U.S. patent application number 11/198460 was filed with the patent office on 2005-12-22 for imaging compositions and methods.
This patent application is currently assigned to Rohm and Haas Electronic Materials LLC. Invention is credited to Barr, Robert K., O'Connor, Corey.
Application Number | 20050282084 11/198460 |
Document ID | / |
Family ID | 35425731 |
Filed Date | 2005-12-22 |
United States Patent
Application |
20050282084 |
Kind Code |
A1 |
Barr, Robert K. ; et
al. |
December 22, 2005 |
Imaging compositions and methods
Abstract
Imaging compositions and methods of using the compositions are
disclosed. The imaging compositions include two discrete
components. One component includes opacifying compounds and the
second component includes sensitizing dyes. The second component is
sensitive to low levels of energy. Application of the low levels of
energy induces a color or shade change in the second component. The
imaging compositions may be applied to a work piece to mark it such
that it may be modified based on the marks.
Inventors: |
Barr, Robert K.;
(Shrewsbury, MA) ; O'Connor, Corey; (Worcester,
MA) |
Correspondence
Address: |
John J. Piskorski
Rohm and Haas Electronic Materials LLC
455 Forest Street
Marlborough
MA
01752
US
|
Assignee: |
Rohm and Haas Electronic Materials
LLC
Marlborough
MA
|
Family ID: |
35425731 |
Appl. No.: |
11/198460 |
Filed: |
August 5, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11198460 |
Aug 5, 2005 |
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10890507 |
Jul 12, 2004 |
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10890507 |
Jul 12, 2004 |
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10773989 |
Feb 6, 2004 |
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10890507 |
Jul 12, 2004 |
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10773990 |
Feb 6, 2004 |
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10890507 |
Jul 12, 2004 |
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10773991 |
Feb 6, 2004 |
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Current U.S.
Class: |
430/270.1 |
Current CPC
Class: |
Y10S 430/127 20130101;
G03C 1/73 20130101; Y10S 430/163 20130101; G03C 1/732 20130101 |
Class at
Publication: |
430/270.1 |
International
Class: |
G03C 001/492 |
Claims
What is claimed is:
1. An imaging composition comprising a first component comprising
one or more opacifying compounds, and a second component comprising
one or more sensitizers.
2. The imaging composition of claim 1, wherein the one or more
opacifying compounds are chosen from pigments, metal salts, silica,
silicates and clays.
3. The imaging composition of claim 1, wherein the one or more
sensitizers are chosen from xanthene compounds and cyclopentanone
based conjugated compounds.
4. The imaging composition of claim 1, wherein the first component
further comprises one or more adhesives.
5. The imaging composition of claim 1, wherein the second component
further comprises one or more color formers.
6. The imaging composition of claim 1, wherein the second component
further comprises one or more micro-encapsulated antioxidants.
7. An imaging composition comprising a first component comprising
one or more opacifying compounds and one or more release agents,
and a second component comprising one or more sensitizers and one
or more release agents.
8. A method comprising: a) providing a first component of an
imaging composition, the first component comprises one or more
opacifying compounds; b) applying the first component of the
imaging composition to a work piece; c) providing a second
component of the imaging composition, the second component
comprises one or more sensitizers; d) applying the second component
of the imaging composition on the first component; e) applying
energy to the imaging composition at powers of 5 mW or less to
affect a color or shade change in the second component of the
imaging composition; and f) executing a task on the work piece as
directed by the color or shade change of the second component of
the imaging composition to modify the work piece.
9. The method of claim 8, further comprising the step of removing
the imaging composition from the work piece by peeling the imaging
composition from the workpiece.
10. The method of claim 8, wherein the work piece is chosen from a
terrestrial vehicle, an aeronautical ship, a marine vessel, a
terrestrial structure, and a textile.
Description
[0001] This Patent Application is a continuation-in-part of
co-pending patent application Ser. No. 10/890,507 filed Jul. 12,
2004, which is a continuation-in-part of co-pending patent
applications Ser. Nos. 10/773,989, 10/773,990, and 10/773,991 filed
Feb. 6, 2004.
[0002] The present invention is directed to imaging compositions
having two separate functional components and methods of using the
imaging compositions. More specifically, the present invention is
directed to imaging compositions having two separate functional
components where one component is opaque and the second component
undergoes a color or shade change upon exposure to energy at low
powers and methods of using the imaging compositions.
[0003] There are numerous compositions and methods employed in
various industries to form images on substrates to mark the
substrates. Such industries include the paper industry, packaging
industry, paint industry, medical industry, dental industry,
electronics industry, textile industry, aeronautical, marine and
automotive industries, and the visual arts.
[0004] Imaging or marking also is employed in proofing products,
photoresists, soldermasks, printing plates and other photopolymer
products. For example, U.S. Pat. No. 5,744,280 discloses
photoimageable compositions allegedly capable of forming monochrome
and multichrome images, which have contrast image properties. The
photoimageable compositions include photooxidants,
photosensitizers, photodeactivation compounds and deuterated leuco
compounds. The leuco compounds are aminotriarylmethine compounds or
related compounds in which the methane (central) carbon atom is
deuterated to the extant of at least 60% with deuterium
incorporation in place of the corresponding hydrido
aminotriaryl-methine. The patent alleges that the deuterated leuco
compounds provide for an increased contrast imaging as opposed to
corresponding hydrido leuco compounds. Upon exposure of the
photoimageable compositions to actinic radiation a phototropic
response is elicited.
[0005] Laser imaging has lately been attracting attention as a
high-speed and efficient marking method and is already put to
practical use in some industries. Many laser imaging techniques
involve irradiating only necessary areas of substrates with laser
light to denature or remove the irradiated area or irradiating a
coated substrate with laser light to remove the irradiated coating
layer thereby making a contrast between the irradiated area (imaged
area) and the non-irradiated area (background).
[0006] Using a laser to mark an article such as a semiconductor
chip is a fast and economical means of marking. There are, however,
certain disadvantages associated with state-of-the art laser
imaging techniques that burn the surface to achieve a desired mark.
For example, a mark burned in a surface by a laser may only be
visible at select angles of incidence to a light source. Further,
oils or other contaminants deposited on the article surface
subsequent to marking may blur or even obscure the laser mark.
Additionally, because the laser actually burns the surface of the
work piece, for bare die imaging, the associated burning may damage
any underlying structures or internal circuitry or by increasing
internal die temperature beyond acceptable limits. Moreover, where
the manufactured part is not produced of a laser reactive material,
a laser reactive coating applied to the surface of a component adds
expense and may take hours to cure.
[0007] Alternatively, laser projectors may be used to project
images onto surfaces. They are used to assist in the positioning of
work pieces on work surfaces. Some systems have been designed to
project three-dimensional images onto contoured surfaces rather
than flat surfaces. The projected images are used as patterns for
manufacturing products and to scan an image of the desired location
of a ply on previously placed plies. Examples of such uses are in
the manufacturing of leather products, roof trusses, and airplane
fuselages. Laser projectors are also used for locating templates or
paint masks during the painting of aircraft.
[0008] The use of scanned laser images to provide an indication of
where to place or align work piece parts, for drilling holes, for
forming an outline for painting a logo or picture, or aligning
segments of a marine vessel for gluing requires extreme accuracy in
calibrating the position of the laser projector relative to the
work surface. Typically six reference points are required for
sufficient accuracy to align work piece parts. Reflectors or
sensors are positioned in an approximate area where the ply is to
be placed. Since the points are at fixed locations relative to the
work and the laser, the laser also knows where it is relative to
the work. Typically, workers hand mark the place where the laser
beam image contacts the work piece with a marker or masking tape to
define the laser image. Such methods are tedious, and the workers'
hands may block the laser image disrupting the alignment beam to
the work piece. Accordingly, misalignment may occur.
[0009] Another problem associated with laser imaging is the
potential for opthalmological damage to the workers. Many lasers
used in marking may cause retinal damage to workers. Generally,
lasers, which generate energy exceeding 5 mW present hazards to
workers.
[0010] The inventors of the present invention have addressed the
problems associated with laser imaging by formulating compositions
which change color or shade by applying energy at powers of 5 mW or
less. Applications of such compositions eliminate the problems
associated with hand marking the places on a work piece where the
laser is directed and at the same time the use of a low power laser
eliminates the potential of opthalmological damage to workers.
[0011] In the applications of such compositions a color or shade
contrast is desired between the compositions and the work pieces
such that the workers may readily distinguish between the work
piece and the colored compositions to accurately modify the work
piece. The greater the color or shade contrast from the work piece
the easier it is for the workers to see the markings and more
rapidly and accurately modify the work piece. This is especially
important in assembly line operations where speed and accuracy are
critical to optimum product output. However, when a work piece is
of a similar color or shade as the color or shade of the markings,
workers find it difficult to accurately locate the markings on the
work piece. Accordingly, speed and accuracy are compromised, and
the efficiency of the manufacturing process is hindered.
[0012] The imaging compositions are not always applied to a bare
work piece. Often the imaging compositions are applied to work
pieces which have been previously treated or coated by various
types of chemical compositions. The inventors have discovered that
such coatings may cause dye compounds of the imaging compositions
to leach out into the coatings and cause undesired chemical
reactions which result in the formation of unwanted color changes.
Such color changes readily interfere with the desired color or
shade contrast between the marks on the imaging compositions and
the work pieces and workers are unable to perform their task. For
example, airplane bodies are often coated with an epoxy primer
material prior to applying paint or any additional coatings to the
bodies. When the imaging compositions are applied to such airplane
bodies, the dyes in the imaging compositions leach into the epoxy
primers and turn the airplane bodies an undesired red.
