U.S. patent application number 11/029324 was filed with the patent office on 2007-12-06 for color forming compositions with improved marking sensitivity and image contrast and associated methods.
Invention is credited to Makarand P. Gore, Vladek P. Kasperchik.
Application Number | 20070281244 11/029324 |
Document ID | / |
Family ID | 36293115 |
Filed Date | 2007-12-06 |
United States Patent
Application |
20070281244 |
Kind Code |
A9 |
Kasperchik; Vladek P. ; et
al. |
December 6, 2007 |
Color forming compositions with improved marking sensitivity and
image contrast and associated methods
Abstract
Compositions and methods for production of color images which
are developable with improved marking sensitivity and image
contrast are disclosed and described. Specifically, a color forming
composition can comprise a polymeric activator phase including a
polymer matrix and an activator dissolved therein, a color former
phase including a color former, and a radiation absorber in thermal
contact with the color former phase. Particularly, the color former
phase can be finely dispersed within the polymeric activator phase
at an average particle size of less than 2 .mu.m.
Inventors: |
Kasperchik; Vladek P.;
(Corvallis, OR) ; Gore; Makarand P.; (Corvallis,
OR) |
Correspondence
Address: |
HEWLETT PACKARD COMPANY
P O BOX 272400, 3404 E. HARMONY ROAD
INTELLECTUAL PROPERTY ADMINISTRATION
FORT COLLINS
CO
80527-2400
US
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20060147833 A1 |
July 6, 2006 |
|
|
Family ID: |
36293115 |
Appl. No.: |
11/029324 |
Filed: |
January 4, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10351188 |
Jan 24, 2003 |
6974661 |
|
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11029324 |
Jan 4, 2005 |
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Current U.S.
Class: |
430/270.1 ;
G9B/23.093; G9B/7.171 |
Current CPC
Class: |
B41M 5/30 20130101; B41M
5/34 20130101; G11B 7/252 20130101; G03F 7/105 20130101; G11B 23/40
20130101 |
Class at
Publication: |
430/270.1 |
International
Class: |
G03C 1/76 20060101
G03C001/76 |
Claims
1. A color forming composition, comprising: a) a polymeric
activator phase including a polymer matrix and an activator
dissolved therein; b) a color former phase including a color
former, said color former phase being finely dispersed within the
polymeric activator phase at an average particle size of less than
2 .mu.m; and c) a radiation absorber in thermal contact with the
color former phase.
2. The composition of claim 1, wherein the color forming
composition has a pre-development state and a post-development
state, the pre-development state having an appearance that is
visually different than the post-development state.
3. The composition of claim 1, wherein the color forming
composition is either colorless or has a first color when in the
pre-development state, and is a second color after development in
the post-development state.
4. The composition of claim 1, wherein the polymer matrix includes
a radiation curable polymer.
5. The composition of claim 4, wherein the radiation curable
polymer is curable at a curing wavelength that is different than a
developing wavelength which would cause the color forming
composition to change or develop color.
6. The composition of claim 5, wherein the curing wavelength is in
the ultraviolet range.
7. The composition of claim 5, wherein the developing wavelength is
in the infrared range.
8. The composition of claim 5, wherein the developing wavelength is
from about 200 nm to about 1200 nm.
9. The composition of claim 2, wherein the polymeric activator
phase further comprises an aromatic stabilizer.
10. The composition of claim 9, wherein the aromatic stabilizer is
configured to stabilize the color former in the post-development
state.
11. The composition of claim 1, wherein the average particle size
of the color former phase is less than about 1.5 .mu.m.
12. The composition of claim 11, wherein the average particle size
of the color former phase is from about 0.2 .mu.m to about 1.5
.mu.m.
13. The composition of claim 11, wherein the average particle size
of the color former phase is from about 0.05 .mu.m to about 1
.mu.m.
14. The composition of claim 13, wherein the average particle size
of the color former phase is from about 0.05 .mu.m to about 0.7
.mu.m.
15. The composition of claim 1, wherein the color former phase
comprises from about 1 wt % to about 40 wt % of the color forming
composition.
16. The composition of claim 1, wherein the color former phase is
distinct and substantially insoluble in the polymeric activator
phase at room temperature, and wherein upon application of heat or
light energy to cause a temperature from about 90.degree. C. to
about 350.degree. C., the polymeric activator phase becomes at
least partially molten or undergoes phase transition, and the color
former phase at least partially melts or undergoes phase transition
therein.
17. The composition of claim 1, wherein the color former phase
further comprises a melting aid having a melting temperature from
about 50.degree. C. to about 150.degree. C.
18. The composition of claim 1, wherein the color former is a leuco
dye.
19. The composition of claim 18, wherein the leuco dye is a
fluoran.
20. The composition of claim 1, wherein the radiation absorber is
dispersed or dissolved within the polymeric activator phase.
21. The composition of claim 1, wherein the radiation absorber is
dispersed or dissolved within the color former phase.
22. The composition of claim 1, wherein a first portion of the
radiation absorber is dispersed or dissolved within the polymeric
activator phase, and wherein a second portion of the radiation
absorber is dispersed or dissolved within the color former
phase.
23. The composition of claim 1 applied to a substrate.
24. The composition of claim 23, wherein the substrate is selected
from the group consisting of polymer, paper, metal, glass, ceramic,
and combinations or composites thereof.
25. The composition of claim 23, wherein the substrate is an
optical disk.
26. A method of forming an image, comprising applying
electromagnetic radiation to a color forming composition sufficient
to develop the color forming composition from a pre-development
state to a post-development state that is visually different than
the pre-development state, said color forming composition,
comprising: a) a polymeric activator phase including a polymer
matrix and an activator dissolved therein; b) a color former phase
including a color former, said color former phase being finely
dispersed within the polymeric activator phase at an average
particle size of less than 2 .mu.m; and c) a radiation absorber in
thermal contact with the color former phase.
27. A method as in claim 26, wherein the electromagnetic radiation
is applied for a duration and at an energy level such that the
color forming composition does not decompose.
28. The method of claim 26, wherein the electromagnetic radiation
is laser energy.
29. The method of claim 26, wherein the electromagnetic radiation
is applied at from about 0.05 J/cm.sup.2 to about 5 J/cm.sup.2.
30. The method of claim 26, wherein the electromagnetic radiation
is applied for about 15 .mu.sec to about 200 .mu.sec.
31. The method of claim 26, wherein the electromagnetic radiation
is applied at a spot size from about 10 .mu.m to about 60
.mu.m.
32. The method of claim 26, wherein the electromagnetic radiation
is applied at a power level from about 15 mW and about 100 mW.
33. The method of claim 26, wherein the electromagnetic radiation
has a wavelength from about 200 nm to about 1200 nm.
34. The method of claim 26, further comprising the preliminary step
of applying the color forming composition to a substrate.
35. The method of claim 34, wherein the color forming composition
is applied to the substrate at a thickness from about 1 .mu.m to
about 15 .mu.m.
36. The method of claim 34, wherein the substrate is selected from
the group consisting of polymer, paper, metal, glass, ceramic, and
combinations or composites thereof.
37. The method of claim 34, wherein the substrate is an optical
disk.
38. The method of claim 26, wherein the polymer matrix includes a
radiation curable polymer.
39. The method of claim 26, wherein the polymeric activator phase
further comprises an aromatic stabilizer configured to stabilize
the color former in the post-development state.
40. The method of claim 26, wherein the average particle size of
the color former phase is less than about 1.5 .mu.m.
41. The method of claim 26, wherein the average particle size of
the color former phase is from about 0.2 .mu.m to about 1.5
.mu.m.
42. The method of claim 26, wherein the average particle size of
the color former phase is from about 0.05 .mu.m to about 1
.mu.m.
43. The method of claim 26, wherein the average particle size of
the color former phase is from about 0.05 .mu.m to about 0.7
.mu.m.
44. The method of claim 26, wherein the color former phase is
distinct and substantially insoluble in the polymeric activator
phase at room temperature, and wherein upon application of heat at
from about 90.degree. C. to about 350.degree. C., the polymeric
activator phase becomes at least partially molten or undergoes
phase transition, and the color former phase at least partially
melts or undergoes phase transition therein.
45. The method of claim 26, wherein the color former phase further
comprises a melting aid having a melting temperature from about
50.degree. C. to about 150.degree. C.
46. The method of claim 26, wherein the color former is a leuco
dye.
47. The method of claim 26, wherein the leuco dye is a fluoran.
48. The method of claim 26, wherein the radiation absorber is
dispersed or dissolved within the polymeric activator phase.
49. The method of claim 26, wherein the radiation absorber is
dispersed or dissolved within the color former phase.
50. The method of claim 26, wherein a first portion of the
radiation absorber is dispersed or dissolved within the polymeric
activator phase, and wherein a second portion of the radiation
absorber is dispersed or dissolved within the color former
phase.
51. The method of claim 26, wherein the electromagnetic radiation
is laser energy, and wherein the laser energy wavelength is greater
than or equal to the particle size of the color former phase prior
to application of the laser energy.
52. The method of claim 26, wherein the electromagnetic radiation
is laser energy, and wherein the particle size of the color former
phase prior to application of the laser energy is no more than two
times larger than the wavelength of the laser energy.
Description
FIELD OF THE INVENTION
[0001] The present invention relates generally to color forming
compositions. More particularly, the present invention relates to
methods and compositions which can form images upon interaction
with energy, such as light energy, with improved marking
sensitivity and image contrast.
BACKGROUND OF THE INVENTION
[0002] Compositions which produce a color change upon exposure to
energy in the form of light or heat are of great interest in
producing images on a variety of substrates. Optical disks
represent a significant percentage of the market for data storage
of software as well as of photographic, video, and/or audio data.
Typically, optical disks have data patterns embedded thereon that
can be read from and/or written to one side of the disk, and a
graphic display or label printed on the other side of the disk.
