Note: Descriptions are shown in the official language in which they were submitted.
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-1-
PREPARATION OF LIGHT-EMITTING, HIGHLY REFLECTIVE AND/OR
METALLIC-LOOKING IMAGES ON A SUBSTRATE SURFACE
TECHNICAL FIELD
The present invention relates generally to compositions and methods for
preparing images on substrates, and more particularly relates to compositions
and methods
for the preparation of light-emitting, highly reflective, and/or metallic-
looking images on
glossy, light emitting, reflective or luminescent substrates. The invention
also relates to
to substrates having light-emitting, highly reflective and/or metallic looking
images thereon.
BACKGROUND ART
Many methods have been used to produce a metallic-looking image on a
substrate. For the most part, these methods involve the use of metallic
pigments and metal
15 containing inks. U.S. Patent Nos. 4,233,195 to Mills, 5,912,283 to
Hashizume et al.,
5,662,738 to Schmid et al., and 5,766,335 to Bujard et al. describe pigments
and ink
formulations that incorporate metallic, usually aluminum, particles. While
different
approaches have been followed to provide enhanced color and pigment variation,
the inks
and pigments used are typically costly and require complicated and expensive
procedures.
20 For example, U.S. Patent No. 5,370,976 to Williamson et al. describes a
metallic color
printing process wherein the image is produced using a four-color separation
process,
involving metallic gold and/or metallic silver separations, and an electronic
masking
system.
Other processes have been developed for producing a metallic-looking image
25 without the use of metallic pigments. U.S. Patent No. 5,656,331 to Kline,
for example,
describes a printed substrate having a metallic finish where the metallic
appearance is
achieved by applying a first layer having the desired final color pattern, a
second layer
comprising a moire dispersion pattern and a third coating of water pearl.
Complex thermal
processing methods have also been used. For example, U.S. Patent No. 5,564,843
to
30 Kawaguchi describes a method of producing a reflective image by printing
the image on the
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-2-
surface of a film using a thermal print head and then affixing the film onto a
reflective
surface.
Reflective surfaces to form metallic-looking images have also been used,
primarily in the marketing and display industries. U.S. Patent No. 5,106,126
to Longobardi
et al. describes a process for reverse printing on a transparent facing
material such as a
MYLAR~ polyester sheet or a glass sheet. The printing must be done as a mirror
image and
the printing steps must be performed in an order that is the reverse of the
order used in
conjunction with conventional printing, making it difficult to use standard
printing
equipment without substantial modification. Also, this method is quite costly.
to A more direct method is provided in U.S. Patent No. 5,733,634 to Karel
wherein a
metallic-looking image is generated by first applying a coating of a white
pigment to the
surface of a reflective substrate, wherein the applied pigment has varying
density across the
surface, and then applying a coating of a colored pigment, also in varying
density across the
surface. Those surface areas having a lower density of white and colored
pigments have a
metallic-looking appearance, as the reflective substrate is visible through
the coating layers.
This method is effective, it requires a separate screened application of the
white dots and is
not suitable for use in conventional ink jet printing or in any other consumer
usable image
production method.
Accordingly, there is a need in the art for a simple and inexpensive process
for the
2o printing of light-emitting, reflective or metallic-looking images.
DISCLOSURE OF THE INVENTION
The present invention features a novel process for producing a light-emitting,
glossy, reflective or metallic-looking image utilizing opaque coating
compositions on a
reflective, glossy, or luminescent substrate wherein the original surface of
the substrate is
initially masked but, after contact with a recording liquid, becomes
transparent, revealing
the glossy, reflective or luminescent substrate through the contacted, coated
area. The
opaque coating compositions are composed of a mixture of a polyacid and a
polybase and
may be used to treat a substrate either during or after manufacture.
Substrates treated with
3o the present opaque coating compositions can be used to yield high quality
light-emitting,
glossy, reflective, or metallic-looking images.
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-3-
It is a primary object of the invention to provide a method for producing a
light-
emitting, glossy, reflective or metallic-looking image comprising the steps of
applying an
opaque coating composition to the surface of a light emitting, glossy,
reflective or
luminescent substrate and contacting the coated substrate with a recording
liquid, wherein
the opaque coating comprises a mixture of a polyacid and a polybase.
Another object of the invention is to provide opaque coatings for the
treatment of
glossy, reflective or luminescent substrates, which provide a light-emitting,
reflective,
glossy, or metallic-looking image when contacted with a recording liquid.
A further object of the invention is to provide an opaquely coated reflective
or
luminescent substrate wherein the opaque coating provides a light-emitting,
reflective,
glossy, or metallic-looking image when contacted with a recording liquid.
Additional objects. advantages and novel features of the invention will be set
forth
in part in the description which follows, and in part will become apparent to
those skilled in
the art upon examination of the following, or may be learned by practice of
the invention.
In a first embodiment, then, a process is provided for producing a light-
emitting,
reflective, glossy, or metallic-looking image comprising the steps of (1)
applying an opaque
coating composition to the surface of a substrate wherein the surface is
selected from the
group consisting of glossy surfaces, reflective surfaces and luminescent
surfaces and (2)
contacting the coated substrate with a recording liquid, wherein the opaque
coating
2o composition is such that it becomes transparent upon contact with a
recording liquid.
In another embodiment of the invention, a substrate is provided having a
surface
selected from the group consisting of glossy surfaces, reflective surfaces and
luminescent
surfaces, coated with an opaque coating composition that becomes transparent
upon contact
with a recording liquid.
In a further embodiment of the invention, a process is provided for producing
a
light-emitting, glossy, reflective or metallic-looking image comprising the
steps of (1)
forming a preselected image or color scheme on top of the surface of a
substrate having a
surface selected from the group consisting of reflective surfaces and
luminescent surfaces,
(2) applying an opaque coating composition on top of the preselected image or
color
scheme, and (3) applying a recording liquid to the coated substrate, wherein
the opaque
coating composition becomes transparent upon contact.
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
_q._
In a still further embodiment of the invention, a substrate is provided having
a
surface selected from the group consisting of reflective surfaces, glossy
surfaces, and
luminescent surfaces, having a preselected image or color scheme on the
surface and
additionally coated with an opaque coating composition that becomes
transparent upon
contact with a recording liquid.
MODES FOR CARRYING OUT THE INVENTION
I. DEFINITIONS AND OVERVIEW
l0 It must be noted that, as used in the specification and the appended
claims, the
singular forms "a," "an" and "the" include plural referents unless the context
clearly dictates
otherwise. Thus, for example, reference to "an image-enhancing agent" in a
composition
means that more than one image-enhancing agent can be present in the
composition,
reference to "a polyacid" includes mixtures of polyacids, reference to "a
polybase" includes
15 mixtures of polybases, and the like.