[0013] Accordingly, there is still a need for improved imaging
compositions for marking a work piece.
[0014] Imaging compositions include a first component including one
or more opacifying compounds, and a second component including one
or more sensitizers. The first component of the imaging
compositions inhibits the leaching of compounds from the second
component into coatings on work pieces on which the imaging
compositions are applied. The first component also provides a color
or shade contrast between the second component of the imaging
compositions and the work pieces. The second component may be
imaged by exposing the compositions to energy levels of 5 mW or
less.
[0015] In another aspect the imaging compositions include a first
component including one or more opacifying compounds and one or
more release agents, and a second component including one or more
sensitizers and one or more release agents.
[0016] The imaging compositions also may include one or more film
forming polymers, adhesives, plasticizers, flow agents, chain
transfer agents, organic acids, accelerators, surfactants,
thickeners, monomers, rheology modifiers, release agents, diluents
and other optional components to tailor the compositions for a
particular imaging method and work piece. The imaging compositions
may be applied to a work piece to form an image on the work piece
for workers to modify the work piece to make an article.
[0017] In a further aspect methods of imaging include providing a
first component of a composition including one or more opacifying
compounds; applying the first component of the composition to a
work piece; providing a second component of the composition
including one or more sensitizers; applying the second component of
the composition on the first component; exposing the composition to
energy at powers of 5 mW or less to affect a color or shade change
in the second component; and executing a task on the work piece as
directed by the color or shade change of the second component of
the composition to modify the work piece. The energy may be applied
selectively to form an imaged pattern on the work piece.
[0018] The image may be used as a mark to drill holes for
fasteners, to join parts together, to align segments of parts, and
to form an outline for making a logo or picture on articles such as
terrestrial vehicles, aeronautical ships, marine vessels,
terrestrial structures and textiles. Since the compositions may be
promptly applied to the work piece and the image promptly formed by
application of energy at intensities of 5 mW or less to create a
color or shade contrast, workers no longer need to be adjacent the
work piece to mark laser beam images with a hand-held marker or
tape in the fabrication of articles. Accordingly, the problems of
blocking light caused by the movement of workers hands and the
slower and tedious process of applying marks by workers using a
hand-held marker or tape is eliminated. Further, the low powers of
energy, which are used to cause the color or shade change,
eliminate or at least reduce the potential for opthalmological
damage to workers.
[0019] The imaging compositions may be applied to the work piece by
methods which include, but are not limited to, spray coating,
brushing, roller coating, ink jetting, dipping and immersion.
Energy sources for applying a sufficient amount of energy to create
the color or shade change include laser, infrared and ultraviolet
light generating devices and apparatus.
[0020] In one aspect the imaging compositions are peelable from the
work piece avoiding the use of undesirable solvents or developers.
Such solvents and developers may be carcinogenic and potentially
contaminate the environment, thus costly waste treatment is used to
reduce environmental pollution. Accordingly, the imaging
compositions provide for more efficient manufacturing than many
conventional alignment and imaging processes, and also may reduce
the amount of waste treatment.
[0021] As used throughout this specification, the following
abbreviations have the following meaning, unless the context
indicates otherwise: .degree. C.=degrees Centigarde; IR=infrared;
UV=ultraviolet; gm=gram; mg=milligram; L=liter; mL=milliliter; wt
%=weight percent; erg=1 dyne cm=10.sup.-7 joules; J=joule;
mJ=millijoule; nm=nanometer=10.sup.-9 meters; cm=centimeters;
mm=millimeters; W=watt=1 joule/second; and mW=milliwatt;
ns=nanosecond; .mu.sec=microsecond; Hz=hertz; .mu.m=microns; and
T.sub.g=glass transition temperature; .DELTA.=delta=mathematical
symbol designating a change in a variable.
[0022] The terms "polymer" and "copolymer" are used interchangeably
throughout this specification. "Actinic radiation" means radiation
from light that produces a chemical change. "Photofugitive
response" means that the application of energy causes a colored
material to fade or become lighter. "Phototropic response" means
that the application of energy causes material to darken. "Changing
shade" means that the color fades, or becomes darker.
"(Meth)acrylate" includes both methacrylate and acrylate, and
"(meth)acrylic acid" includes both methacrylic acid and acrylic
acid. "Diluent" means a carrier or vehicle, such as solvents or
solid fillers. "Opacity" means the property of being impervious to
light rays, i.e. not transparent or translucent. "Opaque" means
nontransparent and nontranslucent. "Translucent" means
semitransparent. "Transparent" means a passage of rays of the
visible spectrum.
[0023] Unless otherwise noted, all percentages are by weight and
are based on dry weight or solvent free weight. All numerical
ranges are inclusive and combinable in any order, except where it
is logical that such numerical ranges are constrained to add up to
100%.
[0024] Imaging compositions include a first component including one
or more opacifying compounds, and a second component including one
or more sensitizers. The first component of the imaging
compositions inhibits leaching of compounds from the second
component into coatings on work pieces on which the imaging
compositions are applied. The first component also provides a color
or shade contrast between the second component of the imaging
compositions and the work pieces. Further, including one or more
opacifying compounds in the first component, increases the rate of
color or shade change of the second component. The second component
may be imaged by exposing the compositions to energy levels of 5 mW
or less.
[0025] The first component including one or more opacifying
compounds is applied to the work piece. The first component is
dried then the second component including the one or more
sensitizers is applied on the dried first component. The second
component is then dried and the imaging composition is then imaged
with energy at 5 mW or less. Workers then modify the work piece
based on the imaged composition. The composition may be removed
from the work piece by any suitable method. Typically, the
composition is peeled from the work piece.
[0026] Often a work piece may be sufficiently dark in color or
shade such as to reduce the contrast between the imaged second
component and the work piece, thus compromising accurate
modification of the work piece. Including opacifying compounds in
the second component causes a reflection of a portion of the
applied energy, thus requiring longer exposure times to affect the
color or shade change. By including the opacifying compounds in the
first component, faster color and shade changes are achieved in the
second component.
[0027] The imaging compositions may be applied to a work piece by
any suitable method including, but not limited to, spraying,
brushing, roller coating, ink jetting, dipping and immersion. The
compositions may be removed from the work piece by any suitable
method such as with a developer, stripper or by peeling the
unwanted portions from work pieces. Typically, the compositions are
peeled by hand or by using a suitable device or apparatus known in
the art such as a knife or scrapper. Peelable compositions avoid
the use of environmentally hazardous solvents and developers, and
reduce the amount of waste.
[0028] Any suitable opacifying compound which provides a desired
color or shade contrast between the second component and the work
piece may be used. Such compounds are used in the first component
in amounts of 1 wt % to 80 wt %, or such as from 5 wt % to 50 wt %,
or such as 10 wt % to 20 wt %.
[0029] Opacifying compounds include, but are not limited to,
pigments (inorganic and organic), metal salts, silica, silicates
and clays. Organic pigments include, but are not limited to,
indigo, phthalocyanine, para red and flavanoids such as red,
yellow, blue, orange and ivory colors. Inorganic pigments include,
but are not limited to, oxides such as titanium dioxide, zirconium
oxide, ceric oxide, antimony trioxide, arsenic pentoxide, aluminum
oxide, zinc oxide, cobalt oxide, cadmium oxide, chromium oxide,
magnesium oxide, iron oxide and lead oxide. Also, mixed phase
titanates and mixed phase oxides may be included. Metal salts
include, but are not limited to, sulfides, sulfates, carbonates and
hydroxides. Typically, the opacifying compounds are inorganic
pigments. More typically, the opacifying compounds are inorganic
pigments such as titanium dioxide, aluminum oxide, zinc oxide and
silicates. Most typically the opacifying compounds are inorganic
pigments such as titanium dioxide, aluminum oxide and zinc oxide.
The opacifying compounds have an average size of 0.01 .mu.m to 10
.mu.m, or such as from 0.5 .mu.m to 5 .mu.m, or such as from 1
.mu.m to 3 .mu.m.
[0030] In addition to the opacifying agents, the first component
may include, but is not limited to, one or more additives such as
film forming polymers, diluents, thickeners, rheology modifiers,
adhesives, plasticizers, flow agents, organic acids, surfactants
and release agents to tailor the first component for compatibility
with the second component and the work piece. Typically, such
additives are included in the first component as in the second
component.
[0031] Film forming polymers are included in the first component to
function as binders. Any film forming polymer may be employed in
the first component provided the polymers do not cause the
opacifying agents to agglomerate or concentrate out of the first
component. Suitable film forming polymers for the first component
include, but are not limited to, the film forming polymers
described below for the second component. The film forming polymers
are included in the first component in amounts from 10 wt % to 95
wt %, or such as from 15 wt % to 80 wt %, or such as from 25 wt %
to 65 wt % of the first component.
[0032] Optionally, an adhesive may be included in the first
component. The adhesive may be a permanent adhesive, a
semi-permanent, a repositionable adhesive, a releasable adhesive,
or freezer category adhesive. Many such adhesives may be classified
as hot-melt, hot-melt pressure sensitive, and pressure sensitive
adhesives. Typically, the releasable adhesives are pressure
sensitive adhesives. Typically, releasable, pressure sensitive
adhesives are used. Such releasable, pressure sensitive adhesives
include, but are not limited to, acrylics, polyurethanes,
poly-alpha-olefins, silicones, combinations of acrylate pressure
sensitive adhesives and thermoplastic elastomer-based pressure
sensitive adhesives, and tackified and natural rubbers. Adhesives
may be included in the first component in amounts of from 0.5 wt %
to 15 wt %, or such as from 5 wt % to 10 wt % of the first
component.