[0003] In order to identify the contents of the optical disk,
printed patterns or graphic display information can be provided on
the non-data, or label, side of the disk. The patterns or graphic
display can be both decorative and provide pertinent information
about the data content of the disk. In the past, commercial
labeling has been routinely accomplished using screen-printing
methods. While this method can provide a wide variety of label
content, it tends to be cost ineffective for production of less
than about 400 customized disks because of the fixed costs
associated with preparing a stencil or combination of stencils and
printing the desired pattern or graphic display.
[0004] In recent years, the significant increase in the use of
optical disks for data storage by consumers has increased the
demand to provide customized labels to reflect the content of the
optical disk. Most consumer available methods of labeling are
limited to either handwritten descriptions which lack professional
appearance, quality and variety, or preprinted labels which may be
affixed to the disk, but which can also adversely affect the disk
performance upon spinning at high speeds.
[0005] Recently, color forming compositions have been developed
which can be developed using energy sources such as lasers in order
to form an image. However, many of these color forming compositions
have development sensitivities that result in slower development
time and/or less than acceptable contrast. Thus, the need still
exists for improvement in color forming compositions with improved
marking sensitivity and image contrast.
SUMMARY OF THE INVENTION
[0006] It has been recognized that it would be advantageous to
provide rapidly developable color forming compositions with
improved marking sensitivity, which can also be used to provide
images with improved image contrast, even under fast development
conditions. In one aspect of the present invention, a color forming
composition can include a polymeric activator phase including a
polymer matrix and an activator dissolved therein, a color former
phase including a color former, and a radiation absorber in thermal
contact with the color former phase. Particularly, the color former
phase can be finely dispersed within the polymeric activator phase
at an average particle size of less than 2 .mu.m.
[0007] In another embodiment, a method of forming an image can
comprise applying electromagnetic radiation to a color forming
composition sufficient to develop the color forming composition
from a pre-development state to a post-development state that is
visually different than the pre-development state. The color
forming composition can comprise a polymeric activator phase
including a polymer matrix and an activator dissolved therein, a
color former phase including a color former, and a radiation
absorber in thermal contact with the color former phase. Again, the
color former phase can be finely dispersed within the polymeric
activator phase at an average particle size of less than 2
.mu.m.
[0008] Additional aspects and advantages of the invention will be
apparent from the detailed description which follows.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
[0009] Reference will now be made to exemplary embodiments and
specific language will be used herein to describe the same. It will
nevertheless be understood that no limitation of the scope of the
invention is thereby intended. Alterations and further
modifications of the inventive features described herein and
additional applications of the principles of the invention as
described herein, which would occur to one skilled in the relevant
art and having possession of this disclosure, are to be considered
within the scope of the invention. Further, before particular
embodiments of the present invention are disclosed and described,
it is to be understood that this invention is not limited to the
particular process and materials disclosed herein as such may vary
to some degree. It is also to be understood that the terminology
used herein is used for the purpose of describing particular
embodiments only and is not intended to be limiting, as the scope
of the present invention will be defined only by the appended
claims and equivalents thereof.
[0010] In describing and claiming the present invention, the
following terminology will be used.
[0011] The singular forms "a," "an," and "the" include plural
referents unless the context clearly dictates otherwise. Thus, for
example, reference to "a radiation absorber" includes reference to
one or more of such materials.
[0012] As used herein, the term "color forming composition"
typically includes a color former, an activator, a radiation
absorber, and a polymer matrix. These components can work together
upon exposure to radiation to develop the color former, thereby
creating a color from a colorless material, or alternatively,
causing a color to change from a first color to another color. In
other words, an undeveloped color former can be colorless or may
have some color which changes upon development to a different
color. Though the term "color forming composition" describes the
presence of four compositional components, these compositions do
not have to be present in a single phase or layer. For example,
though it preferred to have the radiation absorber admixed with one
or both of the phases in the color forming composition due to
development speed concerns, the radiation absorber can be in a
separate layer.
[0013] As used herein, the term "color former" refers to any
composition which changes color upon application of energy. Color
formers are typically leuco dyes, photochromic dyes, or the like.
In accordance with embodiments of the present invention, the color
former will be present as part of a discontinuous phase that is
finely dispersed within a continuous polymeric phase. The term
"color former" does not infer that color is generated from scratch,
as it includes materials that can change in color, as well as
materials that can become colored from a colorless or more
transparent state.
[0014] The term "activator" refers to compounds or materials that,
upon the presence of energy (such as heat generated by a laser and
a radiation absorber), can react or otherwise interact with a color
former to modify or create color within a color forming
composition. Activators can be any material that reacts or
interacts with color formers to cause color creation or change of
the color former. In some embodiments, multiple activators can be
used, e.g., multiple activator systems having from coequal
performance value to systems having a primary activator and
secondary activator(s). In one embodiment, for example, the
activator can be an acidic compound or material that donates a
proton necessary to develop a certain class of leuco dye.
[0015] As used herein, "radiation absorber" refers generally to a
radiation sensitive agent that can generate heat or otherwise
transfer energy to surrounding molecules upon exposure to radiation
at a specific wavelength. When admixed with and/or in thermal
contact with a leuco dye and/or a corresponding activator, a
radiation absorber can be present in sufficient quantity so as to
produce energy sufficient to at least partially develop the color
former.
[0016] As used herein, "developing," "development," or the like
refers to an interaction or reaction which affects the color former
to produce a visible change in its appearance, e.g., from colorless
or transparent to colored or from a first color to a second color.
In one embodiment, the color former can be a leuco dye that is
reduced by an acidic activator to generate a color or change in
color.
[0017] For purposes of the present invention, the term "color" or
"colored" refers to absorbance and reflectance properties that are
preferably visible, including properties that result in black,
white, or traditional color appearance. In other words, the terms
"color" or "colored" includes black, white, and traditional colors,
as well as other visual properties, e.g., pearlescent, reflective,
translucent, transparent, etc.
[0018] As used herein, "thermal contact" refers to the spatial
relationship between a radiation absorber and other members of the
color forming composition (including the color former and/or the
activator). For example, when a radiation absorber is heated by
interaction with laser radiation, the energy generated by the
absorber should be sufficient to cause the color former of color
forming composition to darken, lighten, become colored, or
otherwise change in visible perception, such as through a chemical
reaction. Thermal contact can include close proximity between a
radiation absorber and other members of the color forming
composition, which allows for energy transfer from the absorber
toward the color former and/or activator. Thermal contact can also
include actual contact between a radiation absorber and one or more
other members of the color forming composition, such as in
immediately adjacent layers, or in an admixture including some or
all of the other constituents. In accordance with embodiments of
the present invention, the radiation absorber can be present within
a color former phase, within a polymeric activator phase, and/or
layered with respect to the color former/polymeric activator
dispersion. If fast development times are desired, in one
embodiment, mixing radiation absorbers with the polymeric activator
phase and the color former phase can reduce melt times, resulting
in rapid mixing of the phases.
[0019] As used herein, the term "coating composition," or other
similar referents typically refers to carrier having various
components dissolved or dispersed therein. The carrier can be a
liquid or paste-like carrier, or can be one of the components of
the color forming composition per se, e.g., polymer matrix, etc. In
one embodiment, the composition can comprise a color former phase
finely dispersed in a polymeric activator phase. Other components
can be present in one or both of these phases. Color forming
compositions can be spin-coatable in one embodiment, or can be
configured for other application methods as well, e.g., printing
such as by offset, ink-jet, gravure, roller coating, screen
printing, spraying, or other application methods known to those
skilled in the art. Once the coating composition is applied to a
substrate, it can be referred to as simply a "coating."
[0020] As used herein, "optical disk" is meant to encompass audio,
video, multi-media, and/or software disks that are machine readable
in a CD and/or DVD drive, or the like. Examples of optical disk
formats include writeable, recordable, and rewriteable disks such
as DVD, DVD-R, DVD-RW, DVD+R, DVD+RW, DVD-RAM, CD, CD-ROM, CD-R,
CD-RW, and the like. Other like formats may also be included, such
as similar formats and formats to be developed in the future.
[0021] As used herein, "graphic display" can include any visible
character or image found on an optical disk. Typically, the graphic
display is found prominently on one side of the optical disk,
though this is not always the case.
[0022] As used herein, "data" is typically used with respect to the
present disclosure to include the non-graphic information contained
on the optical disk that is digitally or otherwise embedded
therein. Data can include audio information, video information,
photographic information, software information, and the like.
Alternatively, the term "data" is sometimes used to describe the
information a computer or other processor uses to draw from in
order to mark an image on a color-forming composition in accordance
with embodiments of the present invention.
[0023] Concentrations, amounts, and other numerical information may
be presented herein in a range format. It is to be understood that
such range format is used merely for convenience and brevity and
should be interpreted flexibly to include not only the numerical
values explicitly recited as the limits of the range, but also to
include all the individual numerical values or sub-ranges
encompassed within that range as if each numerical value and
sub-range is explicitly recited. For example, a size range of about
1 .mu.m to about 200 .mu.m should be interpreted to include not
only the explicitly recited limits of 1 .mu.m to about 200 .mu.m,
but also to include individual sizes such as 2 .mu.m, 3 .mu.m, 4
.mu.m, and sub-ranges such as 10 .mu.m to 50 .mu.m, 20 .mu.m to 100
.mu.m, etc.
[0024] In accordance with the present invention, a color forming
composition can include a polymeric activator phase including a
polymer matrix and an activator dissolved therein, a color former
phase including a color former, and a radiation absorber in thermal
contact with the color former phase. Particularly, the color former
phase can be finely dispersed within the polymeric activator phase
at an average particle size of less than 2 .mu.m. The color forming
composition as a whole can have a pre-development state and a
post-development state. The pre-development state typically has a
first visual appearance that is visually different than the
post-development state. For example, the color forming composition
can either be colorless or have a first color when in the
pre-development state, and is of a second color after development
when in the post-development state.