"Aqueous based ink" refers to ink composed of an aqueous carrier medium and a
colorant, such as dye or pigment dispersions. An aqueous carrier medium is
composed of
water or a mixture of water and one or more water-soluble organic solvents.
Exemplary
aqueous based ink compositions are described in detail below.
20 "Colorant" as used herein is meant to encompass dyes, pigments, stains, and
the like
compatible for use with the opaque coating compositions of the invention.
The term "coating," as used herein to refer to the application of an opaque
coating
composition of the invention to a substrate, is intended to include
application of a coating to
a substrate surface with the composition.
25 The term "organic solvent" is used herein in its conventional sense to
refer to a
liquid organic compound, typically a monomeric organic material in the form of
a liquid,
preferably a relatively non-viscous liquid, the molecular structure of which
contains
hydrogen atoms, carbon atoms, and optionally other atoms as well, and which is
capable of
dissolving solids, gases or liquids.
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-5-
The term "fluid resistance" is used herein to describe the resistance of a
printed
substrate to penetration by a fluid, with the term "water resistance"
specifically referring to
resistance of a substrate to penetration by water.
The term "luminescence", as used herein, is meant light emitted by radiative
dissipation from an electronically excited state of a molecule. The term
"fluorescence" is
used to signify luminescence between states of identical multiplicity,
typically between the
lowest excited singlet state and the singlet ground state of the molecule. The
term
"phosphorescence" is used to signify luminescence between states of differing
multiplicity,
typically between the lowest excited triplet state and the singlet ground
state.
The term "transparent" is used herein to signify a material capable of
transmitting
light so that objects or images can be seen as if there were no intervening
material.
"Textile" or "textile substrate" as used herein refers to any cellulose-based
or non-
cellulose based textile material suitable for use as a printing substrate in
connection with the
coatings and/or methods of the invention. In general, where appropriate, the
textile
substrate has been sized, internally and/or externally, prior to application
of the
compositions of the invention.
The terms "treated textile substrate," "coated textile substrate," "treated
textile
substrate," and "coated textile substrate" are generally used herein to refer
to a textile
substrate that is treated with, i.e., has applied to its surface and/or is
partially or wholly
2o saturated with, the opaque coating of the present invention. The opaque
coating
composition is applied to the substrate in a separate coating operation prior
to image
formation, typically in amounts ranging from fifty (50) to five hundred (500)
pounds per ton
of substrate.
The term "recording liquid" is used herein to signify any ink, aqueous or
solvent
based, ink-gel, gel, or solution that is capable of rendering the opaque
coating composition
transparent or of increasing the amount of light capable of being emitted
through the opaque
coating composition.
The term "opaque" is used herein to signify a material that is not transparent
or is
only slightly translucent, so that images either cannot be seen through it at
all or cannot be
seen as if there were no intervening material. The opaque coating may or may
not contain a
color component.
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-6-
The term "alkyl" as used herein refers to a branched or unbranched saturated
hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl,
isopropyl, n-
butyl, isobutyl, t-butyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl,
tetracosyl and the like,
as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. The
term "lower
alkyl" intends an alkyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon
atoms.
The term "alkylene" as used herein refers to a difunctional, branched or
unbranched
saturated hydrocarbon group of 1 to 24 carbon atoms, including without
limitation
methylene, ethylene, ethane-1,1-diyl, propane-2,2-diyl, propane-1,3-diyl,
butane-1,3-diyl,
and the like. "Lower alkylene" refers to an alkylene group of 1 to 6 carbon
atoms.
The term "alkenyl" as used herein refers to a branched or unbranched
hydrocarbon
group of 2 to 24 carbon atoms containing at least one carbon-carbon double
bond, such as
ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, t-butenyl, octenyl,
decenyl,
tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl and the like. Preferred
alkenyl groups
herein contain 2 to 12 carbon atoms and 2 to 3 carbon-carbon double bonds. The
term
"lower alkenyl" intends an alkenyl group of 2 to 6 carbon atoms, preferably 2
to 4 carbon
atoms, containing one -C=C- bond. The term "cycloalkenyl" intends a cyclic
alkenyl group
of 3 to 8, preferably 5 or 6, carbon atoms.
The term "alkenylene" refers to a difunctional branched or unbranched
hydrocarbon
chain containing from 2 to 24 carbon atoms and at least one carbon-carbon
double bond.
"Lower alkenylene" refers to an alkenylene group of 2 to 6, more preferably 2
to 5, carbon
atoms, containing one -C=C- bond.
The term "alkoxy" as used herein intends an alkyl group bound through a
single,
terminal ether linkage; that is, an "alkoxy" group may be defined as -OR where
R is alkyl as
defined above. A "lower alkoxy" group intends an alkoxy group containing 1 to
6 carbon
atoms.
The term "aryl" as used herein refers to an aromatic species containing 1 to 3
aromatic rings, either fused or linked, and either unsubstituted or
substituted with 1 or more
substituents typically selected from the group consisting of lower alkyl,
halogen, -NHZ and -
NO,. Preferred aryl substituents contain 1 aromatic ring or 2 fused or linked
aromatic rings.
"Halo" or "halogen" refers to fluoro, chloro, bromo or iodo, and usually
relates to
halo substitution for a hydrogen atom in an organic compound.
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
The prefix "poly-" as in "polyacid" or "polybase" is intended to mean that the
compound so designated has two or more acidic groups or two or more basic
groups,
respectively. Thus, the term "polyacid" herein encompasses a diacid, and the
term
"polybase" herein encompasses a dibase.
The term "polymer" is used herein in its conventional sense to refer to a
compound
having two or more monomer units, and is intended to include homopolymers as
well as
copolymers. The term "monomer" is used herein to refer to compounds that are
not
polymeric.
"Optional" or "optionally" means that the subsequently described event or
to circumstance may or may not occur, and that the description includes
instances where said
event or circumstance occurs and instances where it does not. For example, the
phrase
"optionally substituted" aromatic ring means that the aromatic ring may or may
not be
substituted and that the description includes both an unsubstituted aromatic
ring and an
aromatic ring bearing one or more substituents.
The present invention is based upon the discovery that an opaque coating
composition comprising a mixture of a polyacid and a polybase is effective in
masking the
original surface of a glossy, reflective or luminescent substrate when coated
or printed
thereon, but upon contact with a solution or ink, e.g., upon printing, becomes
more
transparent, thereby increasing the amount of light reflected or emitted from
the substrate's
2o surface, revealing the glossy, reflective or luminescent substrate through
the contacted area.