[0033] One or more amphoteric surfactants may be included in the
first component to act as release agents such that the imaging
compositions may be readily peeled from a work piece. Suitable
amphoteric surfactants include those described below for the second
component of the imaging compositions. The amphoteric surfactants
are included in the first component in the same amounts as in the
second component.
[0034] One or more diluents may be included in the first component.
Such diluents include, but are not limited to, water and organic
solvents. Examples of suitable organic solvents are described below
for the second component of the imaging compositions.
[0035] Sensitizers employed in the second component are compounds
which are activated by energy to change color or shade, or upon
activation cause one or more other compounds to change color or
shade. The second component includes one or more photosensitizers
activated by visible light energy at powers of 5 mW or less.
Generally, such sensitizers are included in amounts of from 0.005
wt % to 10 wt %, or such as from 0.05 wt % to 5 wt %, or such as
from 0.1 wt % to 1 wt % of the second component.
[0036] Sensitizers, which are activated in the visible range,
typically are activated at wavelengths of from above 300 nm to less
than 600 nm, or such as from 350 nm to 550 nm, or such as from 400
nm to 535 nm. Such sensitizers include, but are not limited to,
xanthene compounds and cyclopentanone based conjugated
compounds.
[0037] Suitable xanthene compounds include, but are not limited to,
compounds having the general formula: 1
[0038] where X is hydrogen, sodium ion, or potassium ion; Y is
hydrogen, sodium ion, potassium ion or --C.sub.2H.sub.5; R.sub.1 is
hydrogen, Cl.sup.-, Br.sup.-, or I.sup.-; R.sub.2 is hydrogen,
Cl.sup.-, Br.sup.-, or I.sup.-; R.sub.3 is hydrogen, Cl.sup.-,
Br.sup.-, I.sup.-, or --NO.sub.2; R.sub.4 is hydrogen, --NO.sub.2,
Cl.sup.-, Br.sup.-, or I.sup.-; R.sub.5 is hydrogen, Cl.sup.- or
Br.sup.-; R.sub.6 is hydrogen, Cl.sup.-, or Br.sup.-; R.sub.6 is
hydrogen, Cl.sup.-, or Br.sup.-; R.sub.7 is hydrogen, Cl.sup.-, or
Br.sup.-; and R.sub.8 is hydrogen, Cl.sup.-, or Br.sup.-.
[0039] Examples of such xanthene compounds are compounds such as
fluorescein and derivatives thereof such as the halogenated
xanthenes such as
2',4',5',7'-tetrabromo-3,4,5,6-tetrachlorofluorescein (phloxin B),
2',4',5',7'-tetraiodofluorescein (erythrosin, erythrosin B, or C.I.
Acid Red 51), 2',4',5',7'-tetraiodo-3,4,5,6-tetrachlorofluorescein
(Rose Bengal), 2',4',5',7',3,4,5,6-octabromofluorescein
(octabromofluorescein), 4,5,6,7-tetrabromoerythrosin,
4',5'-dichlorofluorescein, 2',7'-dichlorofluorescein,
4,5,6,7-tetrachlorofluorescein, 2',4',5',7'-tetrachlorofluorescein,
dibromofluorescein, Solvent Red 72, diiodofluorescein, eosin B,
eosin Y, ethyl eosin, and salts thereof. Typically, the salts are
alkali metal salts such as the sodium and potassium salts. Such
xanthene compounds typically are used in amounts of from 0.05 wt %
to 2 wt %, or such as from 0.25 wt % to 1 wt %, or such as from 0.1
wt % to 0.5 wt % of the composition.
[0040] Examples of suitable cyclopentanone based conjugated
compounds are cyclopentanone,
2,5-bis-[4-(diethylamino)phenyl]methylene]-, cyclopentanone,
2,5-bis[(2,3,6,7-tetrahydro-1H,5H-benzo[i,j]quinolizin-9--
yl)methylene]-, and cyclopentanone,
2,5-bis-[4-(diethyl-amino)-2-methylphe- nyl]methylene]-. Such
cyclopentanones may be prepared from cyclic ketones and tricyclic
aminoaldehydes by methods known in the art.
[0041] Examples of such suitable conjugated cyclopentanones have
the following formula: 2
[0042] where p and q independently are 0 or 1, r is 2 or 3; and
R.sub.9 is independently hydrogen, linear or branched
(C.sub.1-C.sub.10)aliphatic, or linear or branched
(C.sub.1-C.sub.10)alkoxy, typically R.sub.9 is independently
hydrogen, methyl or methoxy; R.sub.10 is independently hydrogen,
linear or branched (C.sub.1-C.sub.10)aliphatic,
(C.sub.5-C.sub.7)ring, such as an alicyclic ring, alkaryl, phenyl,
linear or branched (C.sub.1-C.sub.10)hydroxyalkyl, linear or
branched hydroxy terminated ether, such as
--(CH.sub.2).sub.v--O--(CHR.sub.20).sub.w--OH, where v is an
integer of from 2 to 4, w is an integer of from 1 to 4, and
R.sub.20 is hydrogen or methyl and carbons of each R.sub.10 may be
taken together to form a 5 to 7 membered ring with the nitrogen, or
a 5 to 7 membered ring with the nitrogen and with another
heteroatom chosen from oxygen, sulfur, and a second nitrogen. Such
sensitizers may be activated at powers of 5 mW or less.
[0043] Other sensitizers which are activated in the visible light
range include, but are not limited to, N-alkylamino aryl ketones
such as bis(9-julolidyl ketone),
bis-(N-ethyl-1,2,3,4-tetrahydro-6-quinolyl)keton- e and
p-methoxyphenyl-(N-ethyl-1,2,3,4-tetrahydro-6-quinolyl)ketone;
visible light absorbing dyes prepared by base catalyzed
condensation of an aldehyde or dimethinehemicyanine with the
corresponding ketone; visible light absorbing squarylium compounds;
1,3-dihydro-1-oxo-2H-indene derivatives; any of the coumarin based
dyes which include, but are not limited to, ketocoumarin, and
3,3'-carbonyl bis(7-diethylaminocoumarin), coumarin 6, coumarin 7,
coumarin 99, coumarin 314 and dimethoxy coumarin 99; halogenated
titanocene compounds such as bis(eta.5-2,4-cyclopentadien-
-1-yl)-bis(2,6-difluro-3-(1H-pyrrol-1-yl)-phenyl) titanium; and
compounds derived from aryl ketones and
p-dialkylaminoarylaldehydes. Methods of making the foregoing
sensitizers are known in the art or disclosed in the literature.
Also, many are commercially available.
[0044] Optionally, the second component may include one or more
photosensitizers that are activated by UV light. Such sensitizers
which are activated by UV light are typically activated at
wavelengths of from above 10 nm to less than 300 nm, or such as
from 50 nm to 250 nm, or such as from 100 nm to 200 nm. Such UV
activated sensitizers include, but are not limited to, polymeric
sensitizers having a weight average molecular weight of from 10,000
to 300,000 such as polymers of
1-[4-(dimethylamino)phenyl]-1-(4-methoxyphenyl)-methanone,
1-[4-(dimethylamino)phenyl]-1-(4-hydroxyphenyl)-methanone and
1-[4-(dimethylamino)phenyl]-1-[4-(2-hydroxyethoxy)-phenyl]-methanone;
free bases of ketone imine dyestuffs; amino derivatives of
triarylmethane dyestuffs; amino derivatives of xanthene dyestuffs;
amino derivatives of acridine dyestuffs; methine dyestuffs; and
polymethine dyestuffs. Methods of preparing such compounds are
known in the art. Typically, such UV activated sensitizers are used
in amounts of from 0.05 wt % to 1 wt %, or such as from 0.1 wt % to
0.5 wt % of the second component.
[0045] Optionally, the second component may include one or more
photosensitizers that are activated by IR light. Such sensitizers
which are activated by IR light are typically activated at
wavelengths of from greater than 600 nm to less than 1,000 nm, or
such as from 700 nm to 900 nm, or such as from 750 nm to 850 nm.
Such IR activated sensitizers include, but are not limited to,
infrared squarylium dyes, and carbocyanine dyes. Such dyes are
known in the art and may be made by methods described in the
literature. Typically, such dyes are included in the compositions
in amounts of from 0.05 wt % to 3 wt %, or such as from 0.5 wt % to
2 wt %, or such as from 0.1wt % to 1 wt % of the second
component.
[0046] Photoreducing agents also may be used in the second
component. Compounds which may function as photoreducing agents
include, but are not limited to, one or more quinone compounds such
as pyrenequinones such as 1,6-pyrenequinone and 1,8-pyrenequinone;
9,10-anthrquinone, 1-chloroanthraquinone, 2-chloro-anthraquinone,
2-methylanthrquinone, 2-ethylanthraquinone,
2-tert-butylanthraquinone, octamethylanthraquinone,
1,4-naphthoquinone, 9,10-phenanthrenequinone,
1,2-benzaanthrquinone, 2,3-benzanthraquinone,
2-methyl-1,4-naphthoquinone, 2,3-dichloronaphthoquinone,
1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, sodium salt
of anthraquinone alpha-sulfonic acid,
3-chloro-2-methylanthraquinone, retenequinone,
7,8,9,10-tetrahydronaphthacenequinone, and
1,2,3,4-tetrahydrobenz(a)anthr- acene-7,12-dione.