[0025] In another embodiment, a method of forming an image can
comprise applying electromagnetic radiation to a color forming
composition sufficient to develop the color forming composition
from a pre-development state to a post-development state that is
visually different than the pre-development state. The color
forming composition can comprise a polymeric activator phase
including a polymer matrix and an activator dissolved therein, a
color former phase including a color former, and a radiation
absorber in thermal contact with the color former phase. Again, the
color former phase can be finely dispersed within the polymeric
activator phase at an average particle size of less than 2
.mu.m.
[0026] Upon application of suitable electromagnetic radiation, such
as in the form of a laser, the radiation absorber and color former
are heated sufficiently to develop the color former. In particular,
the compositions and methods of the present invention provide the
ability to reduce the energy requirements for developing color
forming compositions in accordance with embodiments of the present
invention. For example, a lower amount of energy is required to
melt, diffuse, or heat to a desired reaction temperature when small
particles are used, and thus, faster write times and contrast can
be achieved. Specific polymer matrices, color formers, radiation
absorbers, activators, and other optional components of the color
forming composition can each affect the development properties and
long-term stability of the color forming composition and are
discussed in more detail below.
[0027] Polymeric Activator Phase
[0028] The color forming compositions of the present invention
include a polymer activator phase, which comprises at least a
polymer matrix and an activator. In one embodiment, the polymeric
activator phase can include a radiation-curable polymer with an
acidic (proton-donating) activator dispersed or preferably
dissolved therein. As mentioned above, a color former phase is
finely dispersed within the polymeric activator phase. Various
polymer matrix materials can influence the development properties
of the color forming composition such as development speed, light
stability, and wavelengths which can be used to develop the color
forming composition.
[0029] Acceptable polymer matrix materials can include, by way of
example, UV curable polymers such as acrylate derivatives,
oligomers, and monomers. These materials are often included or
assembled as part of a photo package. A photo package can include a
light absorbing species which initiates reactions for curing of a
lacquer. Such light absorbing species can be sensitized for curing
using UV or electron beam curing systems, and include, by way of
example, benzophenone derivatives. Other examples of
photoinitiators for free radical polymerization monomers and
pre-polymers can include, but are not limited to, thioxanethone
derivatives, anthraquinone derivatives, acetophenones, and benzoine
ethers.
[0030] In particular embodiments of the invention, it can be
desirable to choose a polymer matrix which is cured by a form of
radiation that does not also develop the color former or otherwise
decrease the stability of the color forming composition at the
energy input and flux necessary to cure the coatings. Thus, the
polymer matrix can be curable at a curing wavelength which is other
than the developing wavelength of the color forming composition.
For example, in one embodiment, the curing wavelength can be in the
ultraviolet (UV) range and the developing wavelength can be in the
infrared range. Alternatively, the curing wavelength and the
developing wavelength can both be in the UV range, but may be
different enough such that the curing wavelength does not
substantially cause undesired development of the color forming
composition. For example, selecting a first UV wavelength of 405 nm
for the developing wavelength and a second UV wavelength of about
200 nm to about 380 nm for the curing wavelength of the polymer
matrix may provide an effective system for curing the polymer
without prematurely developing the color forming composition.
[0031] Radiation curable polymers can include certain
photoinitiators for initiating curing upon exposure to radiation.
Suitable photoinitiator should also have light absorption band
which is not obscured by the absorption band of the radiation
absorber (as will be discussed hereinafter), otherwise the
radiation absorber can interfere with photoinitiator activation,
and thus, prevent proper curing of the coating. Therefore, in one
practical embodiment, a photoinitiator light absorption band can
lie within the UV region, e.g., from about 200 nm to about 380 nm,
and the absorber band can lie outside of this range, e.g., about
390 to about 1100 nm. In practice, the lower end of the radiation
absorber band probably would overlap with the UV wavelength range
used for polymer curing. However, a working system design is
possible because the energy flux required for development of a
color former is about ten times higher than needed for initiation
of polymer curing. In yet another embodiment, the absorber has a
dual function; one of sensitization of UV cure under cure
conditions (relatively low energy flux), and another of providing
energy for marking during the marking function. This is possible
because the energy flux during cure is typically an order of
magnitude lower than needed for producing a mark.
[0032] Polymer matrix materials based on cationic polymerization
resins can include photo-initiators including aromatic diazonium
salts, aromatic halonium salts, aromatic sulfonium salts, and
metallocene compounds. Additional examples of curing agents are
.alpha.-aminoketones, .alpha.-hydroxyketones, phosphineoxides
available from Ciba-Geigy under the name of Irgacure and Darocure
agents, and sensitizers such as 2-isopropyl-thioxanthone. One
specific example of a suitable polymer matrix is Nor-Cote CDG-1000
(a mixture of UV curable acrylate monomers and oligomers) which
contains a photoinitiator (hydroxy ketone) and organic solvent
acrylates, e.g., methyl methacrylate, hexyl methacrylate,
beta-phenoxy ethyl acrylate, and hexamethylene acrylate, available
from Nor-Cote. Other suitable components for polymer matrix
materials can include, but are not limited to, acrylated polyester
oligomers, such as CN293 and CN294 as well as CN-292 (low viscosity
polyester acrylate oligomer), SR-351 (trimethylolpropane
triacrylate), SR-395(isodecyl acrylate) and
SR-256(2(2-ethoxyethoxy)ethyl acrylate), all of which are available
from Sartomer Co.
[0033] Additionally, binders can be included as part of the polymer
matrix. Suitable binders can include, but are not limited to,
polymeric materials such as polyacrylate from monomers and
oligomers, polyvinyl alcohols, polyvinyl pyrrolidines,
polyethylenes, polyphenols or polyphenolic esters, polyurethanes,
acrylic polymers, and mixtures thereof. For example, the following
binders can be used in the color forming composition of the present
invention: cellulose acetate butyrate, ethyl acetate butyrate,
polymethyl methacrylate, polyvinyl butyral, and mixtures
thereof.
[0034] In short, the polymer matrix of the polymeric activator
phase can be a single polymer or a group of polymers. The polymers
can act as a solute of the polymeric activator phase, or can be
dissolved or dispersed in another material, such as a solvent or
another component of the phase. If multiple polymers are present,
the polymers can be blended, crosslinked, or otherwise combined. In
one embodiment, the polymer matrix can include a radiation curable
polymer or system of polymers, oligomers, and/or monomers, etc.
Though the polymer matrix is integral to the polymeric activator
phase, it can be present in any of a number of forms.
[0035] The polymeric activator phase also includes an activator,
which depending on the color former used in the color former phase,
can be a reducing agent. Typical activators that can be used
include any of a variety of acids. For example, the activator can
be an acidic phenolic compound. Further, these activators can be
readily dissolvable in the polymer matrix under the conditions
which the dispersion is to be prepared and/or stored.
[0036] Non-limiting examples of suitable activators include
bis-phenol A, bis-phenol S, p-hydroxy benzyl benzoate, TG-SA
(Phenol, 4,4-.alpha.-sulfonylbis[2-(2-propenyl)), and poly-phenols.
Examples of additional acidic materials that can be used as
activators include any Lewis acid, without limitation, phenols,
carboxylic acids, cyclic sulfonamides, protonic acids, zinc
chloride, magnesium carboxylates, zinc carboxylates, calcium
carboxylates, transition metal salts and other compounds having a
pKa of less than about 7.0, and mixtures thereof. Specific phenolic
and carboxylic secondary activators can include, without
limitation, boric acid, oxalic acid, maleic acid, tartaric acid,
citric acid, succinic acid, benzoic acid, stearic acid, gallic
acid, salicylic acid, 1-hydroxy-2-naphthoic acid, o-hydroxybenzoic
acid, m-hydroxybenzoic acid, 2-hydroxy-p-toluic acid, 3,5-xylenol,
thymol, p-t-butylphenyl, 4-hydroxyphenoxide,
methyl-4-hydroxybenzoate, 4-hydroxyacetophenone, .alpha.-naphthol,
naphthols, catechol, resorcin, hydroquinone, 4-t-octylcatechol,
4,4'-butylidenephenol, 2,2'-dihydroxydiphenyl,
2,2'-methylenebis(4-methyl-6-t-butyl-phenol),
2,2'-bis(4'-hydroxyphenyl)propane,
4,4'-isopropylidenebis(2-t-butylphenol),
4,4'-secbutylidenediphenol, pyrogallol, phloroglucine,
phlorogluocinocarboxylic acid, 4-phenylphenol,
2,2'-methylenebis(4-chlorophenyl), 4,4'-isopropylidenediphenol,
4,4'-isopropylidenebis(2-chlorophenol),
4,4'-isopropylidenebis(2-methylphenol),
4,4'-ethylenebis(2-methylphenol),
4,4'-thiobis(6-t-butyl-3-methylphenol), bisphenol A and its
derivatives (such as 4,4'-isopropylidenediphenol,
4-4'-cyclohexylidenediphenol, p,p'-(1-methyl-n-hexylidene)diphenol,
1,7-di(4-hydroxyphenylthio)-3,5-dioxaheptane), 4-hydroxybenzoic
esters, 4-hydroxyphthalic diesters, phthalic monoesters,
bis(hydroxyphenyl)sulfides, 4-hydroxyarylsulfones,
4-hydroxyphenylarylsulfonates,
1,3-di[2-(hydroxyphenyl)-2-propyl]benzenes,
1,3-dihydroxy-6(.alpha.,.alpha.-dimethylbenzyl)benzene,
resorcinols, hydroxybenzoyloxybenzoic esters, bisphenolsulfones,
bis-(3-allyl-4-hydroxyphenyl)sulfone (TG-SA), bisphenolsulfonic
acids, 2,4-dihydroxy-benzophenones, novolac type phenolic resins,
polyphenols, saccharin, 4-hydroxy-acetophenone, p-phenylphenol,
benzyl-p-hydroxybenzoate(benzalparaben),
2,2-bis(p-hydroxyphenyl)propane, p-tert-butylphenol,
2,4-dihydroxy-benzophenone, and p-benzylphenol.