Any conventional printing method may be used to form the image, e.g.,
printing, such as,
ink jet printing, including drop-on-demand and continuous printing, off set
printing, gravure
printing, flexographic printing; brush stenciling; spray painting, etc. All
that is required is
that a recording liquid be contacted with the opaque coating composition to
form the image.
The method is even adaptable to non-mechanical imaging methods, e.g., drawing,
handwriting and painting with aqueous inks, markers, or pens.
The coated substrates react rapidly with a number of colorants. Because
colorants
react quickly with the opaque coating, the recording liquid contacted, treated
substrates are
fast drying and do not require a separate curing step. This fast-drying
characteristic
provides for images that are "non-sticky," thus allowing the printed substrate
to be handled
immediately after formation. Processes for producing light-emitting,
reflective or metallic-
WO 01/70508 CA 02403469 2002-09-19 pCT/USO1/08816
_g_
looking images using opaque coating compositions, the opaque coating
compositions
themselves, substrates coated with the opaque coatings, described herein, and
other features
of the invention are described in greater detail below.
II. PROCESS FOR PRODUCING METALLIC-LOOKING IMAGES ON COATED SUBSTRATES
In one aspect, then, the invention features a method for producing a light-
emitting,
glossy, reflective or metallic-looking image on a substrate surface by first
applying to a
glossy, reflective or luminescent substrate surface an opaque coating
composition
comprising a mixture of a polyacid and a polybase and then contacting the
treated substrate
1o with a recording liquid, e.g., applying an ink or solution. In a preferred
embodiment, the
recording liquid comprised an ink that contains a colorant having ionizable,
nucleophilic or
otherwise reactive groups capable of reacting with the opaque coating agent in
the opaque
coating composition. Non-ionizable colorants such as dispersed pigment type
ink are also
suitable.
A. THE SUBSTRATE:
A wide variety of substrates can be used, provided that the substrate surface
is light-
emitting reflective, glossy, or luminescent. The substrate may be comprised of
a material
that inherently provides a light-emitting, reflective, glossy, or luminescent
surface, or a
2o substrate that does not have these characteristics may be used so long as
it is coated or
treated with a light-emitting, reflective, glossy, or luminescent material to
provide the
desired surface. The substrates may be flexible or rigid, porous or nonporous,
and cellulosic
or non-cellulosic.
Suitable substrates with which the present compositions and methods can be
used
include, but are not limited to, paper, polymeric substrates, textiles,
inorganic substrates,
metallic sheets, laminates, foil laminated polymer sheets, metallized polymer
sheets, and the
like. Examples of specific substrates that may be used include, for example:
polymeric
films, sheets, coatings, and solid blocks, comprised of, for example,
polyesters (including
"MYLAR°" flexible film), vinyl polymers, polysulfones, polyurethanes,
polyacrylates,
polyimides, or the like; metallic films, sheets, coatings, foils and solid
blocks, comprised of,
for example, aluminum, brass. copper, or the like; inorganic substrates in the
form of films,
WO 01/70508 CA 02403469 2002-09-19 pCT/USOl/08816
-9-
sheets, coatings, objects, and solid blocks, comprised, of, for example,
glass, metal oxides,
silicon-containing ceramics, and the like; textiles having a reflective or
luminescent surface;
and laminates such as a paper/polymeric film, polymeric film/metal foil
laminate, or
paper/metal foil laminate. The nature of the substrate is not, however,
critical; it must be
emphasized that any substrate having a light emitting, reflective, glossy, or
luminescent
surface can be used in conjunction with the invention to produce a glossy,
reflective , light
emitting, or metallic-looking image when contacted with a recording liquid.
When the substrate is not itself, light-emitting, reflective, glossy, or
luminescent, it
must be treated to provide a light-emitting, reflective, glossy, or
luminescent surface. For
example, a layer of a metallic foil or reflective polymeric film can be
laminated to the
substrate, or the substrate surface may be coated or treated with reflective
or luminescent
materials, e.g., luminescent dyes from the fluorescein, rhodamine, pyrene and
porphyrin
families. After such a treatment, the light-emitting, reflective, or
luminescent surface may
be coated with a transparent coating that does not interfere with the opaque
coating
composition.
In one embodiment, the substrate is comprised of a paper/foil laminate or a
polymer
film that has been metallized by sputtering or other processes. The paper
layer may be
formed from any convenient type of printing paper stock of desired weight. The
paper
substrate is preferably in the form of a flat or sheet structure of variable
dimensions.
"Paper" is meant to encompass printing paper (e.g., inkjet printing or
conventional printing
paper such as gravure, litho, etc. ), writing paper, drawing paper, and the
like, as well as
board materials such as cardboard, poster board, Bristol board, and the like.
Numerous
paper compositions are well known and various types of additives which can be
incorporated into paper for different purposes are also well known and widely
described; see
for instance, Blair (ed.), The Lithographers Manual, (7th Edn.: 1983), Chapter
13, Sections
8and9.
To prepare a paper/metal foil laminate, a reflective layer is applied to the
paper
portion of the substrate by using a suitable coating method such as spraying,
to deposit a
metal-containing coating onto the paper surface, or by adhering a metallicized
sheet such as
thin metal foil to the paper surface. While the foil or coating may be applied
only in selected
areas, it is preferred in most cases to have the entire surface of the paper
covered with the
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-10-
reflective layer. Papers with preapplied foil coverings forming paper foils
are also available
commercially and may be used herein. These commercial paper/foil laminates are
available
in a range of thicknesses and weights, such that foil papers with any desired
degree of
flexibility or stiffness can be selected. Those skilled in the art will be
readily able to select
the appropriate type of paper, foil or paper/foil laminate for use with the
desired type and
weight of final product to be produced.
In another embodiment, the substrate is a reflective or glossy textile or a
textile that
has been treated with a luminescent material. In general, the opaque coating
compositions
and printing methods of the invention can be used with any textile substrate
amenable to use
with such coating compositions and methods so long as the textile has a light-
emitting,
reflective or luminescent surface. Suitable textile substrates for use with
the present
invention include textiles having natural, synthetic, cellulose-based, or non-
cellulose-based
fibers or any combination thereof. Exemplary textile substrates include, but
are not limited
to, textiles having hydroxy group-containing fibers such as natural or
regenerated cellulosic
fibers (cotton, rayon, and the like); nitrogen group-containing fibers such as
polyacrylonitrile; natural or synthetic polyamides (including wool, silk, or
nylon); and/or
fibers having acid-modified polyester and polyamide groups. The substrates may
be
additionally pre-treated or after-treated with resins or other substances
compatible with the
coating compositions and methods of the invention, and may be finished or
unfinished. The
textile substrate may also be sized prior to application of the opaque coating
composition.
Alternatively, the present coating compositions may be incorporated into an
external sizing
process, so that sizing and coating is conducted in a single step.