[0047] Other compounds which may function as photoreducing agents
include, but are not limited to, acyl esters of triethanolamines
having a formula:
N(CH.sub.2CH.sub.2OC(O)--R.sub.11).sub.3 (III)
[0048] where R.sub.11 is alkyl of 1 to 4 carbon atoms, and 0 to 99%
of a C.sub.1 to C.sub.4 alkyl ester of nitrilotriacetic acid or of
3,3',3"-nitrilotripropionic acid. Examples of such acyl esters of
triethanolamine are triethanolamine triacetate and
dibenzylethanolamine acetate.
[0049] One or more photoreducing agent may be used in the second
component to provide the desired color or shade change. Typically,
one or more quinone is used with one or more acyl ester of
triethanolamine to provide the desired reducing agent function.
Photoreducing agents may be used in the compositions in amounts of
from 0.05 wt % to 50 wt %, or such as from 5 wt % to 40 wt %, or
such as 20 wt % to 35 wt %.
[0050] Suitable color formers in the second component include, but
are not limited to, leuco-type compounds. Such leuco-type compounds
include, but are not limited to, aminotriarylmethanes,
aminoxanthenes, aminothioxanthenes, amino-9,10-dihydroacridines,
aminophenoxazines, aminophenothiazines, aminodihydrophenazines,
antinodiphenylmethines, leuco indamines, aminohydrocinnamic acids
such as cyanoethanes and leuco methines, hydrazines, leuco indigoid
dyes, amino-2,3-dihydroanthraquinone- s, tetrahalo-p,p'-biphenols,
2(p-hydroxyphenyl)-4,5-diphenylimidazoles, and phenethylanilines.
Typically, the aminotriarylmethane leuco dyes, such as the o-methyl
substituted dyes, are used. The o-methyl substitution is believed
to make the structure non-planar and more resistant to oxidation
than many other leuco-type dyes. Color formers are included in
amounts of from 0.1 wt % to 5 wt %, or such as from 0.25 wt % to 3
wt %, or such as from 0.5 wt % to 2 wt % of the second
component.
[0051] Oxidizing agents also may be included in the second
component to influence the color or shade change. Typically such
oxidizing agents are used in combination with one or more color
formers. Compounds, which may function as oxidizing agents include,
but are not limited to, hexaarylbiimidazole compounds such as
2,4,5,2',4',5'-hexaphenylbiimidazol- e,
2,2',5-tris(2-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4,5-diphenylbiimida-
zole (and isomers),
2,2'-bis(2-ethoxyphenyl)-4,4',5,5',-tetraphenyl-1,1'-b-
i-1H-mimidazole, and
2,2'-di-1-naphthalenyl-4,4',5,5'-tetraphenyl-1'-bi-1H- -imidazole.
Other suitable compounds include, but are not limited to,
halogenated compounds with a bond dissociation energy to produce a
first halogen as a free radical of not less than 40 kilocalories
per mole, and having not more than one hydrogen attached thereto; a
sulfonyl halide having a formula: R'--SO.sub.2--X' where R' is an
alkyl, alkenyl, cycloalkyl, aryl, alkaryl, or aralkyl and X' is
chlorine or bromine; a sulfenyl halide of the formula: R"--S--X"
where R" and X" have the same meaning as R' and X' above; tetraaryl
hydrazines, benzothiazolyl disulfides, polymetharylaldehydes,
alkylidene 2,5-cyclohexadien-1-ones, azobenzyls, nitrosos, alkyl
(T1), peroxides, and haloamines. Typical examples of suitable
halogenated sulfones include tribromomethyl aryl sulfones such as
tribromomethylphenyl sulfone, tribromomethyl p-tolyl sulfone,
tribromomethyl 4-chlorophenyl sulfone, tribromomethyl 4-bromophenyl
sulfone, and tribromomethyl phenyl sulfone. Such compounds are
included in the second component in amounts of from 0.25 wt % to 10
wt %, or such as from 0.5 wt % to 5 wt %, or such as from 1 wt % to
3 wt %. Methods are known in the art for preparing the compounds
and many are commercially available.
[0052] Film forming polymers may be included in the second
component to function as binders. Any film forming binder may be
employed provided that the film forming polymers do not adversely
interfere with the desired color or shade change, and have a
T.sub.g of from -60.degree. C. to greater than 80.degree. C. or
such as from -60.degree. C. to 80.degree. C., or such as from
greater than -60.degree. C. to greater than 40.degree. C., or such
as from 0.degree. C. to 35.degree. C. The film forming polymers are
included in amounts of from 10 wt % to 90 wt %, or such as from 15
wt % to 70 wt %, or such as from 25 wt % to 60 wt %. Typically, the
film forming polymers are derived from a mixture of acid functional
monomers and non-acid functional monomers. Suitable acid functional
monomers include, but are not limited to, (meth)acrylic acid,
maleic acid, fumaric acid, citraconic acid,
2-acrylamido-2-methylpropanes- ulfonic acid, 2-hydroxyethyl acrylol
phosphate, 2-hydroxypropyl acrylol phosphate, and
2-hydroxy-alpha-acrylol phosphate.
[0053] Suitable non-acid functional monomers include, but are not
limited to, esters of (meth)acrylic acid such as methyl acrylate,
2-ethyl hexyl acrylate, n-butyl acrylate, n-hexyl acrylate, methyl
methacrylate, hydroxyl ethyl acrylate, butyl methacrylate, octyl
acrylate, 2-ethoxy ethyl methacrylate, t-butyl acrylate,
1,5-pentanediol diacrylate, N,N-diethylaminoethyl acrylate,
ethylene glycol diacrylate, 1,3-propanediol diacrylate,
decamethylene glycol diacrylate, decamethylene glycol
dimethacrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethyylol
propane diacrylate, glycerol diacrylate, tripropylene glycol
diacrylate, glycerol triacrylate, 2,2-di(p-hydroxyphenyl)-propane
dimethacrylate, triethylene glycol diacrylate,
polyoxyethyl-2,2-di(p-hydr- oxyphenyl)-propane dimethacrylate,
triethylene glycol dimethacrylate, polyoxypropyltrimethylol propane
triacrylate, ethylene glycol dimethacrylate, butylenes glycol
dimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol
trimethacrylate, 2,2,4-trimethyl-1,3-pentanediol dimethacrylate,
pentaerythritol trimethacrylate, 1-phenyl
ethylene-1,2-dimethacrylate, pentaerythritol tetramethacrylate,
trimethylol propane trimethacrylate, 1,5-pentanediol
dimethacrylate; styrene and substituted styrene such as 2-methyl
styrene and vinyl toluene and vinyl esters such as vinyl acrylate
and vinyl methacrylate.
[0054] When the film forming polymer has a T.sub.g of -60.degree.
C. to 0.degree. C., the film forming polymers typically have from
0.1 wt % to 6 wt % of the total weight of the polymer at least one
carboxy functional monomer, or such as from 0.5 wt % to 6 wt %, or
such as from 1 wt % to 5 wt % of at least one carboxy functional
monomer. When the film forming polymer has a T.sub.g of greater
than 0.degree. C. to greater than 80.degree. C., and one or more
bases are included in the composition to maintain a pH range of 3
to 11 or such as from 8 to 11, the polymer may optionally include,
as polymerized units, carboxy functional monomers in amounts of
from 0.1 wt % to 6 wt %, based on the total weight of the dry film
forming polymer, or such as from 0.5 wt % to 6 wt %, or such as
from 0.1 wt % to 5 wt % of the total weight of the dry film forming
polymer.
[0055] Other suitable polymers include, but are not limited to,
nonionic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone,
hydroxyl-ethylcellulose, and hydroxyethylpropyl methylcellulose.
Also polymers such as polyvinyl acetate may be used.
[0056] Amphoteric surfactants may be included in the second
component to function as release agents such that the compositions
may be peeled from a work piece. Such surfactants also stabilize
particles of the polymers during and after aqueous emulsion
polymerization, or other dispersion polymerizations. Suitable
amphoteric surfactants are those which have weakly acidic
functionalities such as carboxy functionalities, and have
isoelectric points of from pH 3 to pH 8. Such amphoteric
surfactants may be included in the second component in amounts of
from 0.1 wt % to 6 wt %, or such as from 0.25 wt % to 5 wt %, or
such as from 0.5 wt % to 4 wt % of the film forming binder polymer.
Such amphoteric surfactants include, but are not limited to, amino
carboxylic acids, amphoteric imidazoline derivatives, betaine,
fluorocarbon and siloxane versions thereof, macromolecular
amphoteric surfactants and mixtures thereof.
[0057] Any of the aminocarboxylic acids may have carboxy moieties
present in either protonated form or in carboxylate form. Where
more than one carboxy group is present on a molecule, those carboxy
groups may all be in protonated form, in carboxylate form, or they
may be present as some mixture of protonated and carboxylate forms.
Furthermore, the ratio of protonated to unprotonated carboxy
moieties may vary from one molecule to another, otherwise
identical, molecule in a given system. Cations present as counter
ions for the carboxylate moieties include cations of lithium,
sodium, potassium, amines (i.e., ammonium cations derived from
protonation or other quaternary substitution of amines), zinc,
zirconium, calcium, magnesium, and aluminum. Any of the
aminocarboxylic acids may have amino moieties present in either
protonated (ammonium) or free amine form (i.e., as deprotonated
primary, secondary, or tertiary amine). Where more than one amino
group is present on a molecule, those amino groups may all be in
protonated form, in free amine form, or they may be present as some
mixture of protonated and free amine forms. Again, the ratio of
protonated to unprotonated amine moieties may vary from one
molecule to another, otherwise identical, molecule in a given
system. Anions present as counter ions for the ammonium moieties
include chloride, bromide, sulfate, carbonate, hydroxide, formate,
acetate, propionate and other carboxylate anions.