[0037] Typically, the activator will be present in the color
forming composition as a whole at from 2 wt % to about 80 wt %.
Because the activator is present in the polymeric activator phase,
it will typically remain predominantly in this phase until the
polymeric activator phase becomes at least partially molten and the
color former phase begins to melt with the polymeric activator
phase. In other words, by including the activator in the polymeric
activator phase, the activator is kept substantially separated from
the color former phase until the composition is heated. Upon
heating with laser energy coming in contact with a radiation
absorber, the polymeric activator phase can become molten and the
particles of the color former phase become melted therein. Upon
melting, the activator contacts the color former, thereby causing a
modification in color of the color former, e.g., leuco dye.
[0038] In addition to the polymer matrix and the activator, other
optional ingredients can also be present in the polymeric activator
phase. For example, in embodiments where fluoran-type leuco dyes
(or other similar color formers) are used in the color former
phase, the polymeric activator phase can also include a stabilizer
capable of stabilizing the fluoran leuco dye after melting the two
phases together, i.e. when the leuco dye is in its post-development
colored state. Specifically, the post-development colored state of
a fluoran leuco dye can have an open lactone ring. Image fade that
can occur with many Leuco-dye-based thermochromic coatings can be
related to leuco dye crystallization from after an amorphous melt.
For the above reasons, an aromatic species capable of stabilizing
the post-development leuco dye in the amorphous phase can provide
image stabilization by retarding/preventing leuco dye
crystallization. Exemplary aromatic stabilizers that can be used to
stabilize post-development leuco dyes, i.e. after melt, include,
but are not limited to zinc salts such as zinc stearate, zinc
hexanoate, zinc salicylate, and zinc acetate; carboxylates such as
calcium monobutylphthalate and sulfonyl urea derivatives; and
phenolic compounds such as bisphenol-A, sulfonyl diphenol, TG-SA,
and zinc or calcium salts thereof. As a general guideline, the
color forming compositions of the present invention can include
from about 1 wt % to about 40 wt % of this or another type of
stabilizer. Preferably, the stabilizer can be present at from about
2 wt % to about 20 wt % of the total composition.
[0039] Color Former Phase
[0040] Color forming compositions of the present invention can
include a color former phase dispersed within the polymeric
activator phase discussed above. Typically, the color former phase
is substantially insoluble in the polymer matrix, exists distinct
from the polymer matrix at room temperature, and is finely
dispersed within the polymer matrix. The dispersion can be formed
using color former particles prepared by any known method such as
mixing, rolling, milling, or the like, provided a sub-2 .mu.m
average particle size can be achieved in the dispersion. In most
cases, it can be desirable to uniformly disperse the color former
phase throughout the polymer matrix. Dispersing the color former
phase within the polymer matrix allows for increased contact of the
leuco dye with activator material and/or other energy transfer
materials, which are discussed below in more detail. Further, a
dispersion of color former phase within the polymer matrix can be
formed as a single composition, e.g., a paste, which can then be
coated on a substrate in a single step. The volume of color former
phase dispersed within the polymer matrix can vary considerably
depending on the concentration and type of color former used, as
well as a number of other factors such as desired development
speed, desired color intensity of developed color former, and the
like. However, as a general guideline, the color former phase
volume percent in the polymer matrix can be from about 1% to about
50%, and in some cases from about 10% to about 30%.
[0041] In accordance with embodiments of the present invention, it
has been discovered that color forming phase particle size is
related to multiple desirable properties. Specifically, including
the color former phase as a fine dispersion, i.e. less than 2
.mu.m, within the polymeric activator phase has several advantages
over embodiments that utilize larger color former phase particles.
These advantages seem to become enhanced even further as the
particle size is reduced. In accordance with this recognition, in a
preferred embodiment, the average particle size of the color former
phase can be less than about 1.5 .mu.m, such as from about 0.05
.mu.m to about 1.5 .mu.m, or from about 0.2 .mu.m to about 1.5
.mu.m. In another embodiment, the average particle size of the
color former phase can be from about 0.05 .mu.m to about 1 .mu.m,
and still in another embodiment, the average particle size of the
color former phase is from about 0.05 .mu.m to about 0.7 .mu.m. In
each of these embodiments, typically, the color former phase is
distinct and substantially insoluble in the polymeric activator
phase (typically at room temperature), and upon application of heat
at from about 90.degree. C. to about 350.degree. C., the polymeric
activator phase becomes at least partially molten and the color
former phase at least partially melts therein. Similar effects are
observed by delivery of energy using light and an absorber as a
source of enegy. Further, more complete melting can improve or
increase image contrast in some embodiments. Thus, in one
embodiment, substantially complete to even complete melting of the
color former phase in the polymeric activator phase can be
preferred.
[0042] Without being bound by any particular theory, there are at
least two likely reasons why these very small color former phase
particle sizes provide improvement in marking sensitivity and/or
image contrast. First, by decreasing the size of the particles of
the color former phase, the surface area is increased, and thus,
the surface area to volume ratio is also increased. A larger
surface area to volume ratio facilitates faster melting of the
color former phase particles as well as faster mixing of the molten
color former particles with molten polymeric activator phase. As a
result, faster imaging is possible. Further, more contrast can also
be achieved by creating a more complete mix at the same or even
faster write time typically used for these types of technologies. A
second benefit is related to the particle size of the color former
phase compared to the wavelength of the radiant energy used to heat
the color forming composition as a whole. Typical lasers used for
marking optical disks, for example, include those that range in
wavelength from about 200 nm to about 1200 nm, i.e., 0.2 .mu.m to
about 1.2 .mu.m. By providing particles that are roughly of the
same order of magnitude or smaller compared to the wavelength of
the laser that is used, light scattering is minimized or removed.
In other words, light scattering caused by interaction of laser
radiation with larger color former phase particles can result in
partial reflection of the laser beam, causing unnecessary energy
loss. By reducing the particle size to from slightly larger (about
the same order of magnitude) to even below the wavelength of the
imaging radiation, light scattering and/or energy depleting
reflection is reduced or eliminated. Hence, improved absorption
efficiency of the coating can be achieved, which translates into
higher marking sensitivity of the color forming composition, higher
contrast in some embodiments, and the ability to write images at
higher speeds. Though not required, in one detailed embodiment, the
laser energy wavelength is greater than or equal to the particle
size of the color former phase prior to application of the laser
energy. In another embodiment, the particle size of the color
former phase prior to application of the laser energy is no more
than two times larger than the wavelength of the laser energy
(based on average particle size compared to wavelength).
[0043] The color former phase can include a variety of materials,
but must include at least one color former. Exemplary color formers
include leuco dyes, photochromic dyes, or the like. Fluoran leuco
dyes have been shown to be particularly practical in accordance
with embodiments of the present invention, though other leuco dyes
can also be used. In one aspect of the present invention, the leuco
dye can be a fluoran, phthalide, aminotriarylmethane, or mixture
thereof. This being said, almost any known color forming dye can be
used, as long as the color development criteria discussed herein
are met. Suitable leuco dyes include, but are not limited to,
fluorans, phthalides, aminotriarylmethanes, aminoxanthenes,
aminothioxanthenes, amino-9,10-dihydro-acridines,
aminophenoxazines, aminophenothiazines, aminodihydro-phenazines,
aminodiphenylmethanes, aminohydrocinnamic acids (cyanoethanes,
leuco methines) and corresponding esters,
2(p-hydroxyphenyl)-4,5-diphenylimidazoles, indanones, leuco
indamines, hydrozines, leuco indigoid dyes,
amino-2,3-dihydroanthraquinones, tetrahalo-p,p'-biphenols,
2(p-hydroxyphenyl)-4,5-diphenylimidazoles, phenethylanilines,
phthalocyanine precursors (such as those available from Sitaram
Chemicals, India), and mixtures thereof.
[0044] As mentioned, fluoran based leuco dyes have proven
exceptionally useful for incorporation into the color forming
compositions of the present invention. Several non-limiting
examples of suitable fluoran based leuco dyes include
3-diethylamino-6-methyl-7-anilinofluorane,
3-(N-ethyl-p-toluidino)-6-methyl-7-anilinofluorane,
3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluorane,
3-diethylamino-6-methyl-7-(o,p-dimethylanilino)fluorane,
3-pyrrolidino-6-methyl-7-anilinofluorane,
3-piperidino-6-methyl-7-anilinofluorane,
3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorane,
3-diethylamino-7-(m-trifluoromethylanilino)fluorane,
3-dibutylamino-6-methyl-7-anilinofluorane,
3-diethylamino-6-chloro-7-anilinofluorane,
3-dibutylamino-7-(o-chloroanilino)fluorane,
3-diethylamino-7-(o-chloroanilino)fluorane,
3-di-n-pentylamino-6-methyl-7-anilinofluoran,
3-di-n-butylamino-6-methyl-7-anilinofluoran,
3-(n-ethyl-n-isopentylamino)-6-methyl-7-anilinofluoran,
3-pyrrolidino-6-methyl-7-anilinofluoran,
1(3H)-isobenzofuranone,4,5,6,7-tetrachloro-3,3-bis[2-[4-(dimethylamino)ph-
enyl]-2-(4-methoxyphenyl)ethenyl],
2-anilino-3-methyl-6-(N-ethyl-N-isoamylamino)fluorane (S-205
available from Nagase Co., Ltd), and mixtures thereof.