The fibers of the textile substrate may be in any suitable form compatible
with the
selected image forming process. e.g., loose yarns, or fabrics. Fabrics are a
convenient and
preferred form. The fibers may be blended with other fibers that are
susceptible to treatment
with the opaque coating composition of the invention. or with fibers that may
prove less
susceptible to such treatment.
CA 02403469 2002-09-19
WO 01/70508 PCT/USOI/08816
-11-
B. THE OPAQUE COATING COMPOSITION:
The opaque coating composition is then applied to the light-emitting,
reflective,
glossy, or luminescent surface. The opaque coating composition may be applied
in any
conventional manner, e.g., using a Meyer rod, slot die, roller, knife,
dipping, painting,
spraying, etc. Generally, coating is accomplished by dip coating, reverse roll
coating,
extrusion coating, or the like. If the substrate is a paper or thin polymeric
film and the
coating composition is applied on-machine, in order to achieve acceptable
manufacture
speeds of about 100 to 2000 feet per minute, preferably 100-1000 feet per
minute, it is
recommended that the weight of the substrate, e.g., sized paper, be greater
than about 30
grams per square meter.
The opaque coating compositions are composed of an opaque coating agent that
comprises a mixture of a polyacid and a polybase. In addition to the opaque
coating agent,
the coating composition can include components such as film-forming binders,
pigments,
and other additives.
The opaque coating compositions can be readily prepared from commercially
available starting materials and/or reagents, are compatible with additional
binders or
additives, can be used with a variety of substrates, are compatible with a
variety of printing
methods, including conventional and digital printing methods (particularly ink
jet printing,
including drop-on-demand printing and continuous printing), and can also be
used with
existing commercial manufacturing methods and equipment, including, for
example, paper
production processes and equipment. The opaque coating composition is
inexpensive to
prepare, and relatively small amounts are required to provide a coated
substrate suitable
herein. The opaque coating compositions are also easy to handle due to their
solubility in
water, and do not require the use of large volumes of organic solvents.
The opaque coating agent typically represents approximately 5% to 95%,
preferably
about 10% to 95%, of the opaque coating composition, based upon total solids
weight of the
composition after drying.
The polyacid and polybase, which together represent the "opaque coating
agent,"
may be either monomeric or polymeric. That is, the opaque coating agent may be
composed
of any suitable combination of: 1 ) a monomeric polyacid and a monomeric
polybase; 2) a
polymeric polyacid and a polymeric polybase; 3) a polymeric polyacid and a
monomeric
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-12-
polybase; and/or 4) a monomeric polyacid and a polymeric polybase. The opaque
coating
agent may also be comprised of more than one different type of polyacid or
polybase and
compositions comprised of, for example, a monomeric polyacid, a monomeric
polybase,
and a polymeric polybase or a monomeric poly acid, a polymeric polyacid, and a
monomeric and/or polymeric polybase and the like are also possible. The
selection of these
combinations for use as the opaque coating agent in the present compositions
will vary
according to a variety of factors such as the nature of the substrate to be
treated, the colorant
to be used in printing on the treated substrate, etc. The relative ratios of
the polyacid and
polybase within the mixture will also vary according to such factors, but
typically the ratio
of base to acid is in the range of approximately 0.5:1 to 10:1, more typically
in the range of
approximately 1:1 to 3:1.
In general, the pH of the coating composition having a polyacid/polybase
opaque
coating agent is generally in the range of about 6- 12, preferably at least
about 7.5- 10. The
pH is maintained by the addition of appropriate bases such ammonia, primary,
secondary,
and tertiary alkyl amines, ethanolamines, diamine, and the like.
In general, monomeric polyacids will contain two or more carboxylic, sulfonic
and/or phosphonic acid groups. Exemplary monomeric polyacids have the
structural
formula (I)
(I) [R -(LX -COOH)y)Z
wherein: R is selected from the group consisting of alkyl, alkenyl, aryl of 1
to 3 rings which
may be fused or linked, and 5- and 6-membered heterocyclic rings having from 1
to 3
heteroatoms selected from N, S and O; L is an alkylene or alkenylene chain
containing 1 to
8 carbon atoms; x is 0 or l; y is an integer in the range of 2 to 10
inclusive; and z is 1, 2 or
3, with the provisos that (a) if w is 0 and x is 0, then y is 2 and z is 2,
and (b) if z is 2 or 3,
the distinct R groups are covalently linked to each other.
Specific examples of preferred monomeric polyacids include, but are not
necessarily
limited to, oxalic acid, malefic acid, succinic acid, methylsuccinic acid,
malonic acid, adipic
3o acid, glutaric acid, fumaric acid, dihydroxyfumaric acid, malic acid,
mesaconic acid,
itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-, 1,3-
and 1,4-
WO 01/70508 CA 02403469 2002-09-19 pCT/US01/08816
-13-
cyclohexane dicarboxylic acids, 1,2,3-cyclohexane tricarboxylic acid, 1,2,4-
cyclohexane
tricarboxylic acid, 1,3,5-cyclohexane tricarboxylic acid, 1,2- and 1,3-
cyclopentane
dicarboxylic acids, citric acid, tartaric acid, dihydroxyterephthalic acid,
1,2,3-, 1,2,4- and
1,2,5-benzene tricarboxylic acids, tricarballylic acid, 1,2,4,5-benzene
tetracarboxylic acid,
norbornene tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid,
1,2,3,4,5,6-
benzene hexacarboxylic acid, aspartic acid, glutamic acid, and combinations
thereof.
In general, monomeric polybases useful herein contain two or more primary,
secondary or tertiary amino groups. Exemplary monomeric polybases have the
structural
formula (II)
(II) [R -(LX -NR'RZ)y]Z
wherein R' and R' are hydrogen, alkyl, alkoxy, or hydroxyl-substituted alkoxy,
and R, L, x,
y and z are as defined with respect to the monomeric polyacid.
Specific examples of monomeric polybases include, but are not limited to,
ethylenediamine, 1,2-propane diamine, 1,3-propanediamine, 1,2,3-
triaminopropane, cis-1,2-
cyclohexanediamine, traps-1,2-cyclohexanediamine, 1,3-
bis(aminomethyl)cyclohexane, o-,
m- and p-phenylenediamine, tetramethyl o-, m- and p-phenylenediamine,
hexamethylenediamine, hexamethylenetetraamine, diethylenetriamine,
2o tetraethylenepentamine, pentaethylenehexamine, pentamethyl
diethylenetriamine, tris(2-
aminoethyl)amine, 1,1,4,7,10,10-hexamethyl triethylenetetramine, tetramethyl p-
phenylenediamine, tetramethylethylenediamine, triethylenetetraamine, 4,4'-
bipyridyl, and
combinations thereof.