[0058] Suitable aminocarboxylic acids include, but are not limited
to: .alpha.-aminocarboxylic acids having the general formula
R.sub.12--NH--CH.sub.2COOH, where R.sub.12.dbd.C.sub.4-C.sub.20
linear or branched, alkyl, alkenyl, or fluoro or silicone
functional hydrophobe group; and .beta.-aminocarboxylic acids
having the general structures: R.sub.12--NH--CH.sub.2CH.sub.2COOH
and R.sub.12N(CH.sub.2CH.sub.2COOH).su- b.2, where
R.sub.12.dbd.C.sub.4-C.sub.20 linear or branched, alkyl, alkenyl,
or fluoro or silicone functional hydrophobe group,
.beta.-aminocarboxylic acids are available from Henkel Corporation,
King of Prussia, Pa., under the name DERIPHAT.TM.. Unless otherwise
stated, the DERIPHAT.TM. ampholytes have the general formula
R.sub.13--NHCH.sub.2CH.sub.2COOH, where R.sub.13=residue of coconut
fatty acids, residue of tallow fatty acids, lauric acid, myristic
acid, oleic acid, palmitic acid, stearic acid, linoleic acid, other
C.sub.4-C.sub.20 linear or branched, alkyl, alkenyl, and mixtures
thereof DERIPHAT.TM. ampholytes useful in the present invention
include: sodium-N-coco-.beta.-aminopropionate (DERIPHAT.TM. 151,
flake 97% active); N-coco-.beta.-aminopropionic acid (DERPHAT.TM.
151C, 42% solution in water);
N-lauryl/myristyl-.beta.-aminopropionic acid (DERIPHAT.TM.
17.degree. C., 50% in water); disodium-N-tallow-.beta.-imin-
odipropionate, R.sub.14N(CH.sub.2CH.sub.2COONa).sub.2,
(DERIPHAT.TM. 154, flake 97% active);
disodium-N-lauryl-.beta.-iminodipropionate (DERIPHAT.TM. 160, flake
97% active); and partial sodium salt of
N-lauryl-.beta.-iminodipropionic acid,
R.sub.14N(CH.sub.2CH.sub.2COOH)(CH- .sub.2CH.sub.2COONa),
(DERIPHAT.TM. 16.degree. C., 30% in water). Useful
polyaminocarboxylic acids include
R.sub.14C(.dbd.O)NHC.sub.2H.sub.4(NHC.s-
ub.2H.sub.4).sub.yNHCH.sub.2COOH and R.sub.14-substituted
ethylenediaminetetraacetic acid (EDTA), where
R.sub.14.dbd.C.sub.4-C.sub.- 20 linear or branched, alkyl or
alkenyl, and y=0-3.
[0059] Amphoteric imidazoline derivatives useful include those
derived from variously substituted 2-alkyl-2-imidazolines and
2-alkenyl-2-imidazolines which have nitrogen atoms at the 1 and 3
positions of the five-membered ring and a double bond in the 2,3
position. The alkyl or alkenyl group may be a C.sub.4-C.sub.20
linear or branched chain. The amphoteric imidazoline derivatives
are produced via reactions in which the imidazoline ring opens
hydrolytically under conditions allowing further reaction with such
alkylating agents as sodium chloroacetate, methyl (meth)acrylate,
ethyl (meth)acrylate, and (meth)acrylic acid. Useful amphoteric
surfactants derived from the reaction of
1-(2-hydroxyethyl)-2-(R.sub.1)-2-imidazolines with acrylic acid or
acrylic acid esters, where R.sub.15=residue of coconut fatty acids,
are:
[0060] cocoamphopropionate,
R.sub.15--(.dbd.O)NHCH.sub.2CH.sub.2N(CH.sub.2-
CH.sub.2OH)(CH.sub.2CH.sub.2COONa);
[0061] cocoamphocarboxypropionic acid,
R.sub.15--C(.dbd.O)NHCH.sub.2CH.sub.2N(CH.sub.2CH.sub.2COOH)(CH.sub.2CH.su-
b.2CH.sub.2CH.sub.2COOH);
[0062] cocoamphocarboxypropionate,
R.sub.15--C(.dbd.O)NHCH.sub.2CH.sub.2N(CH.sub.2CH.sub.2COONa)(CH.sub.2CH.s-
ub.2CH.sub.2CH.sub.2COONa);
[0063] cocoamphoglycinate,
R.sub.15--(.dbd.O)NHCH.sub.2CH.sub.2N(CH2CH.sub-
.2OH)(CH.sub.2COONa); and
[0064] cocoamphocarboxyglycinate,
[R.sub.5--C(.dbd.O)NHCH.sub.2CH.sub.2N.sup.+(CH.sub.2CH.sub.2OH)(CH.sub.2C-
OONa).sub.2OH.sup.-.
[0065] Surface-active inner salts containing at least one
quaternary ammonium cation and at least one carboxy anion are
called betaines. The nomenclature for betaines derives from the
single compound (trimethylammonio)acetate which is called betaine
and exists as an inner salt. Betaines useful as amphoteric
surfactants in the claimed invention include compounds of the
general formulae: R.sub.16N.sup.+(CH.sub.3).sub.-
2CH.sub.2COO.sup.-;
R.sub.16CONHCH.sub.2CH.sub.2CH.sub.2N.sup.+(CH.sub.3).-
sub.2COO.sup.-; and
R.sub.16--O--CH.sub.2--N.sup.+(CH.sub.3).sub.2CH.sub.2- COO.sup.-,
where R.sub.16.dbd.C.sub.4-C.sub.20 linear or branched, alkyl,
alkenyl, or fluoro or silicone functional hydrophobe group.
Specific examples of betaines include N-dodecyl-N,N-dimethylglycine
and cocamidopropyl betaine and (MONATERIC.TM. CAB available from
Mona Industries).
[0066] Typically, when fluorocarbon substituents are attached to
amphoteric surfactants, those substituents are perfluoroalky
groups, branched or unbranched, having 6 to 18 carbon atoms.
However, these substituents may instead be partially fluorinated.
They may also bear aryl functionality. Examples of fluorocarbon
amphoteric surfactants include fluorinated alkyl FLUORAD.TM. FC100
and fluorinated alkyl ZONYL.TM. FSK, produced by 3M and Dupont,
respectively.
[0067] Typical siloxane functional amphoteric surfactants have, for
example, the structures: 3
[0068] wherein R.sub.17 represents an amphoteric moiety and m+n=3
to 50. An example is the polyalkyl betaine polysiloxane copolymer
ABIL.TM. B9950 available from Goldschmidt Chemical Corporation.
[0069] Macromolecular amphoteric surfactants useful in the claimed
invention include: proteins, protein hydrolysates, derivatives of
protein hydrolysates, starch derivatives, and synthetic amphoteric
oligomers and polymers. Of particular utility are those
macromolecular ampholytes bearing carboxy functionality.
[0070] Typically the imaging compositions are within a pH range of
from 3 to 11 or such as from 4 to 7. Optionally, a base may be
employed to maintain the desired pH. To assist in maintaining the
second component within a desired pH range, any suitable base may
be used. Examples of such bases include calcium carbonate, zinc
oxide, magnesium oxide, calcium hydroxide or mixtures thereof.
Bases are present in the imaging compositions in amounts of greater
than 0.2 moles/100 gm of polymer to 2 moles/100 gm of polymer, or
such as from 0.3 moles/100 gm of polymer to 1.75 moles/100 gm of
polymer, or such as from 0.4 moles/100 gm of polymer to 1.5
moles/100 gm of polymer.
[0071] Optionally, polyvalent metal cations may be included to form
an ionic bond with a carboxylic acid group on one or more of the
monomers which compose the polymers. Any suitable polyvalent cation
may be used which forms an ionic bond with the carboxylic acid
groups to achieve cross-linking. Such cations include, but are not
limited to, Mg.sup.2+, Sr.sup.2+, Ba.sup.2+, Ca.sup.2+, Zn.sup.2+,
Al.sup.3+, Zr.sup.4+ or mixtures thereof. Such polyvalent cations
are included in the imaging compositions in amounts of 0.001 to 0.1
moles/100 gm of dry polymer, or such as from 0.01 to 0.08 moles/100
gm of dry polymer, or such as from 0.02 to 0.05 moles/100 gm of dry
polymer.
[0072] When one or more bases containing polyvalent cations are
included in combination with another source of polyvalent cations,
the sum of the amounts of base and polyvalent metal cation is
greater than 0.2 to 2 moles/100 gm of polymer, or such as from 0.3
to 1.75 moles/100 gm of polymer, or such as from 0.4 to 1.5
moles/100 gm of polymer.
[0073] Optionally, antioxidants may be included in the second
component to stabilize the color or shade change to ambient
radiation. The antioxidants are believed to arrest the oxidation of
color formers when the compositions are exposed to ambient
radiation. Arresting the oxidation of the color formers inhibits
further color or shade change from ambient radiation. Accordingly,
a color or shade contrast between the portions of the composition
marked by exposure to low intensity energy, such as by a laser, and
the portions not exposed to the low intensity energy, but only to
ambient radiation, are maintained or stabilized. Any suitable
antioxidant which arrests the oxidation of color formers may be
used. Examples of such antioxidants are hindered phenols and
hindered amines.