Aminotriarylmethane leuco dyes can also be used in the present
invention such as tris(N,N-dimethylaminophenyl)methane (LCV);
deutero-tris(N,N-dimethylaminophenyl)methane (D-LCV);
tris(N,N-diethylaminophenyl)methane(LECV);
deutero-tris(4-diethylaminolphenyl)methane (D-LECV);
tris(N,N-di-n-propylaminophenyl)methane (LPCV);
tris(N,N-din-butylaminophenyl)methane (LBCV);
bis(4-diethylaminophenyl)-(4-diethylamino-2-methyl-phenyl)methane
(LV-1);
bis(4-diethylamino-2-methylphenyl)-(4-diethylamino-phenyl)methane
(LV-2); tris(4-diethylamino-2-methylphenyl)methane (LV-3);
bis(4-diethylamino-2-methylphenyl)(3,4-dimethoxyphenyl)methane
(LB-8); aminotriarylmethane leuco dyes having different alkyl
substituents bonded to the amino moieties wherein each alkyl group
is independently selected from C.sub.1-C.sub.4 alkyl; and
aminotriaryl methane leuco dyes with any of the preceding named
structures that are further substituted with one or more alkyl
groups on the aryl rings wherein the latter alkyl groups are
independently selected from C.sub.1-C.sub.3 alkyl. Other color
formers can also be used in connection with the present invention
and are known to those skilled in the art. A more detailed
discussion of some of these types of leuco dyes can be found in
U.S. Pat. Nos. 3,658,543 and 6,251,571, each of which are hereby
incorporated by reference in their entireties. Examples are found
in Chemistry and Applications of Leuco Dyes, Muthyala, Ramaiha,
ed.; Plenum Press, New York, London; ISBN: 0-306-45459-9, which is
incorporated herein by reference.
[0045] Typically, the leuco dye can be present in color forming
compositions of the present invention at from about 1 wt % to about
40 wt %. Although amounts outside this range can be successfully
used, depending on the other components of the composition, amounts
from about 5 wt % to about 20 wt % frequently provide adequate
results.
[0046] In order to reduce development times and increase
sensitivity to an applied radiation source, the color former phase
can further include a melting aid. Suitable melting aids can have a
melting temperature from about 50.degree. C. to about 150.degree.
C. and often from about 70.degree. C. to about 120.degree. C.
Melting aids are typically crystalline organic solids which can be
melted and mixed with a particular color former. For example, most
color formers are also available as a solid particulate which is
soluble in standard liquid solvents. Thus, the color former and
melting aid can be mixed and heated to form a molten mixture. Upon
cooling, a color former phase of color former and melting aid is
formed which can then be ground into a powder. In some embodiments
of the present invention, the percent of color former and melting
aid can be adjusted to minimize the melting temperature of the
color former phase without interfering with the development
properties of the leuco dye. When used, the melting aid can
comprise from about 2 wt % to about 25 wt % of the color former
phase.
[0047] A number of melting aids can be effectively used in the
color forming compositions of the present invention. Several
non-limiting examples of suitable melting aids include m-terphenyl,
p-benzyl biphenyl, alpha-napthyl benzylether,
1,2-bis(3,4)dimethylphenyl ethane, and mixtures thereof. Suitable
melting aids can also include aromatic hydrocarbons (or their
derivatives) which provide good solvent characteristics with the
leuco dye and radiation absorbers used in the formulations and
methods of the present invention. In addition to dissolving the
color former and radiation absorber, the melting aid can also
assist in reducing the melting temperature of the color former and
stabilize the color former phase in the amorphous state (or at
least slow down recrystallization of the color former phase into
individual components). In general, any material having a high
solubility and/or miscibility with the color former to form a glass
or co-crystalline phase with the dye, and alters the melting
property of the dye is useful in this process. For example,
aromatic hydrocarbons, phenolic ethers, aromatic acid-esters, long
chain (C6 or greater) fatty acid esters, polyethylene wax, or the
like can also be suitable melting aids.
[0048] Additional materials can also be included in the color
former phase such as, but not limited to, stabilizers,
anti-oxidants, non-leuco colorants, radiation absorbers, and the
like.
[0049] Radiation Absorber
[0050] A radiation absorber can also be included in the color
forming compositions of the present invention. The radiation
absorber is typically present as a component which can be used to
optimize development of the color forming composition upon exposure
to radiation at a predetermined exposure time, energy level,
wavelength, etc. The radiation absorber can act as an energy
antenna, providing energy to surrounding areas upon interaction
with an energy source. As a predetermined amount of energy can be
provided by the radiation absorber, matching of the radiation
wavelength and intensity to the particular absorber used can be
carried out to optimize the system. Optimizing the system includes
a process of selecting components of the color forming composition
which can result in a rapidly developable composition under a fixed
period of exposure to radiation at a specified power. For example,
compositions of the present invention can be optimized for
development using at a predetermined wavelength of laser energy,
e.g., 405 nm, 650 nm, 780 nm, 980 nm, or 1084 nm, in which the
color forming composition exposed to the radiation is developed in
less than a predetermined period of time, e.g., less than 100
.mu.sec. However, "optimized" does not necessarily indicate that
the color forming composition is developed most rapidly at a
specific wavelength, but rather that the composition can be
developed within a specified time frame using a given radiation
source. An optimized composition can also indicate an ambient light
stability over extended periods of time, i.e. several months to
years. Thus, an optimized composition results from a combination of
all components of the color forming composition in affecting
development characteristics and stability. To illustrate, in
formulating the color forming composition of the present invention,
an optimized composition can depend on a variety of factors, since
each component can affect the development properties, e.g., time,
color intensity, etc. For example, a color forming composition
having a radiation antenna with a maximum absorption of about 780
nm may not develop most rapidly at 780 nm. Other components and the
specific formulation can result in an optimized composition at a
wavelength which does not correspond to the maximum absorption of
the radiation antenna. Thus, the process of formulating an
optimized color forming composition can include testing
formulations to achieve a desired development time using a specific
intensity and wavelength of energy to form an acceptable color
change.
[0051] The radiation absorber can be configured to be in a
heat-conductive relationship with the color formers of the present
invention. For example, the radiation absorber can be included
within the color former phase, the polymer matrix, and/or a
separate layer. Thus, the radiation absorber can be admixed with or
in thermal contact with the color forming composition. Typically,
the radiation absorber can be present in both the color former
phase and the polymeric activator phase. In this way, substantially
the entire color forming composition in an exposed area can be
heated quickly and substantially simultaneously. Alternatively, the
radiation absorber can be applied as a separate layer which can be
optionally spin-coatable or screen-printable, for example.
Consideration can also be given to choosing the radiation absorber
such that any light absorbed in the visible range does not
adversely affect the graphic display or appearance of the color
forming composition either before or after development.
[0052] Suitable radiation antenna can be selected from a number of
radiation absorbers such as, but not limited to, aluminum quinoline
complexes, porphyrins, porphins, indocyanine dyes, phenoxazine
derivatives, phthalocyanine dyes, polymethyl indolium dyes,
polymethine dyes, guaiazulenyl dyes, croconium dyes, polymethine
indolium dyes, metal complex IR dyes, cyanine dyes, squarylium
dyes, chalcogeno-pyryloarylidene dyes, indolizine dyes, pyrylium
dyes, quinoid dyes, quinone dyes, azo dyes, and mixtures or
derivatives thereof. Other suitable antennas can also be used in
the present invention and are known to those skilled in the art and
can be found in such references as Infrared Absorbing Dyes,
Matsuoka, Masaru, ed., Plenum Press, New York, 1990 (ISBN
0-306-43478-4) and Near-Infrared Dyes for High Technology
Applications, Daehne, Resch-Genger, Wolfbeis, Kluwer Academic
Publishers (ISBN 0-7923-5101-0), both of which are incorporated
herein by reference.
[0053] Consideration can also be given to choosing the radiation
antenna such that any light absorbed in the visible range does not
adversely affect the graphic display or appearance of the color
forming composition either before or after development. For
example, in order to achieve a visible contrast between developed
areas and non-imaged or non-developed areas of the coating, the
color former can be chosen to form a color that is different than
that of the background. For example, color formers having a
developed color such as black, blue, red, magenta, and the like can
provide a good contrast to a more yellow background. Optionally, an
additional non-color former colorant can be added to the color
forming compositions of the present invention or the substrate on
which the color forming composition is placed. Any known non-color
former colorant can be used to achieve almost any desired
background color for a given commercial product. Although the
specific color formers and antennae discussed herein are typically
separate compounds, such activity can also be provided by
constituent groups of binders and/or color formers which are
incorporated in the activation and/or radiation absorbing action of
color former. These types of color former/radiation absorbers are
also considered to be within the scope of the present
invention.
[0054] Various radiation antennas can act as an antenna to absorb
electromagnetic radiation of specific wavelengths and ranges.
Generally, a radiation antenna which has a maximum light absorption
at or in the vicinity of the desired development wavelength can be
suitable for use in the present invention. For example, in one
aspect of the present invention, the color forming composition can
be optimized within a range for development using infrared
radiation having a wavelength from about 720 nm to about 900 nm in
one embodiment. Common CD-burning lasers have a wavelength of about
780 nm and can be adapted for forming images by selectively
developing portions of the color forming composition. Radiation
antennae which can be suitable for use in the infrared range can
include, but are not limited to, polymethyl indoliums, metal
complex IR dyes, indocyanine green, polymethine dyes such as
pyrimidinetrione-cyclopentylidenes, guaiazulenyl dyes, croconium
dyes, cyanine dyes, squarylium dyes, chalcogenopyryloarylidene
dyes, metal thiolate complex dyes, bis(chalcogenopyrylo)polymethine
dyes, oxyindolizine dyes, bis(aminoaryl)polymethine dyes,
indolizine dyes, pyrylium dyes, quinoid dyes, quinone dyes,
phthalocyanine dyes, naphthalocyanine dyes, azo dyes,
hexafunctional polyester oligomers, heterocyclic compounds, and
combinations thereof.