The polymeric polyacids contain carboxylic, sulfonic and/or phosphonic acid
groups, but most preferably contain carboxylic acid groups. Examples of
polymeric
polyacids include, without limitation, poly(acrylic acid), poly(acrylonitrile-
acrylic acid),
polystyrene-acrylic acid), poly(butadiene-acrylonitrile acrylic acid),
poly(butylacrylate-
acrylic acid), poly(ethyl acrylate-acrylic acid), poly(methacrylate-acrylic
acid), poly(methyl
methacrylate-acrylic acid), poly(methyl methacrylate-styrene-acrylic acid),
polyvinyl
pyrrolidone-acrylic acid), polystyrene-co-malefic acid), poly(methyl
methacrylate-styrene-
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-14-
co-malefic), polyethylene-propylene-acrylic acid), polypropylene-acrylic
acid), alginic
acid, phytic acid, and combinations thereof.
The polymeric polybases comprise nitrogenous polymers that may have pendant
primary, secondary or tertiary amine groups and/or nitrogenous moieties in the
backbone,
i.e., -NH- or -NX- groups, where X is typically alkyl of 2 to 8 carbon atoms,
lower acyl, or -
(CHZ)mR3 wherein m is an integer in the range of 1 to 10 and R3 is hydroxyl or
-OR's wherein
R4 is C,-C4 alkyl. For example, the basic polymer may be a copolymer
containing first
monomer units having the structure -CH,-CH,-NH-, second monomer units having
the
structure -CH,-CHz-NX- wherein X is as defined above, and optionally third
monomer units
having the structure -CH,-CH(COOH)-. Exemplary polymeric polybases include,
but are
not limited to, polyethyleneimine, polyvinylpyridine, polyallylamine
(including N-alkylated
and N,N-dialkylated polyallylamines), polyvinylaziridine, polyimidazole,
polylysine,
chitosan, poly(amino and alkylated amino)ethylenes, ethoxylated
polyethyleneimine,
propoxylated polyethyleneimine, polyvinylpyrrolidone, dimethylaminoacrylate,
polyvinylpyrrolidone diethylaminoacrylate, vinyl pyrrolidone-
dimethylaminopropyl
methacrylamide copolymer and combinations thereof.
The opaque coating composition preferably includes a film-forming binder,
i.e., a
substance that provides for improved strength of a substrate upon application
thereto.
"Film-forming binders" used in connection with the compositions of the
invention include
2o any film-forming binders that are compatible with the selected opaque
coating agent and
other components of the coating composition. Exemplary film-forming binders
include, but
are not necessarily limited to: polysaccharides and derivatives thereof, e.g.,
starches,
cellulosic polymers, dextran and the like; polypeptides (e.g., collagen and
gelatin); and
synthetic polymers, particularly synthetic vinyl polymers such as polyvinyl
alcohol),
polyvinyl phosphate), polyvinyl pyrrolidone), vinyl-pyrrolidone-vinyl acetate
copolymers,
vinyl acetate-acrylic acid copolymers, vinyl alcohol-vinyl acetate copolymers,
vinyl
pyrrolidone-styrene copolymers, and polyvinyl amine), synthetic acrylate
polymers and
copolymers such as poly(acrylic acid-co-methacrylate), polyvinyl-co-acrylate),
poly(vinylpyrrolidone-co-dimethylaminopropyl-methacrylamide), and the like,
and water-
3o soluble or water-dispersible polyesters such as sulfopolyesters (e.g., as
available from
Eastek).
CA 02403469 2002-09-19
VVO 01/70508 PCT/USO1/08816
-15-
Polysaccharide binders: Starches, as noted above, represent one category of
suitable
film-forming binders for use herein. Suitable starches may be any of a variety
of natural,
converted, and synthetically modified starches. Exemplary starches include,
but are not
necessarily limited to, starch (e.g., SLS-280 (St. Lawrence Starch)), cationic
starches (e.g.,
Cato-72 (National Starch), hydroxyalkylstarch, wherein the alkyl has at least
one carbon
atom and wherein the number of carbon atoms is such that the material is water
soluble,
preferably from about 1 to about 10 carbon atoms, such as methyl, ethyl,
propyl, butyl, or
the like (e.g., hydroxypropyl starch #02382 (PolySciences, Inc.), hydroxyethyl
starch
#06733 (PolySciences, Inc.), Penford Gum 270 and 280 (Penford), and Film-Kote
(National
to Starch)), starch blends (see, e.g., U.S. Pat. No. 4,872,951, describing a
blend of cationic
starch and starch treated with an alkyl or alkenyl succinic anhydride (ASA),
preferably 1-
octenyl succinic anhydride (OSA)), and the like. The film-forming binder can
also be a
synthetically produced polysaccharide, such as a cationic polysaccharide
esterified by a
dicarboxylic acid anhydride (see, e.g., U.S. Pat. No. 5,647,898). Additional
saccharide
binders include cellulosic materials such as alkyl celluloses, aryl
celluloses, hydroxy alkyl
celluloses, alkyl hydroxy alkyl celluloses, hydroxy alkyl celluloses,
dihydroxyalkyl
cellulose, dihydroxyalkyl cellulose, hydroxy alkyl hydroxy alkyl cellulose,
halodeoxycellulose, amino deoxycellulose, dialkylammonium halide hydroxy alkyl
cellulose, hydroxyalkyl trialkyl ammonium halide hydroxyalkyl cellulose,
dialkyl amino
alkyl cellulose, carboxy alkyl cellulose salts, cellulose sulfate salts,
carboxyalkylhydroxyalkyl cellulose and the like). Still additional film-
forming binders of
this type include dextran (e.g., dialkyl aminoalkyl dextran, amino dextran,
and the like),
carrageenan, Karaya gum, xanthan, guar and guar derivatives, (e.g.,
carboxyalkyl
hydroxyalkyl guar, cationic guar, and the like), and gelatin.