[0074] Hindered phenols include one or two sterically bulky groups
bonded to the carbon atom or atoms contiguous to the hydroxyl
group-bonded carbon atom to sterically hinder the hydroxyl group.
Examples of such hindered phenols are
2,6-di-tert-butyl-4-methylphenol,
2,2'-methylene-bis(4-methyl-6-tertbutylphenol),
2,6-methylene-bis(2-hydro-
xy-3-tert-butyl-5-methyl-phenyl)4-methylphenol,
2,2'-methylene-bis(4-ethyl- -6-tert-butylphenol),
2,6-bis(2'-hydroxy-3'-tert-butyl-5'-methylbenzyl)4-m- ethyl-phenol,
2,4,4-trimethylphenyl-bis(2-hydroxy-3,5-dimethylphenyl)metha- ne,
2,2'-methylene-bis[4-methyl-6-(1-methylcyclohexyl)]phenol,
2,5-di-tert-butyl-4-methoxyphenol,
4,4'-butylidenebis(6-tert-butyl-3-meth- yl-phenol), and
1,1,3-tris(2-methyl-4-hydroxy-5-tertbutyl-phenyl)butane.
[0075] Hindered amines include one or two sterically bulky groups
bonded to the carbon atom or atoms adjacent to a nitrogen atom to
sterically hinder the nitrogen. The nitrogen itself may have bulky
groups bonded to it. Examples of suitable hindered amines include
2,2,6,6-tetraalkylpiperi- dine compounds including N-substituted
2,2,6,6-tetraalkylpiperidine compounds. Such compounds contain a
group having a formula: 4
[0076] where R.sub.18 hydrogen, (C.sub.1-C.sub.18)alkyl,
(C.sub.1-C.sub.6)hydroxyalkyl, cyanomethyl,
(C.sub.3-C.sub.8)alkenyl, (C.sub.3-C.sub.8)alkynyl,
(C.sub.7-C.sub.12)aralkyl which may be unsubstituted or substituted
in the alky moiety by hydroxyl, (C.sub.1-C.sub.8)alkanoyl or
(C.sub.3-C.sub.5)alkenoyl; and R.sub.19 is hydrogen or methyl.
[0077] The antioxidants may be micro-encapsulated in any suitable
microcapsule formulation and by any suitable micro-encapsulating
method. The microcapsule prevents mutual contact of the antioxidant
contained in the microcapsule with the other materials outside of
the microcapsule by the isolating action of the microcapsule wall
at room and storage temperatures. The microcapsules have increased
permeability of their contents upon application of sufficient heat
or pressure. Permeation may be controlled by selecting suitable
microcapsule wall materials and microcapsule core materials.
Examples of suitable wall materials include polyurethanes,
polyureas, polyamides, polyesters, polycarbonates and combinations
thereof. Typically, polyurethanes and polyureas are used to make
the microcapsule wall.
[0078] The microcapsules may be formed by emulsifying the core
material containing the antioxidant and subsequently forming a wall
around drops of the emulsified core material. In preparation of the
microcapsule, a reactant which forms the wall is added to the
inside or outside of the drops. Specific procedures for forming
microcapsules are described, for example, in U.S. Pat. No.
3,726,804, U.S. Pat. No. 3,796,696, U.S. Pat. No. 4,962,009, and
U.S. Pat. No. 5,244,769.
[0079] Solvents suitable for forming the emulsion with the
antioxidant include, but are not limited to, organic compounds such
as phosphoric acid esters, phthalic acid esters, (meth)acrylic acid
esters, other carboxylic acid esters, fatty acid amides, alkylated
biphenyls, alkylated terphenyls, alkylated naphthalenes,
diarylethanes, chlorinated paraffins, and mixtures thereof.
[0080] Auxiliary solvents may be added to the above-described
organic solvents. Such solvents include, but are not limited to,
ethyl acetate, isopropyl acetate, butyl acetate, methylene
chloride, cyclohexanone, and mixtures thereof.
[0081] Protective colloids or surface active agents may be added to
the aqueous phase for stabilizing the emulsified drops.
Water-soluble polymers may be used as the protective colloids. An
example of a suitable water-soluble polymer is carboxyl-modified
polyvinyl alcohol.
[0082] The size of the microcapsules may vary in size. Typically,
the microcapsules have an average diameter of 0.5 .mu.m to 15
.mu.m, or such as from 0.75 .mu.m to 10 .mu.m, or such as from 1
.mu.m to 5 .mu.m.
[0083] Optionally, one or more chain transfer agents may be used in
the second component. Such chain transfer agents function as
accelerators. Chain transfer agents or accelerators increase the
rate at which the color or shade change occurs after exposure of
energy. Any compound which accelerates the rate of color or shade
change may be used. Accelerators may be included in the second
component in amounts of from 0.01 wt % to 25 wt %, or such as from
0.5 wt % to 10 wt %. Suitable accelerators include, but are not
limited to, onium salts, and amines.
[0084] Suitable onium salts include, but are not limited to, onium
salts in which the onium cation is iodonium or sulfonium such as
onium salts of arylsulfonyloxybenzenesulfonate anions, phosphonium,
oxysulfoxonium, oxysulfonium, sulfoxonium, ammonium, diazonium,
selononium, arsonium, and N-substituted N-heterocyclic onium in
which N is substituted with a substituted or unsubstituted
saturated or unsaturated alkyl or aryl group.
[0085] The anion of the onium salts may be, for example, chloride,
or a non-nucleophilic anion such as tetrafluoroborate,
hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate,
triflate, tetrakis-(pentafluorophosphate) borate, pentafluoroethyl
sulfonate, p-methyl-benzyl sulfonate, ethylsulfonate,
trifluoromethyl acetate and pentafluoroethyl acetate.
[0086] Examples of typical onium salts are diphenyl iodonium
chloride, diphenyliodonium hexafluorophosphate, diphenyl iodonium
hexafluoroantimonate, 4,4'-dicumyliodonium chloride,
dicumyliodonium hexafluorophosphate,
N-methoxy-a-picolinium-p-toluene sulfonate,
4-methoxybenzene-diazonium tetrafluoroborate,
4,4'-bis-dodecylphenyliodon- ium-hexafluoro phosphate,
2-cyanoethyl-triphenylphosphonium chloride,
bis-[4-diphenylsulfonionphenyl]sulfide-bis-hexafluoro phosphate,
bis-4-dodecylphenyliodonium hexafluoroantimonate and
triphenylsulfonium hexafluoroantimonate.
[0087] Suitable amines include, but are not limited to primary,
secondary and tertiary amines such as methylamine, diethylamine,
triethylamine, heterocyclic amines such as pyridine and piperidine,
aromatic amines such as aniline and n-phenyl glycine, quaternary
ammonium halides such as tetraethylammonium fluoride, and
quaternary ammonium hydroxides such as tetraethylammonium
hydroxide. The triethanolamines of formula III also have
accelerator activity.
[0088] Plasticizers also may be included in the second component.
Any suitable plasticizer may be employed. Plasticizers may be
included in amounts of from 0.5 wt % to 15 wt %, or such as from 1
wt % to 10 wt % of the second component. Suitable plasticizers
include, but are not limited to, phthalate esters such as
dibutylphthalate, diheptylphthalate, dioctylphthalate and
diallylphthalate, glycols such as polyethylene glycol and
polypropylene glycol, glycol esters such as triethylene glycol
diacetate, tetraethylene glycol diacetate, and dipropylene glycol
dibenzoate, phosphate esters such as tricresylphosphate,
triphenylphosphate, amides such as p-toluenesulfoneamide,
benzenesulfoneamide, N-n-butylacetoneamide, aliphatic dibasic acid
esters such as diisobutyl-adipate, dioctyladipate,
dimethylsebacate, dioctylazelate, dibutylmalate, triethylcitrate,
tri-n-butylacetylcitrate, butyl-laurate,
dioctyl-4,5-diepoxycyclohexane-1,2-dicarboxylate, and glycerine
triacetylesters.
[0089] One or more flow agents also may be included in the second
component. Flow agents may be included in amounts of from 0.05 wt %
to 5 wt % or such as from 0.1 wt % to 2 wt % of the second
component. Suitable flow agents include, but are not limited to,
copolymers of alkylacrylates. An example of such alkylacrylates is
a copolymer of ethyl acrylate and 2-ethylhexyl acrylate.
[0090] Optionally, one or more organic acids may be employed in the
second component. Organic acids may be used in amounts of from 0.01
wt % to 5 wt %, or such as from 0.5 wt % to 2 wt %. Suitable
organic acids include, but are not limited to, formic acid, acetic
acid, propionic acid, butyric acid, valeric acid, caproic acid,
caprylic acid, capric acid, lauric acid, phenylacetic acid, benzoic
acid, phthalic acid, isophthalic acid, terephthalic acid, adipic
acid, 2-ethylhexanoic acid, isobutyric acid, 2-methylbutyric acid,
2-propylheptanoic acid, 2-phenylpropionic acid,
2-(p-isobutylphenyl)propionic acid, and
2-(6-methoxy-2-naphthyl)propionic acid.
[0091] Optionally, one or more non-ionic and ionic surfactants may
be used. Surfactants may be included in the compositions in amounts
of from 0.5 wt % to 10 wt %, or such as from 1 wt % to 5 wt % of
the component. Suitable non-ionic surfactants include, but are not
limited to, polyethylene oxide ethers, derivatives of polyethylene
oxides, aromatic ethoxylates, acetylenic ethylene oxides and block
copolymers of ethylene oxide and propylene oxide. Suitable ionic
surfactants include, but are not limited to, alkali metal, alkaline
earth metal, ammonium, and alkanol ammonium salts of alkyl
sulfates, alkyl ethoxy sulfates, and alkyl benzene sulfonates.