[0055] Several specific polymethyl indolium compounds which can be
used are available from Aldrich Chemical Company, and include
2-[2-[2-chloro-3-[2-(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)-ethy-
lidene]-1-cyclopenten-1-yl-ethenyl]-1,3,3-trimethyl-3H-indolium
perchlorate;
2-[2-[2-Chloro-3-[2-(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)-ethy-
lidene]-1-cyclopenten-1-yl-ethenyl]-1,3,3-trimethyl-3H-indolium
chloride;
2-[2-[2-chloro-3-[(1,3-dihydro-3,3-dimethyl-1-propyl-2H-indol-2-ylidene)e-
thylidene]-1-cyclohexen-1-yl]ethenyl]-3,3-dimethyl-1-propylindolium
iodide;
2-[2-[2-chloro-3-[(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene-
)ethylidene]-1-cyclohexen-1-yl]ethenyl]-1,3,3-trimethylindolium
iodide;
2-[2-[2-chloro-3-[(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)ethylid-
ene]-1-cyclohexen-1-yl]ethenyl]-1,3,3-trimethylindolium
perchlorate;
2-[2-[3-[(1,3-dihydro-3,3-dimethyl-1-propyl-2H-indol-2-ylidene)ethylidene-
]-2-(phenylthio)-1-cyclohexen-1-yl]ethenyl]-3,3-dimethyl-1-propylindolium
perchlorate; and mixtures thereof. Alternatively, the radiation
antenna can be an inorganic compound, e.g., ferric oxide, carbon
black, selenium, or the like. Polymethine dyes or derivatives
thereof such as a pyrimidinetrione-cyclopentylidene, squarylium
dyes such as guaiazulenyl dyes, croconium dyes, or mixtures thereof
can also be used in the present invention. Suitable
pyrimidinetrione-cyclopentylidene infrared antennae include, for
example, 2,4,6(1H,3H,5H)-pyrimidinetrione
5-[2,5-bis[(1,3-dihydro-1,1,3-dimethyl-2H-indol-2-ylidene)ethylidene]cycl-
opentylidene]-1,3-dimethyl-(9Cl) (S0322 available from Few
Chemicals, Germany).
[0056] In another aspect of the present invention, the radiation
antenna can be selected for optimization of the color forming
composition in a wavelength range from about 600 nm to about 720
nm, such as about 650 nm. Non-limiting examples of suitable
radiation antennae for use in this range of wavelengths can include
indocyanine dyes such as
3H-indolium,2-[5-(1,3-dihydro-3,3-dimethyl-1-propyl-2H-indol-2-ylidene)-1-
,3-pentadienyl]-3,3-dimethyl-1-propyl-iodide) (Dye 724 .lamda.max
642 nm),
3H-indolium,1-butyl-2-[5-(1-butyl-1,3-dihydro-3,3-dimethyl-2H-indol-2-yli-
dene)-1,3-pentadienyl]-3,3-dimethyl-,perchlorate (Dye 683
.lamda.max 642 nm), and phenoxazine derivatives such as
phenoxazin-5-ium,3,7-bis(diethylamino)-,perchlorate (oxazine 1
.lamda.max=645 nm). Phthalocyanine dyes having a .lamda.max of
about the desired development wavelength can also be used such as
silicon 2,3-napthalocyanine bis(trihexylsilyloxide) and matrix
soluble derivatives of 2,3-napthalocyanine (both commercially
available from Aldrich Chemical); matrix soluble derivatives of
silicon phthalocyanine (as described in Rodgers, A. J. et al., 107
J. Phys. Chem. A 3503-3514, May 8, 2003), and matrix soluble
derivatives of benzophthalocyanines (as described in Aoudia,
Mohamed, 119 J. Am. Chem. Soc. 6029-6039, July 2, 1997);
phthalocyanine compounds such as those described in U.S. Pat. Nos.
6,015,896 and 6,025,486, which are each incorporated herein by
reference; and Cirrus 715 (a phthalocyanine dye available from
Avecia, Manchester, England having a .lamda.max=806 nm).
[0057] In yet another aspect of the present invention, laser light
having blue and indigo wavelengths from about 300 nm to about 600
nm can be used to develop the color forming compositions.
Therefore, the present invention can provide color forming
compositions optimized within a range for use in devices that emit
wavelengths within this range. Recently developed commercial lasers
found in certain DVD and laser disk recording equipment provide for
energy at a wavelength of about 405 nm. Thus, the compositions of
the present invention using appropriate radiation antennae can be
suited for use with components that are already available on the
market or are readily modified to accomplish imaging. Radiation
antennae which can be useful for optimization in the blue
(.about.405nm) and indigo wavelengths can include, but are not
limited to, aluminum quinoline complexes, porphyrins, porphins, and
mixtures or derivatives thereof. Non-limiting specific examples of
suitable radiation antenna can include
1-(2-chloro-5-sulfophenyl)-3-methyl-4-(4-sulfophenyl)azo-2-pyrazo-
lin-5-one disodium salt (.lamda.max=400 nm); ethyl
7-diethylaminocoumarin-3-carboxylate (.lamda.max=418 nm);
3,3'-diethylthiacyanine ethylsulfate (.lamda.max=424 nm);
3-allyl-5-(3-ethyl-4-methyl-2-thiazolinylidene)rhodanine
(.lamda.max=430 nm) (each available from Organica Feinchemie GmbH
Wolfen), and mixtures thereof. Non-limiting specific examples of
suitable aluminum quinoline complexes can include
tris(8-hydroxyquinolinato)aluminum (CAS 2085-33-8) and derivatives
such as tris(5-cholor-8-hydroxyquinolinato)aluminum (CAS
4154-66-1),
2-(4-(1-methyl-ethyl)-phenyl)-6-phenyl-4H-thiopyran-4-ylidene)-propanedin-
itril-1,1-dioxide (CAS 174493-15-3),
4,4'-[1,4-phenylenebis(1,3,4-oxadiazole-5,2-diyl)]bis N,N-diphenyl
benzeneamine (CAS 184101-38-0),
bis-tetraethylammonium-bis(1,2-dicyano-dithiolto)-zinc(II) (CAS
21312-70-9),
2-(4,5-dihydronaphtho[1,2-d]-1,3-dithiol-2-ylidene)-4,5-dihydro-naphtho[1-
,2-d]1,3-dithiole, all available from Syntec GmbH. Non-limiting
examples of specific porphyrin and porphyrin derivatives can
include etioporphyrin 1 (CAS 448-71-5), deuteroporphyrin IX 2,4 bis
ethylene glycol (D630-9) available from Frontier Scientific, and
octaethyl porphyrin (CAS 2683-82-1), azo dyes such as Mordant
Orange (CAS 2243-76-7), Methyl Yellow (CAS 60-11-7),
4-phenylazoaniline (CAS 60-09-3), Alcian Yellow (CAS 61968-76-1),
available from Aldrich chemical company, and mixtures thereof.
[0058] In each of these embodiments, generally, the radiation
absorber can be present in the color forming composition as a whole
at from about 0.001 wt % to about 10 wt %, and typically, from
about 0.5 wt % to about 1 wt %, although other weight ranges may be
desirable depending on the molar absorbtivity of the particular
radiation absorber.
[0059] Other Optional Ingredients
[0060] The color forming compositions of the present invention can
also include various additional components such as colorants,
liquid vehicles, stabilizers, anti-fade agents, plasticizers, and
other additives known to those skilled in the art.
[0061] For example, in one embodiment, it may be desirable to
include a reducing agent. Specific reducing agent activators than
can be used include 1-phenyl-3-pyrozolidone(phenidone), hydrazine,
formamide, formic acid, hexaarylbiimidazoles (HABI), ascorbic acid,
phenols and substituted phenols, e.g., hydroquinone, and mixtures
thereof.
[0062] In certain embodiments of the present invention, it is
sometimes desirable to add a plasticizer to improve coating
flexibility, durability, and coating performance. Plasticizers can
be either solid or liquid plasticizers. Such suitable plasticizers
are well known to those skilled in the art, as exemplified in U.S.
Pat. No. 3,658,543, which is incorporated herein by reference in
its entirety. Specific examples of plasticizers include, but are
not limited to, cellulose esters such as an o-phenyl phenol
ethylene oxide adduct (commercially available as MERPOL 2660 from
E. I. Du Pont de Nemours & Co., Wilmington, Del.), polyethylene
glycols and substituted phenolethylene oxide adducts such as
nonylphenoxypoly(ethyleneoxy)-ethanol (commercially available as
IGEPAL CO 210 from Aldrich Chemical Co.), acetates, butyrates,
cellulose acetate butyrates, and mixtures thereof. The plasticizer
can be included in either or both of the polymer matrix and the
color former phase.
[0063] Other additives can also be utilized for producing
particular commercial products such as including a colorant to
impart additional desired color to the image. In one embodiment,
these colorants can be non-color formers which can provide a
background color. In one embodiment, optional colorants can be
standard pigments and/or dyes. For example, the use of an opacifier
pigment or other colorant can provide background color to the
substrate. The optional colorants can be added to the color forming
composition, underprinted, or overprinted, as long as the
development of the color former is not prevented from at least some
development due to the presence of the optional colorant.
[0064] In another embodiment, the color forming composition can be
prepared in a solution which is substantially transparent or
translucent. Any suitable liquid carrier, e.g., an alcohol with a
surfactant, can be used which is compatible with a particular color
former, polymer matrix, and/or other components chosen for use. The
liquid carrier can include, but is not limited to, solvents such as
methylethyl ketone, isopropyl alcohol or other alcohols and diols,
water, surfactants, and mixtures thereof. When the color forming
composition is prepared in a solution form, it may be desirable to
underprint a colored coating over at least a portion of the
substrate beneath the color forming composition. The optional
colored coating produces a background color that can be visible
underneath the solution layer. This colored coating can contain
various colorants such as other pigments and/or dyes.