Additional exemplary film-forming binders include resins (e.g., such as
formaldehyde resins such as melamine-formaldehyde resin, urea-formaldehyde
resin,
alkylated urea-formaldehyde resin, and the like), ionic polymers (e.g., poly(2-
acrylamide-2-
methyl propane sulfonic acid, poly(N,N-dimethyl-3,5-dimethylene piperidinium
chloride,
poly(methylene-guanidine), and the like), malefic anhydride and malefic acid-
containing
polymers (e.g., styrene-malefic anhydride copolymers, vinyl alkyl ether-
rnaleic anhydride
copolymers, alkylene-malefic anhydride copolymers, butadiene-malefic acid
copolymers,
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-16-
vinylalkylether-malefic acid copolymers, alkyl vinyl ether-malefic acid
esters, and the like),
acrylamide-containing polymers (e.g., poly(acrylamide), acrylamide-acrylic
acid
copolymers, poly(N,N-dimethyl acrylamide), and the like), poly(alkylene imine)-
containing
polymers (e.g., poly(ethylene imine), polyethylene imine) epichlorohydrin,
alkoxylated
polyethylene imine), and the like), polyoxyalkylene polymers (e.g.,
poly(oxymethylene),
poly(oxyethylene), polyethylene oxide), ethylene oxide/propylene oxide
copolymers,
ethylene oxide/2-hydroxyethyl methacrylate/ethylene oxide and ethylene
oxide/hydroxypropyl methacrylate/ethyleneoxide triblock copolymers, ethylene
oxide-4-
vinyl pyridine/ethylene oxide triblock copolymers, ethylene oxide-
isoprene/ethylene oxide
triblock copolymers, epichlorohydrin-ethylene oxide copolymer, and the like),
etc.
Any of the above exemplary film-forming binders can be used in any effective
relative amounts, although typically the film-forming binder, if present,
represents
approximately 1 wt.% to 50 wt.%, preferably 1 wt.% to 25 wt.%, most preferably
1 wt.% to
wt.% of the opaque coating composition, after drying on a substrate. Starches
and
15 latexes are of particular interest because of their availability and
applicability to a variety of
substrates.
Additional components of the opaque coating composition may be present, and
include, but are not necessarily limited to, inorganic fillers, anti-curl
agents, surfactants,
plasticizers, humectants, UV absorbers, optical brighteners, light fastness
enhancers,
2o polymeric dispersants, dye mordants and leveling agents, as are commonly
known in the art.
Preferred additives are optical brighteners, which generally represents
approximately 0.0
wt.% to 2.0 wt.% of the coating composition after drying on a substrate.
Illustrative
examples of such additives are provided in U.S. Patent Nos. 5,279,885 and
5,537,137. The
opaque coating compositions may also include a crosslinking agent such as
zirconium
acetate, ammonium zirconium carbonate, or the like, for intramolecular and/or
intermolecular crosslinking of the opaque coating agent, and/or a chelating
agent such as
boric acid. Colorants e.g., pigments, dyes, or other colorants, may also be
present in the
opaque coating composition.
While the opaque coating composition can be prepared in an organic solvent, it
is
preferably provided in an aqueous liquid vehicle wherein small amounts of a
water-soluble
organic solvent may be present. The aqueous liquid vehicle will generally be
water,
WO 01/70508 CA 02403469 2002-09-19 pCT/USO1/08816
-17-
although other inorganic compounds which are either water-soluble or water
miscible may
be included as well. It may on occasion be necessary to add a solubilizing
compound
during preparation of the coating composition so that the components dissolve
in the
aqueous liquid vehicle, e.g., an inorganic base such as ammonia and/or an
organic amine.
Suitable organic amines include lower alkyl-substituted amines such as
methylamine,
dimethylamine, ethylamine, and trimethylamine, as well as ethanolamine,
diethanolamine,
triethanolamine, and substituted ethanolamines, typically lower alkyl-
substituted
ethanolamines such as N-methyl and N,N-dimethyl ethanolamines, and morpholine.
Such
compounds are also useful for bringing the pH into the desired range for basic
formulations
as discussed in the preceding section, and, if present, will generally
represent not more than
about 20 wt.% of the composition, and in most cases will represent not more
than about 10
wt.% of the composition.
C. IMAGE FORMATION:
is Once an opaquely coated, reflective, glossy, or luminescent substrate is
produced,
the opaquely coated substrate is contacted with an ink or other solution to
render the coating
transparent; in a preferred embodiment, an image forming step using an aqueous
or solvent
based ink is employed to impart desired colors and form a light-emitting,
reflective,
glossy,or metallic-looking image. The image forming step may employ any of a
variety of
printing techniques, including inkjet printing, laserjet printing,
flexographic printing,
gravure printing and the like, or may employ the use of a writing instrument
such as a pen,
marker, gel pen, rollerball pen, ballpoint pen, and the like. In general, the
image forming
process involves applying, in an imagewise pattern, a recording liquid to a
coated substrate
of the invention. Inkjet printing processes suitable for the method of the
invention are well
known in the art; see, for example, U.S. Patent Nos. 4,601,777; 4,251,824;
4,410,899;
4,412,224; and 4,532,530. Thermal ink transfer printers that use dye
sublimation process
can also form the light-emitting, reflective or metallic-looking images. Hot
melt type inkjet
printers, such as Tektronix ink jet printers that use inks formed of low
melting solids are
also suitable. The light-emitting, reflective or metallic-looking images can
also be produced
using a variety of other printing and imaging processes, such as offset
printing, printing with
WO 01/70508 CA 02403469 2002-09-19 pCT/USO1/08816
-1 g-
pen plotters, drawing, handwriting, painting with ink pens, brush stenciling,
spray painting,
and the like.
In general, inks are used in the formation of the image on the treated
substrates of
the invention. The ink may be any suitable ink containing a colorant, e.g., a
pigment, dye,
or stain, having one or more reactive groups suitable for reacting, either
covalently or
ionically, with a colorant-reactive component of the opaque coating agent
present on the
treated substrate. Aqueous and solvent-based, dye sublimation, or hot melt
inks are all
acceptable. The selection of the specific ink and colorant will vary with the
colorant-
reactive component of the image-enhancing agent. Thus, preferred colorants for
use in
forming an image on a substrate treated with the present image-enhancing
compositions are
those containing one or more ionizable, nucleophilic or otherwise reactive
moieties.
Particularly preferred colorants contained in the inks useful with the
invention are thus dyes
containing acidic groups (e.g., carboxylate, phosphonate, sulfonate or
thiosulfonate
moieties), basic groups (e.g., unsubstituted amines or amines substituted with
1 or 2 alkyl,
typically lower alkyl, groups), and/or nucleophilic or otherwise reactive
moieties (e.g.,
hydroxyl, sulfhydryl, cyano or halo).
The selection of the ink will depend upon the requirements of the specific
application, such as desired surface tension, viscosity, drying time, and the
like. If aqueous
ink is selected, the aqueous liquid vehicle of inks suitable for use in the
invention will
generally be water, although other nonorganic compounds which are either water-
soluble or
water miscible may be included as well. The colorant may be dissolved,
dispersed or
suspended in the aqueous liquid vehicle, and is present in an amount effective
to provide the
dried ink with the desired color and color intensity.