[0092] Thickeners may be included in conventional amounts. Any
suitable thickener may be incorporated in the components.
Typically, thickeners range from 0.05 wt % to 10 wt %, or such as
from 1 wt % to 5 wt %. Suitable thickeners include, but are not
limited to, low molecular weight polyurethanes such as having at
least three hydrophobic groups interconnected by hydrophilic
polyether groups. The molecular weight of such thickeners ranges
from 10,000 to 200,000. Other suitable thickeners include
hydrophobically modified alkali soluble emulsions, hydrophobically
modified hydroxyethyl cellulose and hydrophobically modified
polyacrylamides.
[0093] Rheology modifiers may be included in the components in
conventional amounts. Typically rheology modifiers are used in
amounts of from 0.5 wt % to 20 wt %, or such as from 5 wt % to 15
wt %. Rheology modifiers include, but are not limited to, vinyl
aromatic polymers and acrylic polymers.
[0094] Diluents may be included to provide a vehicle or carrier for
the components. Diluents are added as needed. Solid diluents or
fillers are typically added in amounts to bring the dry weight of
the components to 100 wt %. Solid diluents include, but are not
limited to, celluloses. Liquid diluents or solvents are employed to
make solutions, suspensions, dispersions or emulsions of the
components. The solvents may be aqueous or organic, or mixtures
thereof. Organic solvents include, but are not limited to, alcohols
such as methyl, ethyl and isopropyl alcohol, diisopropyl ether,
diethylene glycol dimethyl ether, 1,4-dioxane, terahydrofuran or
1,2-dimethoxy propane, and ester such as butyrolactone, ethylene
glycol carbonate and propylene glycol carbonate, an ether ester
such as methoxyethyl acetate, ethoxyethyl acetate,
1-methoxypropyl-2-acetate, 2-methoxypropyl-1-acetate,
1-ethoxypropyl-2-acetate and 2-ethoxypropyl-1-acetate, ketones such
as acetone and methylethyl ketone, nitriles such as acetonitrile,
propionitrile and methoxypropionitrile, sulfones such as sulfolan,
dimethylsulfone and diethylsulfone, and phosphoric acid esters such
as trimethyl phosphate and triethyl phosphate. Solvents also
include coalescing solvents such as ethers. Examples of such ethers
include ethylene glycol phenyl ether and tripropylene glycol
n-butyl ether.
[0095] Additional optional additives which may be included in the
components include, but are not limited to, defoaming agents,
coalescing monomers, preservatives and mold inhibitors. They are
included in conventional amounts.
[0096] The first and second components of the imaging compositions
may be prepared by any suitable method. One method is to solubilize
or disperse the water-insoluble imaging compounds and other
water-insoluble compounds in a coalescing solvent. Any solvent
which disperses or solubilizes the water-insoluble imaging
compounds may be used. Such coalescing solvents include, but are
not limited to, ester alcohols and glycol ethers. The solution or
dispersion is then emulsified with an aqueous base portion
containing polymer binders and other water-soluble compounds.
Conventional emulsification methods may be used to prepare oil in
water emulsions.
[0097] The components of the imaging compositions may be in the
form of a concentrate. In such concentrates, the solids content may
range from 80 wt % to 98 wt %, or such as from 85 wt % to 95 wt %.
Concentrates may be diluted with water, one or more organic
solvents, or a mixture of water and one or more organic solvents.
Concentrates may be diluted such that the solids content ranges
from 5 wt % to less than 80 wt %, or such as from 10 wt % to 70 wt
%, or such as from 20 wt % to 60 wt %.
[0098] The imaging compositions may be applied to a work piece by
any suitable method. Such methods include, but are not limited to,
spray coating, brushing, roller coating, ink jetting, dipping and
immersion.
[0099] Upon application of a sufficient amount of energy to the
imaging compositions, a photofugitive or a phototropic response
occurs. The amount of energy may be from 0.2 mJ/cm.sup.2 and
greater, or such as from 0.2 mJ/cm.sup.2 to 100 mJ/cm.sup.2, or
such as from 2 mJ/cm.sup.2 to 40 mJ/cm.sup.2, or such as from 5
mJ/cm.sup.2 to 30 mJ/cm.sup.2.
[0100] The second component of the imaging compositions undergoes
color or shade changes with the application of intensities of 5 mW
of energy or less (i.e., greater than 0 mW), or such as from less
than 5 mW to 0.01 mW, or such as from 4 mW to 0.05 mW, or such as
from 3 mW to 0.1 mW, or such as from 2 mW to 0.25 mW or such as
from 1 mW to 0.5 mW. Typically, such intensities are generated with
light sources in the visible range. Other photosensitizers and
energy sensitive compounds, which may be included in the second
component of the imaging compositions, may elicit a color or shade
change upon exposure to energy from light outside the visible
range. Such photosensitizers and energy sensitive compounds are
included to provide a more pronounced color or shade contrast with
that of the response caused by the application of 5 mW or less.
Typically photosensitizers and energy sensitive compounds, which
form the color or shade contrast with photosensitizers activated by
energy at intensities of 5 mW or less, elicit a phototropic
response.
[0101] While not being bound by theory, one or more color or shade
changing mechanisms are believed involved to provide a color or
shade change after energy is applied. For example, when a
photofugitive response is induced, the one or more sensitizers
release a free radical to activate the one or more photoreducing
agents to reduce the one or more sensitizers to affect the color or
shade change in the composition. When a phototropic response is
induced, for example, free radicals from one or more sensitizers
induce a redox reaction between one or more leuco-type compounds
and one or more oxidizing agents to affect the color or shade
change. Some formulations have combinations of photofugitive and
phototropic responses. For example, exposing a composition to
artificial energy, i.e., laser light, generates a free radical from
one or more sensitizers which then activates one or more
photoreducing agents to reduce the sensitizer to cause a
photofugitive response, and then exposing the same composition to
ambient light to cause one or more oxidizing agents to oxidize one
or more leuco-type compounds.
[0102] Any suitable energy source may be used to induce the
photofugitive or phototropic response. Examples of suitable energy
sources include, but are not limited to, lasers, including lasers
generated from hand held lasers and 3-D imaging systems, and flash
lamps. Operating wavelengths of lasers may range from IR through
UV. An example of a suitable laser is a neodymium (Nd) doped YAG
laser operating at frequencies of 473 nm and 532 nm.
[0103] The imaging compositions provide a rapid and efficient means
of changing the color or shade of a work piece or of placing an
image on a work piece. After the imaging composition is applied to
a work piece, a sufficient amount of energy is applied to the
imaging composition to change its color or shade. The energy may be
applied selectively to the imaging compositions. Generally, the
color or shade change is stable. The term "stable" means that the
color or shade change lasts at least 10 seconds, or such as from 20
minutes to 2 days, or such as from 30 minutes to 8 hours. Certain
formulations which are sensitive to light at 473 nm are stable
indefinitely under controlled conditions where blue light is
filtered.
[0104] The image may be used as a mark or indicator to drill holes
for fasteners to join parts together, cutting portions of the work
piece and masking such as in the assembly of terrestrial vehicles
such as automobiles, trucks, terrestrial and amphibious military
vehicles, aeronautical ships such as airplanes and interplanetary
vessels, marine vessels such as ships and boats, and terrestrial
structures such as houses, buildings in general and furniture; and
to form an outline for making a logo or picture on parts of
terrestrial vehicles, aeronautical ships, marine vessels,
terrestrial structures, and textiles. Since the compositions may be
promptly applied to a work piece and the image promptly formed by
application of energy to create color or shade contrast, workers no
longer need to work adjacent the work piece to mark laser beam
images with hand-held ink markers or tape in the fabrication of
articles. Accordingly, the problems of blocking laser beams caused
by workers using the hand-held markers and tape are eliminated.
[0105] Further, the reduction of human error increases the accuracy
of marking. This is important when the marks are used to direct the
alignment of parts where accuracy in fabrication is critical to the
reliable and safe operation of the machine.
EXAMPLE 1
Imaging Composition
[0106] A primer or first component of the imaging composition has a
formula as disclosed in Table 1 below.
1 TABLE 1 Compounds Percent Weight Film forming acrylic polymer
binder 80 Zinc oxide 10 Cocoamphopropionate 5 Ethylene glycol
phenyl ether 1 Water 4
[0107] The acrylic polymer is a latex polymer which may be prepared
by known methods in the art, or may be obtained commercially from
Rohm and Haas Company of Philidelphia, Pa. under the tradename
RHOPLEX.TM. E-1801. The liquid compounds are blended together at
room temperature to form an emulsion. The zinc oxide particles with
an average size of 1 .mu.m are then blended with the emulsion at
room temperature to form a suspension. The suspension has a white
appearance due to the zinc oxide pigment.
[0108] The second component or photosensitive component has a
formula as disclosed in Table 2 below. The compounds are combined
at room temperature under red light.
2 TABLE 2 Compounds Weight Percent Copolymer of styrene and acrylic
acid 25 Calcium carbonate 20 Cyclopentanone-2,5-bis[[4- 0.5
(diethylamino)phenyl]methylene]- Leuco Crystal Violet 1
o-chloro-hexaarylbiimidazole 6.5 1,2-naphoquinone 0.5
Triethanolamine triacetate 1.5 Polyalkyl betaine polysiloxane
copolymer 2 Ester alcohol 8 Water 35
[0109] Copolymers of styrene and acrylic acid are known and methods
for preparing them may be found in the literature. They also are
commercially available from Rohm and Haas Company under the
tradename RHOPLEX.TM. P-376. The copolymer is mixed in water with
the polyalkyl betaine polysiloxane copolymer to form an aqueous
suspension. Calcium carbonate is added to the suspension to
maintain a pH of 8 to 11.