[0065] In one embodiment of the present invention, the color
forming composition can be applied to a substrate. The composition
can be applied to the substrate using any known technique such as
spin-coating, screen printing, sputtering, spray coating,
ink-jetting, or the like. A variety of substrates can be used such
as polymer, paper, metal, glass, ceramic, and combinations or
composites thereof. In one embodiment, the color forming
composition can be applied to an optical disk, and thus, select
portions thereof can be subsequently developed using a laser or
other radiation source. Suitable coating thicknesses can be from
about 1 .mu.m to about 15 .mu.m.
[0066] The color forming composition can be prepared in a number of
ways for application to a substrate. Often, the liquid carrier can
be used which can be at least partially removed through known
solvent removal processes. Typically, at least a portion of the
liquid carrier can be driven off or allowed to evaporate after the
coating process is complete. Alternatively, in some embodiments, it
may not be necessary to use a liquid carrier, as the polymer matrix
can be used as a carrier. Further, various additional components,
such as lubricants, surfactants, and materials imparting moisture
resistance, can also be added to provide mechanical protection to
the color forming composition. Other overcoat compositions can also
be used and are well known to those skilled in the art.
[0067] In one aspect of the present invention, the color forming
composition can be spin-coatable or screen-printable. In order to
provide desirable color forming properties and spin-coatability,
various factors such as viscosity and solids content can also be
considered. The color forming compositions of the present invention
can have less than about 10 wt % solids, which typically provides
good coating properties. For example, in one aspect, the solids
content of a spin-coatable color forming composition can be from
about 5 wt % to about 9 wt %.
[0068] Radiation Application for Development
[0069] Once the color forming composition is applied to the
substrate, the conditions under which the color forming
compositions of the present invention are developed can be varied.
For example, one can vary the electromagnetic radiation wavelength,
heat flux, and exposure time. The amount of energy which is to be
applied depends partially on the activation energy of the
development reaction of the color former and the specific radiation
absorber chosen. However, the energy applied is typically
sufficient to develop the color former without also chemically
decomposing the color forming composition or damaging the
substrate. Such an energy level is typically well below the energy
required for decomposition of the color forming composition.
Variables such as spot size, focus, and laser power will also
affect any particular system design and can be chosen based on the
desired results. With these variables fixed at predetermined
values, the radiation source can then direct electromagnetic
radiation to the color forming composition in accordance with data
received from a signal processor. Further, color former and/or
radiation absorber concentration and proximity to one another can
also be varied to affect the development times and the optical
density of the developed image.
[0070] Typically, an image to be formed on the surface can be
digitally stored and then rasterized or spiralized. The resulting
data can be delivered to a radiation source which exposes portions
of the color forming composition to radiation while the optical
disk is spinning. As previously discussed, any number of
electromagnetic radiation sources can be used.
[0071] The color forming compositions of the present invention can
be developed using lasers having from about 15 mW to about 100 mW
power usage, although lasers having a power outside this range can
also be used. Typically, lasers having from about 30 mW to about 50
mW are readily commercially available and work well using the color
forming composition described herein. The spot size generated by
the laser can be determined by radiation that contacts the
substrate at a single point in time. The spot size can be circular,
oblong, or other geometric shape, and can range from about 1 .mu.m
to about 200 .mu.m along a largest dimension and often from about 5
.mu.m to about 60 .mu.m, though smaller or larger sizes can also be
used. In a further aspect, spot sizes of 5 to 25 .mu.m by 50 .mu.m,
as measured across perpendicular major and minor axes, can provide
a good balance between resolution and developing speed.
[0072] Heat flux is a variable that can be altered as well, and can
be from about 0.05 J/cm.sup.2 to about 5.0 J/cm.sup.2in one
embodiment, and from about 0.3 J/cm.sup.2 to about 0.5 J/cm.sup.2
in a second embodiment. In general, a heat flux of less than about
0.5 J/cm.sup.2 can also be used. The color forming compositions of
the present invention can be optimized by adjusting the
concentrations and type of radiation absorber, color former, and
polymer matrix. Heat flux in these ranges allow for development of
color formers in optimized compositions in from about 15 .mu.sec to
about 1 millisecond per dot in some embodiments. As previously
discussed, in part because of the small particle size of the color
former phase, improved sensitivity of the composition can promote
faster image writing. Thus, in one embodiment, the color forming
compositions of the present invention can be optimized for
development in less than about 200 .mu.sec, and in some embodiments
less than about 50 .mu.sec. An exemplary range of development time
that is practical in accordance with embodiments of the present
invention is from about 15 .mu.sec to about 200 .mu.sec. Those
skilled in the art can adjust these and other variables to achieve
a variety of resolutions and developing times.
[0073] In embodiments where the substrate is an optical disk or
other moving substrate, the exposure time will depend on the rate
of motion of the substrate. More specifically, in such embodiments,
the exposure times above refer to the time during which a point on
the substrate is exposed to the radiation. For example, a spot size
of 50 .mu.m along the direction of rotation will result in a single
point oh the substrate traveling through the spot starting at one
edge and traveling to the opposite edge. The total exposure time is
therefore the average time that radiation contacts a particular
point on the substrate or color forming composition.
[0074] Though any laser can be used to provide energy to the color
forming compositions, currently there are many known laser types.
Those of particular interest include those commercially available
which can be incorporated into an optical disk reading and/or
writing device, particularly those in the 200 nm to 1200 nm
wavelength range. However, wavelengths outside of this range are
also included in accordance with embodiments of the present
invention. Exemplary laser types that can be used include
krypton-fluoride excimer (249 nm), xenon-chloride eximer (308 nm),
nitrogen gas (337 nm), organic dye in solution (300 nm to 1000
nm--tunable), krypton ion (335 nm to 800 nm), argon ion (450 nm to
530 nm), helium neon (543 nm, 632.8 nm, and 1150 nm), semiconductor
GaInP family (670 nm to 680 nm), ruby (694 nm), semiconductor
GaAlAs family (750 nm to 900 nm), neodymium YAG (1064 nm),
semiconductor InGaAsP family (1300 nm to 1600 nm),
hydrogen-fluoride chemical (2600 nm to 3000 nm), etc. In addition
to the above, these and other commercially available lasers are
available having wavelengths of: 375 nm, 405 nm, 408 nm, 440 nm,
635 nm, 638 nm, 650 nm, 660 nm, 670 nm, 685 nm, 780 nm, 785 nm, 810
nm, 830 nm, 850 nm, 980 nm, 1084 nm, 1310 nm, and 1550 nm, for
example. These laser-types or others are useable in accordance with
embodiments of the present invention, provided the laser energy is
functional with the color forming compositions in accordance with
embodiments of the present invention.
EXAMPLES
[0075] The following examples illustrate exemplary embodiments of
the invention. However, it is to be understood that the following
are only exemplary or illustrative of the application of the
principles of the present invention. Numerous modifications and
alternative compositions, methods, and systems may be devised by
those skilled in the art without departing from the spirit and
scope of the present invention. The appended claims are intended to
cover such modifications and arrangements. Thus, while the present
invention has been described above with particularity, the
following examples provide further detail in connection with what
is presently deemed to be practical embodiments of the
invention.
Example 1
[0076] a) Preparation of Color Former Particles for Color Former
Phase (Discontinuous Phase)
[0077] About 10 g of m-terphenyl (accelerator) was melted in a
beaker, and the melt was heated to about 110.degree. C. About 100 g
of BK400 was added in small increments to the melt upon constant
stirring. The added BK400 is a leuco-dye
(2'-anilino-3'-methyl-6'-(dibutylamino)fluoran) available from
Nagase Corporation, the structure of which is set forth below as
Formula 1: ##STR1## The temperature of the mixture was increased up
to about 170.degree. C. to 180.degree. C. Stirring was continued
until complete dissolution of BK400 in the melt (usually takes
about 10 to 15 min) was obtained to form an accelerator/leuco dye
solution. Next, about 1.8 g of Cirrus-715 (radiation absorber IR
dye) was added to the melt upon constant stirring. Heating and
stirring was continued for about two to three additional minutes
until the Cirrus-715 was completely dissolved in the melt to form a
leuco dye/antenna/accelerator alloy (eutectic). The temperature of
the leuco-dye/antenna/accelerator alloy was kept to below about
190.degree. C., and was then poured into a pre-cooled freezer tray
lined with aluminum foil. The solidified melt was milled into a
coarse powder and then jet-milled until the average volume-weighted
particle size of the ground alloy was less than about 1.5 .mu.m,
resulting in color former particles that will become the color
former phase.
[0078] b) Preparation of Polymeric Activator Phase (Continuous
Phase)
[0079] About 50 g of m-terphenyl was melted in a beaker. About 50 g
of Cirrus-715 (radiation absorber IR dye) was then dissolved in the
melted m-terphenyl while the temperature of the melt was raised to
about 150.degree. C. to 160.degree. C. The resulting
m-terphenyl/Cirrus-715 alloy was cooled and ground into a coarse
powder. Next, about 8 g of 4-hydroxyphenyl-4'-isopropoxyphenyl
sulfone (activator), 1.7 g of the m-terphenyl/Cirrus-715 alloy, and
about 3.7 g of 4,4-dihydroxydiphenyl sulfone (primary activator)
were dissolved in 49 g Nor-Cote CDG000 UV-lacquer (mixture or
packet of UV-curable acrylate monomers and oligomers) to form a
lacquer/antenna/activator solution or polymeric activator
phase.
[0080] c) Preparation of Color Forming Composition (Fine
Dispersion)
[0081] A UV-curable paste was prepared by mixing (a) about 31 of
the finely milled color former particles with (b) about 60 g of the
polymeric accelerator phase. The paste was screen printed onto a
substrate at a thickness of approximately about 6 .mu.m to about 8
.mu.m to form an imaging medium including an imaging coating. The
imaging coating was UV cured by mercury lamp. Direct marking on the
UV cured imaging coating was carried out using a 45 mW laser having
a wavelength of about 780 nm. A mark of approximately 20 .mu.m by
45 .mu.m was produced using various durations of energy application
from about 30 .mu.sec to about 150 .mu.sec. Upon application of
appropriate energy, the color forming composition of the imaging
coating changed in color from a greenish transparent appearance to
a black color.