In some instances, the dye is contained in a carrier medium composed of ink
and a
water-soluble organic solvent. For applications utilizing such a carrier
medium,
representative solvents include polyols such as polyethylene alcohol,
diethylene glycol,
propylene glycol, and the like. Additional solvents are simple alcohols such
as ethanol,
isopropanol and benzyl alcohol, and glycol ethers, e.g., ethylene glycol
monomethyl ether,
diethylene glycol monoethyl ether. Representative examples of water-soluble
organic
solvents are described in U.S. Patent 5,085,698 and U.S. Patent No. 5,441,561.
Suitable
water soluble organic solvents include, but are not limited to, C,_5-alkanols,
e.g. methanol,
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-19-
ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol and
isobutanol;
amides, e.g., dimethylformamide and dimethylacetamide; ketones and ketone
alcohols, e.g.,
acetone and diacetone alcohol; C,_4 -ethers, e.g. tetrahydrofuran and dioxane;
alkylene
glycols or thioglycols containing a C, -C6 alkylene group, e.g., ethylene
glycol, propylene
glycol, butylene glycol, pentylene glycol and hexylene glycol; poly(alkylene-
glycol)s and
poly(alkylene- thioglycol)s, e.g., diethylene glycol, thiodiglycol,
polyethylene glycol and
polypropylene glycol; polyols, e.g., glycerol and 1,2,6-hexanetriol; lower
alkyl glycol and
polyglycol ethers, e.g., 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol,
2-(2-ethoxyethoxy)-thanol, 2-(2-butoxyethoxy)ethanol, 3-butoxypropan-1-ol,
-[2-(2-methoxyethoxy)-ethoxy]ethanol, 2-[2-(2-ethoxyethoxy)ethoxy]- ethanol;
cyclic esters
and cyclic amides, e.g., optionally substituted pyrollidones; sulpholane; and
mixtures
containing two or more of the aforementioned water soluble organic solvents.
Water
insoluble organic solvents may also be used. Suitable water insoluble organic
solvents
include, but are not limited to, aromatic hydrocarbons, e.g., toluene, xylene,
naphthalene,
tetrahydronaphthalene and methyl naphthalene; chlorinated aromatic
hydrocarbons, e.g.,
chlorobenzene, fluorobenzene, chloronaphthalene and bromonaphthalene; esters,
e.g., butyl
acetate, ethyl acetate, methyl benzoate, ethyl benzoate, benzyl benzoate,
butyl benzoate,
phenylethyl acetate, butyl lactate, benzyl lactate, diethyleneglycol
dipropionate, dimethyl
phthalate, diethyl phthalate, dibutyl phthalate, di(2-ethylhexyl)phthalate;
alcohols having six
or more carbon atoms, e.g. hexanol, octanol, benzyl alcohol, phenyl ethanol,
phenoxy
ethanol, phenoxy propanol and phenoxy butanol; ethers having at least 5 carbon
atoms,
preferably CS_~4 ethers, e.g. anisole and phenetole; nitrocellulose, cellulose
ether, cellulose
acetate; low odour petroleum distillates; turpentine; white spirits; naphtha;
isopropylbiphenyl; terpene; vegetable oil; mineral oil; essential oil; and
natural oil; and
mixtures of any two or more thereof.
Specific examples of suitable colorants include, but are not limited to, the
following:
Dispersol Blue Grains (Zeneca, Inc.), Duasyn Acid Blue (Hoechst Celanese),
Duasyn Direct
Turquoise Blue (Hoechst Celanese), Phthalocyanine blue (C.I. 74160), Diane
blue (C.I.
21180), Pro jet Cyan 1 (Zeneca, Inc.), Pro jet Fast Cyan 2 (Zeneca, Inc.),
Milori blue (an
inorganic pigment equivalent to ultramarine) as cyan colorants; Dispersol Red
D-B Grains
(Zeneca, Inc.), Brilliant carmine 6B (C.I. 15850), Pro jet magenta 1 (Zeneca,
Inc.), Pro jet
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-20-
Fast magenta 2 (Zeneca, Inc.), Brilliant Red F3B-SF (Hoechst Celanese), Red 3B-
SF
(Hoechst Celanese), Acid Rhodamine (Hoechst Celanese), Quinacridone magenta
(C.I.
Pigment Red 122) and Thioindigo magenta (C.I. 73310) as magenta colorants;
Dispersol
Yellow D-7G 200 Grains (Zeneca, Inc.), Brilliant yellow (Hoechst Celanese),
Pro jet yellow
1 (Zeneca, Inc.), Pro jet Fast Yellow 2 (Zeneca, Inc.), benzidine yellow (C.I.
21090 and C.I.
21100) and Hansa Yellow (C.I. 11680) as yellow colorants; organic dyes; and
black
materials such as carbon black, charcoal and other forms of finely divided
carbon, iron
oxide, zinc oxide, titanium dioxide, and the like. Specific and preferred
black colorants
include Acid Black 48 (Aldrich), Direct Black 58756 A (Crompton & Knowles),
BPI
to Molecular Catalytic Gray (Brain Power), Fasday Cool Gray (Hunter Delator),
Dispersol
Navy XF Grains (Zeneca, Inc.), Dispersol Black CR-N Grains (Zeneca, Inc.),
Dispersol
Black XF Grains (Zeneca, Inc.), Disperse Black (BASF), Color Black FW18
(Degussa),
Color Black FW200 (Degussa), Hostafine Black TS (Hoechst Celanese), Hostafine
Black T
(Hoechst Celanese), Duasyn Direct Black (Hoechst Celanese), Pro jet Black 1
(Zeneca,
Inc.) and Pro jet Fast Black 2 (Zeneca, Inc.). Other suitable colorants are
disclosed in U.S.
PatentNos. 4,761,180, 4,836,851, 4,994,110 and 5,098,474.
In an additional aspect of the invention the light-emitting, reflective or
metallic-
looking image is produced by having the image or color scheme printed on the
reflective or
luminescent layer prior to the coating with the opaque coating composition.
The light-
emitting, reflective or metallic-looking image is generated by contacting the
coated
substrate with an aqueous solution that may optionally contain a dye or
colorant, as
discussed above. Embodiments of this type have utility as art or craft
materials. The
coated substrates of the invention may be used as "magic" papers and the like
for children,
wherein a hidden image appears on contact with a solution.
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-21-
EXPERIMENTAL
The following examples are put forth so as to provide those of ordinary skill
in the
art with a complete disclosure and description of how to prepare and use the
compounds
disclosed and claimed herein. Efforts have been made to ensure accuracy with
respect to
numbers (e.g., amounts, temperature, etc.) but some errors and deviations
should be
accounted for. Unless indicated otherwise, parts are parts by weight,
temperature is in °C
and pressure is at or near atmospheric.