[0110] The imaging compounds: leuco crystal violet,
o-chloro-hexaarylbiimidazole, 1,2-naphthaquinone, triethanolamine
triacetate and
cyclopentanone-2,5-bis[[4-(diethylamino)phenyl]methylene]-- are
mixed together in the ester alcohol to form an organic solution. A
commercially available ester alcohol is TEXANOL.TM., which is
available from Eastman Chemical Co., Kingsport, Tenn. The aqueous
suspension is emulsified with the organic solution using a
conventional emulsifier to form an oil in water emulsion.
[0111] The primer is spray coated on a surface of an aluminum
airplane body which is coated with an epoxy primer designated as
BR127 manufactured and sold by American Cyanamide Corporation. The
epoxy primer gives the aluminum surface a dark green appearance.
The primer described in Table 1 provides a white contrast with the
dark green aluminum surface.
[0112] The second component or photosensitive component is spray
coated on the first component. The second component is amber in
appearance. The workers selectively form a pattern of cross-marks
on the imaging composition with a 532 nm green light laser at 5 mW
to designate where holes are to be drilled for fasteners. The
points on the photosensitive layer exposed to the laser turn from
amber to a clear appearance revealing the white primer underlayer.
The white of the cross-marks provides a clear contrast with the
amber and dark green backgrounds such that workers may clearly
determine where they are to drill the holes. After the holes are
drilled the imaging composition is hand peeled from the aluminum
surface and discarded. No developers or strippers are used to
remove the imaging composition.
[0113] There is no indication that any of the dyes such as the
leuco crystal violet or the cyclopentanone sensitizer dye leach out
of the second component and into the epoxy primer. The red color
characteristic of such leaching is not observed. Additionally, the
inclusion of the zinc oxide pigment in the first component is
expected to increase the photospeed of the color change by a
.DELTA.=+0.5 to +1 as measured by a reflection densitometer.
EXAMPLE 2
Imaging Composition
[0114] A primer or first component of an imaging composition is
composed of the compounds disclosed in Table 3 below.
3 TABLE 3 Compounds Weight Percent Vinyl acetate/acrylic copolymer
emulsion 75 2-alkyl-2-imidazoline 4 Titanium dioxide 10 Ethylene
glycol phenyl ether 1 Water 10
[0115] The vinyl acetate/acrylic copolymer is known in the art and
methods of preparing it are well known. Such copolymers are
commercially available from Rohm and Haas Company under the
tradename ROVACE.TM. 661. The imidazoline is mixed with the
ethylene glycol to form a uniform suspension and then added to the
copolymer emulsion and mixed. This mixture is then mixed with water
to form a suspension. The tintanium dioxide pigment with an average
particle size of 0.51 .mu.m is mixed with the suspension to form a
dispersion. The dispersion has a white appearance.
[0116] The following photosensitive component is prepared at room
temperature under red light.
4TABLE 4 Component Weight Percent Vinyl acetate/acrylic copolymer
emulsion 75 2-alkyl-2-imidazoline 2 Vinyl aromatic polymer 4 Leuco
Crystal Violet 1 Tribromo methyl phenyl sulfone 5
2',4',5',7'-tetraiodo-3,4,5,6-tetrachlorofluorescein 1 disodium
salt 2,2'-methylene-bis(4-methyl-6-tertbutylphenol) 1 Ethylene
glycol phenyl ether 1 Water 10
[0117] The copolymer, vinyl aromatic polymer, and the
2-alky-2-imidazoline are mixed in water to form an aqueous
emulsion.
[0118] The imaging components: leuco crystal violet, tribromo
methyl phenyl sulfone,
2',4',5',7'-tetraiodo-3,4,5,6-tetrachlorofluorescein disodium salt,
and micro-encapsulated 2,2'-methylene-bis(4-methyl-6-tertb-
utylphenol) are solubilized in ethylene glycol phenyl ether to form
an organic solution. The aqueous emulsion and the organic solution
are mixed to form an oil in water emulsion imaging composition.
[0119] The first component of the imaging composition is roller
coated on a surface of an aluminum airplane fuselage and dried. The
fuselage is coated with BR127 epoxy primer which gives the aluminum
surface a dark green color. The first component is white and
provides a color contrast with the aluminum surface.
[0120] The second component of the imaging composition is spray
coated on the first component. The second component is translucent
and the white first component is visible under the photosensitive
second component. The second component is then dried.
[0121] Workers selectively image an outline of a company logo on
the second component of the imaging composition using a 3D, 532 nm
Nd:YAG laser at 5 mW. The outline on the second component turns
purple and the white background from the first component provides a
sharp contrast between the purple outline and the dark green
aluminum surface such that workers can readily distinguish the
purple outline.
[0122] The imaging composition is scored along the purple outline
and the portion within the outline is peeled from the fuselage and
discarded leaving an exposed aluminum surface. The exposed aluminum
is then painted to form the logo on the fuselage. The remainder of
the imaging composition is then peeled from the fuselage and
discarded. No developer or organic solvents are used to remove the
imaging composition from the fuselage.
[0123] There is no indication of leaching of the dyes from the
second component into the epoxy primer. No red color characteristic
of such leaching is observed. Additionally, the inclusion of the
pigment in the first component is expected to increase the
photospeed of the color change by a .DELTA.=+0.5 to +1, as measured
by a conventional reflection densitometer.
EXAMPLE 3
Comparative
[0124] The following composition is prepared at room temperature in
an area having ambient light filtered of green light.
5 TABLE 5 Component Weight Percent Copolymer of styrene and acrylic
acid 70 Sodium-N-coco-.beta.-aminopropionate 4 Aluminum oxide 10
Aminotriarylmethane dye 2 Tripropylene glycol n-butyl ether 2
Tribromo methyl sulfone 0.5 n-Phenyl glycine 0.5 Eosin B 1 Water
10
[0125] The sodium-N-coco-.beta.-aminopropionate is mixed with the
styrene and acrylic copolymer to form a suspension. The dye, eosin
B, n-phenyl glycine and sulfone are mixed together with
tripropylene glycol n-butyl ether to form a second suspension. The
two suspensions are mixed and then water is added to the mixture to
form an oil in water emulsion. The mixing process is done at room
temperature.
[0126] The aluminum oxide pigment with an average particle size of
0.5 .mu.m is added to the oil in water emulsion and mixed to form a
dispersion. The mixing is done at room temperature.
[0127] The photosensitive dispersion is then spray coated on an
aluminum plate 5 meters.times.5 meters. The aluminum plate is
coated with a conventional epoxy primer used in priming aluminum
airplane fuselages prior to painting. After application of the
photosensitive dispersion to the primed aluminum plate, the
interface between the aluminum plate and the photosensitive
dispersion begins to turn a red color. The red color expands across
the aluminum and also into the imaging composition. This undesired
color change compromises the color or shade contrast between the
portions of the imaging composition exposed to laser light and the
aluminum plate. Accordingly, workers find it difficult to locate
the marks formed on the imaging composition indicating the marks
for modification of the aluminum plate. The red color is believed
to be caused by the sensitizer dye eosin B leaching into the epoxy
primer on the aluminum plate.
[0128] A primer having a formulation disclosed in the table below
is prepared.
6 TABLE 6 Compound Percent Weight Copolymer of styrene and acrylic
acid 80 Sodium-N-coco-.beta.-aminopropionate 2 Tripropylene glycol
n-butyl ether 3 Aluminum oxide 10 Water 5
[0129] The primer is prepared by mixing the copolymer,
sodium-N-coco-.beta.-aminopropionate and tripropylene glycol
n-butyl ether to form a suspension. Aluminum oxide is added to the
suspension followed by mixing in a conventional sonic mixer with
water added during the process. The mixing is done at room
temperature.
[0130] A photosensitive component is prepared as described in Table
5 above, except that the aluminum oxide pigment is excluded in the
formulation. Water is added to the component to make up the weight
difference and bring the component to 100 wt %.
[0131] The primer described in Table 6 is roller coated on a 5
meters.times.5 meters aluminum plate which is coated with an epoxy
primer used in priming aluminum airplane fuselages prior to
applying paint. The primer is dried and presents a white contrast
with the dark green of the primer coated aluminum plate.
[0132] The photosensitive component is spray coated over the primer
of Table 6 to form an imaging composition on the aluminum plate.
The photosensitive component is dried over the primer or first
component. The photosensitive component is translucent and the
white underlying primer is visible creating a color contrast
between the imaging composition and the dark green aluminum plate.
No red color is observed forming on the aluminum or in the imaging
composition. Accordingly, the eosin B sensitizer dye is not
believed to be leaching from the photosensitive component.
[0133] A 532 nm laser at 5 mW is used to selectively affect a color
change in the imaging composition with cross-marks. The color of
the cross-marks is purple and presents a clear, visible contrast
with the white background of the unexposed portions of the imaging
composition and the dark green aluminum plate. Accordingly, workers
can readily modify the aluminum plate based on the purple
cross-marks.
[0134] In addition to preventing the sensitizer dye from leaching
into the epoxy primer on the aluminum plate, and presenting
improved color contrast over the photosensitive component, the
imaging composition is expected to have an increased photospeed by
a .DELTA.=+0.5 to +1, as measured by a reflection densitometer.
* * * * *