Example 2
[0082] a) Preparation of Color Former Particles for Color Former
Phase (Discontinuous Phase)
[0083] About 10 g of m-terphenyl (accelerator) was melted in a
beaker, and the melt was heated to about 110.degree. C. About 100 g
of BK400 was added in small increments to the melt upon constant
stirring. The added BK400 is a leuco-dye
(2'-anilino-3'-methyl-6'-(dibutylamino)fluoran) available from
Nagase Corporation, the structure of which is set forth in Formula
1 above. The temperature of the mixture was then increased up to
about 170.degree. C. to 180.degree. C. Stirring was continued until
complete dissolution of BK400 in the melt (usually takes about 10
to 15 min) was obtained to form an accelerator/leuco dye solution
melt. About 1.2 g of IR780-iodide (radiation absorber IR dye) was
then added to the melt upon constant stirring. IR780-iodide is also
known as 3H-Indolinium,
2-[2-chloro-3-[91,3-dihydro3,3-dimethyl-1-propyl-2H-indol-2-ylidene)ethyl-
idene]-1-cyclohexen-1yl]ethenenyl]-3,3-dimethyl-1-propyl-,
iodide(9Cl), as shown in Formula 2 as follows: ##STR2## Heating and
stirring was continued for about two to three additional minutes
until the IR dye was completely dissolved in the melt to form a
leuco dye/antenna/accelerator alloy (eutectic). The temperature of
the leuco dye/antenna/accelerator alloy was kept to below about
190.degree. C. The leuco-dye/antenna/accelerator alloy was then
poured into a pre-cooled freezer tray lined with aluminum foil. The
solidified melt was milled into a coarse powder, and then the
pre-milled powder was milled in aqueous dispersion (.about.15%
solids) using Netzsch Mini-Zeta Bead mill with 1 mm zirconia beads.
The milling was stopped when average particle diameter was reduced
to a value of about 0.9 .mu.m to about 1.0 .mu.m. The particles in
the slurry were collected and freeze-dried, resulting in color
former particles that will become the color former phase.
[0084] b) Preparation of Polymeric Activator Phase (Continuous
Phase)
[0085] About 50 g of m-terphenyl was melted in a beaker. About 50 g
of Cirrus-715 (radiation absorber IR dye) was then dissolved in the
melted m-terphenyl while the temperature of the melt was raised to
about 150.degree. C. to 160.degree. C. The resulting
m-terphenyl/Cirrus-715 alloy was cooled and ground into a coarse
powder. Next, about 8 g of 4-hydroxyphenyl-4'-isopropoxyphenyl
sulfone (activator), 1.7 g of the m-terphenyl/Cirrus-715 alloy, and
about 3.7 g of 4,4-dihydroxydiphenyl sulfone (primary activator)
were dissolved in 49 g Nor-Cote CDG000 UV-lacquer (mixture or
packet of UV-curable acrylate monomers and oligomers) to form a
lacquer/antenna/activator solution or polymeric activator
phase.
[0086] c) Preparation of Color Forming Composition (Fine
Dispersion)
[0087] A UV-curable paste was prepared by mixing (a) about 31 of
the finely milled the color former particles with (b) about 60 g of
the polymeric accelerator phase. The paste was screen printed onto
a substrate at a thickness of approximately about 6 .mu.m to about
8 .mu.m to form an imaging medium including an imaging coating. The
coating on the medium was then UV cured by mercury lamp. The
resulting coating had an opalescent semi-transparent look. Direct
marking on the UV cured imaging coating was carried out using a 45
mW laser having a wavelength of about 780 nm. A mark of
approximately 20 .mu.m by 45 .mu.m was produced using various
durations of energy application from about 25 .mu.sec to about 130
.mu.sec. Upon application of appropriate energy, the color forming
composition of the imaging coating changed in color from a greenish
transparent appearance to a black color.
Example 3
[0088] a) Preparation of Color Former Particles for Color Former
Phase (Discontinuous Phase)
[0089] About 10 g of m-terphenyl (accelerator) was melted in a
beaker, and the melt was heated to about 110.degree. C. About 100 g
of BK400 was added in small increments to the melt upon constant
stirring. The added BK400 is a leuco-dye
(2'-anilino-3'-methyl-6'-(dibutylamino)fluoran) available from
Nagase Corporation, the structure of which is set forth in Formula
1 above. The temperature of the mixture was increased up to about
170.degree. C. to 180.degree. C. Stirring was continued until
complete dissolution of BK400 in the melt (usually takes about 10
to 15 min) was obtained to form an accelerator/leuco dye solution.
Next, about 1.8 g of Cirrus-715 (radiation absorber IR dye) was
added to the melt upon constant stirring. Heating and stirring was
continued for about two to three additional minutes until the
Cirrus-715 was completely dissolved in the melt to form a leuco
dye/antenna/accelerator alloy (eutectic). The temperature of the
leuco-dye/antenna/accelerator alloy was kept to below about
190.degree. C., and was then poured into a pre-cooled freezer tray
lined with aluminum foil. The solidified melt was milled into a
coarse powder and then jet-milled until the average volume-weighted
particle size of the ground alloy was less than about 1.5 .mu.m.
Next, this pre-milled powder was further milled in an aqueous
dispersion (.about.15% solids) using Netzsch Mini-Zeta Bead mill
with 1 mm zirconia beads. The milling was stopped when average
particle diameter was reduced to a value of about 0.9 .mu.m to
about 1.0 .mu.m. The resulting slurry was then further milled in
the Netzsch Mini-Zeta Bead mill using tungsten carbide 0.1 mm beads
until the average particle size was reduced to about 0.2 .mu.m to
about 0.3 .mu.m. The resulting slurry containing the color former
particles which will ultimately become the color former phase was
collected and freeze-dried.
[0090] b) Preparation of Polymeric Activator Phase (Continuous
Phase)
[0091] About 87 g of 4-hydroxyphenyl-4'-isopropoxyphenyl sulfone
activator was melted in a beaker. About 13 g of IR780-iodide
(radiation absorber IR dye shown in Formula 2) was then dissolved
in the melted activator while the temperature of the melt was
raised to about 150.degree. C. to 160.degree. C. The resulting
activator/radiation absorber alloy was cooled and ground into a
coarse powder. Next, about 7 g of the activator/radiation absorber
alloy powder and about 3.7 g of 4,4-dihydroxydiphenyl sulfone
(primary activator) were dissolved in 49 g Nor-Cote CDG000
UV-lacquer (mixture or packet of UV-curable acrylate monomers and
oligomers) to form the lacquer/antenna/activator solution or
polymeric activator phase.
[0092] c) Preparation of Color Forming Composition (Fine
Dispersion)
[0093] A UV-curable paste was prepared by mixing (a) about 31 of
the finely milled the color former particles with (b) about 60 g of
the polymeric accelerator phase. The paste was screen printed onto
a substrate at a thickness of approximately about 6 .mu.m to about
8 .mu.m to form an imaging medium including an imaging coating. The
coating on the medium was then UV cured by mercury lamp. The
resulting coating was transparent with noticeable greenish hue.
Direct marking on the UV cured imaging coating was carried out
using a 45 mW laser having a wavelength of about 780 nm. A mark of
approximately 20 .mu.m by 45 .mu.m was produced using various
durations of energy application from about 15-20 .mu.sec to about
100 .mu.sec. Upon application of appropriate energy, the color
forming composition of the imaging coating changed in color from
the greenish transparent appearance to a black color.
Example 4
[0094] The above color forming compositions of eutectics (Examples
1 to 3) with average particle sizes of 2 .mu.m or less has shown
significantly higher contrast and sensitivity than the materials
with larger average particle sizes, e.g., 5 .mu.m, when developed
at similar. To illustrate this, various comparative materials were
prepared in accordance with Example 1, except that each material
utilized a different particle size resulting from different levels
of milling. Particularly, the particle sizes prepared were 2 .mu.m
and 5 .mu.m, as shown in Table 1, and 3.7 .mu.m, 2.3 .mu.m, 1.5
.mu.m, and 0.25 .mu.m as shown in Tables 2 and 3.
[0095] In Table 1 below, legible marks (.DELTA.L* of >10), at
much higher speeds (lower energy input) were obtained using the
composition having a smaller particle size. TABLE-US-00001 TABLE 1
Particle size, .mu.m 2 5 Speed for Mark (.DELTA.L* of 10), m/sec
0.75 0.25 Contrast of mark at 0.25 m/Sec, .DELTA.L* 32 12
[0096] In Tables 2 and 3 below, particle size was also shown to
impact write speed and contrast performance. Specifically, in Table
2 below, the following test conditions for write speed were
established: maximum 780 nm laser spot linear velocity necessary to
mark with contrast .DELTA.L*.gtoreq.20 (Laser Power=38 mW/marking
density=1040 tracks per inch). The results of this analysis are
shown, as follows: TABLE-US-00002 TABLE 2 Particle size, .mu.m
Linear velocity, m/sec 3.7 0.32 2.3 0.4 1.5 0.52 0.25 0.67
[0097] In Table 3, contrast was determined marking with 780 nm
laser (Power=38 mW; marking density=1040 tracks per inch) at laser
spot Linear Velocity=0.6 m/sec, the results being shown as follows:
TABLE-US-00003 TABLE 3 Particle size, .mu.m Contrast, .DELTA.L* 3.7
9.38 2.3 12.67 1.5 16.23 0.25 21.29
[0098] It is to be understood that the above-referenced
arrangements are illustrative of the application for the principles
of the present invention. Numerous modifications and alternative
arrangements can be devised without departing from the spirit and
scope of the present invention while the present invention has been
described above in connection with the exemplary embodiments(s) of
the invention. It will be apparent to those of ordinary skill in
the art that numerous modifications can be made without departing
from the principles and concepts of the invention as set forth in
the claims.
* * * * *