example 2 is as follows:
1 Approximate Approximate Approximate Silver Thickness 1.sup.st
Polymer Thickness Silver Thickness 3.sup.rd Incident Encapsulating
2.sup.nd Encapsulating Encapsulating Angle Layer (nm) Layer (nm)
Layer (nm) L* A* B* 0 50 250 4 70 48 -30 10 50 250 4 71 48 -28 20
50 250 4 73 45 -22 30 50 250 4 76 37 -10 40 50 250 4 80 24 7 50 50
250 4 84 10 27 60 50 250 4 88 1 36 70 50 250 4 90 0 27 0 50 75 4 73
4 37 0 50 100 4 53 50 -51 0 50 125 4 78 -47 -21 0 50 150 4 96 -9 14
0 50 175 4 95 2 24 0 50 200 4 91 0 41 0 50 225 4 84 11 30 0 50 250
4 70 48 -30 0 50 275 4 68 26 -36 0 50 300 4 79 -46 -11 0 50 325 4
90 -43 23 0 50 350 4 93 -10 44 0 50 400 4 83 34 -2
[0039] The L*a*b* data characterizes the appearance of the sample.
L* is the lightness/darkness component, a* describes the red/green
color component, b* represents the blue/yellow component.
EXAMPLE 2
Preparation of Ag/polydivinylbenzene/Ag CEM
[0040] Fifty grams of silver coated borosilicate flake is placed in
a 1 liter oven dried morton flask containing 650 ml of mineral
spirits (boiling point 179-210.degree. C.) previously dried over
anhydrous magnesium sulfate. A condenser containing drierite
desiccant is fitted to one neck of the 3-neck morton flask with a
stirring shaft and temperature probe fitted to the other two necks.
The suspension is stirred at 250 rpm=s and heated to 100.degree. C.
To the heated suspension is added 0.82 grams of benzoyl peroxide
crystals followed by 7.4 grams (0.057 moles) of divinylbenzene
(technical purity, 80% mixture of isomers). The reaction is allowed
to stir at 100.degree. C. for 18 hours and then cooled to
45.degree. C. The entire suspension is then filtered on an 11 cm
Buchner funnel using #2 Whatman filter paper, rinsed with ethanol
and the product dried at 120.degree. C. The calculated yield of the
PDVB is 82% and calculated film thickness is 300 nanometers. The
resulting PDVB coating is visibly transparent and does not decrease
the high reflectivity of the silver coated borosilicate flake.
[0041] Ten grams of the above PDVB encapsulated silver coated flake
is dispersed in 100 ml of distilled water in a 250 ml 3-neck flask.
A stirring shaft, pH meter and temperature probe are fitted to the
3-neck flask. The suspension is stirred at 250 rpms. To the
suspension is added a colloidal solution of 0.10 grams of tin
chloride in 100 ml of distilled water. After 10 minutes of
stirring, the suspension is filtered on an 11 cm Buchner funnel
using #2 Whatman filter paper and rinsed with distilled water. The
rinsed presscake is then transferred to a 250 ml 3-neck morton
flask fitted with a stirring shaft, pH meter and temperature probe.
A solution of 1.0 grams of dextrose in 75 ml of distilled water is
added to the flask and stirred at 250 rpm=s. Through the
temperature probe port of the flask a solution of 1.0 grams silver
nitrate in 100 ml of distilled water containing a molar excess of
2-amino-2-methyl propanol is added at 10 ml per minute.
[0042] After a few minutes, the slurry displays a brilliant
greenish to gold color flop. The entire suspension is then filtered
on an 11 cm Buchner funnel using #2 Whatman filter paper, rinsed
with distilled water and the product dried at 120.quadrature.C. In
bulk powder form the product exhibits pronounced color effects
based on viewing angle varying from green to gold to red
interference effects.
EXAMPLE 3
[0043] Silver coated borosilicate particles are introduced into a
modified plow type mixer as described in FIG. 1. The reactor
consists of refractory tube 1 containing a ceramic boat 2 filled
with polymer precursor dichloro-di-p-xylylene. The precursor is
volatilized in the tube and enters the pyrolysis furnace 3
operating at a temperature of about 600.degree. C. Under elevated
temperature, the precursor is converted into a highly reactive
monomeric vapor. Encapsulation and polymerization of the
particulate material involves the pyrolysis cleavage of the
methylene-methylene bonds in dichloro-di-p-xylylene resulting in
two molecules of reactive monomer chloro-p-xylylene. The reactive
monomer is transported to the main chamber of the evacuated mixer
while being maintained at about 0.1 torr by vacuum pump 10. As the
reactive monomer enters the aerosolized cloud of particles 11
through the tapered ceramic tube 5, it is adsorbed on the particle
surfaces followed by instantaneous polymerization. Mechanical
aerosolization of the powders is achieved by mixing blades 6 driven
by motor 8 having a shaft 7 extending into the mixer 4 through
vacuum seal 9. The resulting microencapsulated particles have a
uniform optical quality coating of parylene. The powder is
eventually removed from the reactor and the final silver coating is
applied as in Example 2.
EXAMPLE 4
[0044] A HIO-CEM prepared according to example 2 is incorporated
into polypropylene step chips at 1% concentration. The step chips
are appropriately named since they have graduating thickness at
each step across the face of the chip. The graduating steps allow
one to examine the different effect of the HIO-CEM based on polymer
thickness.
EXAMPLE 5
[0045] A HIO-CEM prepared according to example 2 is incorporated
into a nail enamel. 10 g of the HIO-CEM is mixed with 82 g of
suspending lacquer SLF-2, 4 g lacquer 127P and 4 g ethyl acetate.
The suspending lacquer SLF-2 is a generic nail enamel consisting of
butyl acetate, toluene, nitrocellulose, tosylamide/formaldehyde
resin, isopropyl alcohol, dibutyl phthalate, ethyl acetate,
camphor, n-butyl alcohol and silica.
EXAMPLE 6
[0046] A 10% by weight HIO-CEM from example 2 is sprayed in a
polyester TGIC powder coating from Tiger Drylac using a PGI corona
Gun #110347. The HIO-CEM is mixed in a clear polyester system and
sprayed over a RAL 9005 black pigmented polyester powder. The
HIO-CEM is highly attracted to the ground metal panel due to its
electrical properties. Additionally, due to its high affinity to
orient closely to the surface it produces a finish that is high in
distinctness of image (DOI). It does not require an additional
clear coat to reduce protrusion often caused by traditional
pearlescent and metal flake pigments.
EXAMPLE 7
[0047] A 10% dispersion of the HIO-CEM prepared according to
example 2 is mixed into a clear acrylic urethane basecoat clearcoat
paint system DBX-689 (PPG) along with various PPG tints to achieve
desired color. The tint pastes consist of organic or inorganic
colorants dispersed at various concentrations in a solventborne
system suitable with the DMD Deltron Automotive Refinish paint line
from PPG. The complete formulation is sprayed using a conventional
siphon feed spraygun onto 4.times.12" curved automotive type panels
supplied by Graphic Metals. The panel is clear coated with PPG 2001
high solids polyurethane clear coat and air dried.
[0048] Various changes and modifications can be made in the process
and products of the invention without departing from the spirit and
scope thereof. The various embodiments disclosed herein were for
the purpose of illustration only and were not intended to limit the
invention.
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