Also, in these examples, unless otherwise stated, the abbreviations and terms
1o employed have their generally accepted meanings. Abbreviations and
tradenames are as
follows (note that suppliers of each material are indicated as well):
Joncryl 62 =Joncryl 62°, arcrylic polymer (SC Johnson);
Epomine 1050 = Epomine 1050°, polyethylene imine (Nippon Shokubai, Co
Ltd.);
ISP 937 =ISP 937°, polyvinylpyrrolidone-dimethylaminomethacrylate
(ISP);
15 PVA 5235 = PVA 523S°, polyvinyl alcohol, binder (Airvol
5235°, Air Product);
Acusol 445 =Acusol 445°, acrylate copolymer (Rohm & Haas Co.)
Alcosperse 409 = Alcosperse 409°,polyacrylic acid (Alco Chemical);
Surfynol SE-F =Surfynol SE-F°, surfacant (Air Product);
Lupasol SKA =Lupasol SKA°' ethoxylated polyethylenimine (BASF);
2o Rhophex AR-74 = Rhophex AR-74°, acrylic polymer (Rohm & Haas Co.);
Silica=Aerosil MOX 170°, fumed silica (Degussa).
EXAMPLE 1
25 PROCEDURE FOR METALLIC PRINTING
The following components were blended for 20 minutes in a high shear mixer,
producing a thick solution.
Joncryl 62 25.0g
ISP 937 lO.Og
30 Alcosperse 409 4.0g
Lupasol SKA 8.0g
PVA 523S 27.3g
Surfynol SE-F 1.0g
Liquor Ammonia 24.0g
35 Water 20.0g
WO 01/70508 CA 02403469 2002-09-19 pCT/USO1/08816
-22-
Metal foil laminated sheets were then coated with the solution using No. 20,
30 and 40
Meyer rods. The coated sheets were allowed to dry and upon drying, the coating
became
white and opaque. A Hewlett Packard 850 inkjet printer was then used to print
an image
onto one of the coated sheets. After drying the printed sheet for 2 minutes at
room
temperature, a metal-looking image was obtained.
F,X A MPT .F 7
METALLIC PRINTING USING A TWO-COMPONENT SYSTEM
The above given general procedure can also be used as two component system and
l0 components can be mixed prior to use. The following components were
obtained by
blended the listed constituents for 10 minutes at 4000 rpm in a high shear
mixer. Each
component was then labeled and stored in a separate vial.
Component A Component B
Joncryl 62 62.5g Lupasol SKA 20.0g
ISP 937 25.0g PVA 5235 68.25g
Alcosperse 409 lO.Og Liquor Ammonia 30.0g
Surfynol SE-F 2.5g
Liquor Ammonia 30.0g
Water 50.0g
lO.Og of Component A and 6.57g of Component B were weighed, combined and
manually
shaken for one minute and then applied onto metallized sheet using No. 20, 30
and 40
Meyer rods. The coated sheets were allowed to dry and upon drying, the coating
became
white and opaque. A Hewlett Packard 850 inkjet printer was then used to print
an image
onto one of the coated sheets. After drying the printed sheet for 2 minutes at
room
temperature, a metal-looking image was obtained.
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-23-
FXAMPI.F.
PROCEDURE FOR METALLIC PRINTING
The procedure of Example 1 was repeated using the following using a coating
solution containing the following components:
Joncryl 62 62.5g
ISP 937 25.0g
PVA 523S 68.25g
Acusol 445 1 O.Og
l0 Surfynol SE-F 3.0g
Lupasol SKA 20.0g
Liquor Ammonia 25.0g
Water 100.0g
F.x A Mpt .F. 4
PROCEDURE FOR METALLIC PRINTING
The procedure of Example 1 was repeated using a coating solution containing
the
following components:
Joncryl 62 29.55g
ISP 937 lO.Og
PVA 523S 13.65g
Acusol 445 4.0g
Surfynol SE-F 1.2g
Lupasol SKA 8.0g
Liquor Ammonia 30.0g
Water 60.0g
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-24-
FXAMPT,F S
PROCEDURE FOR METALLIC PRINTING
The procedure of Example 1 was repeated using a coating solution containing
the
following components:
Joncryl 62 25.0g
ISP 937 lO.Og
PVA 5235 27.3g
Alcosperce 409 4.0g
l0 Surfynol SE-F 0.4g
Lupasol SKA 8.0g
Liquor Ammonia 30.0g
Isopropyl Alcohol lO.Og
Water 40.0g
FXAMPT.F ~t
OPAQUE COATING COMPOSITIONS
Table 1 summarizes exemplary opaque coating compositions in accordance with
the
invention. Each of the representative formulations was prepared using the
methods
described in Example 1 and used to coat metallized sheets, which were then
printed on
using an aqueous ink and an inkjet printer. The resulting images so prepared
were found to
have the metallic-looking appearance described herein.
CA 02403469 2002-09-19
WO 01/70508 PCT/USO1/08816
-25-
00
0
n
I ~ I I I I 0
4
O N O O O O OO
O
N t n ~ O O
l D N D i M N N ~ C3
t . N
I ~ I I I I
O ~ O O ~ OO~
O N O
O 1 O M
p O OM
N .- i ~ .- , 0 M tD UN
~ 0
I I I I
0 0 cn 0 0 o
rt o ~
~
N N ~ O ~ ~ ~ ~t CJN
I I I I I
O O M O O O
~ rt O ~
O Is
C~ N .-~ N (~ O n
O
.
..,
,
I I I I
I
O O O M O O
O tn c ' O~O
.>O lf~ O I~ t
y., ~ N M .-~ N N O
z
o
.>~ O ri r I I I I I qp
p
., .-. o m o c o o~t
N i
~1 tn O Is tn
~ O
O ~ N N .~ N N O ~ N C7~
CCS
O
O
I I I I I
~
a o o M o~o
~i o ~
c~S u o n ~ o 0 0
N M .-~ N M O N N C3.-~
O I I I I
O
__ _, ~ ~
~
~ O 00 ~ O
N .-~.-t .-i .-iO O N N U'
n I I I I
O
O ~ ~ OI~
O 1~ ~
N .-i~ N .~ O O ~ O
O I I I I
0 o M o 0
' o ~ . 'r m o 0 0~
.
N ~ -~ N ~t O ~ N N C7O~
O N
_ M
tt7
( 0
!Q O
O O V
v a ~ ~ N O v c a
O _ ~
~ Q a~ ~
o _ = r. _ L o o ~ a a
_ _ N O
N ~ ~ ~ ~ ~N
~ ~
o c o a ~ L o ~ o r' cc
__
a n ~ N ~ '
.' ~y
v - 4r N a n c ~ in ~ ~a a
> .
