[0001] This invention relates to an ink jet recording element and a printing method using
the element. More particularly, this invention relates to an ink jet recording element
containing a multiplicity of particles.
[0002] In a typical ink jet recording or printing system, ink droplets are ejected from
a nozzle at high speed towards a recording element or medium to produce an image on
the medium. The ink droplets, or recording liquid, generally comprise a recording
agent, such as a dye or pigment, and a large amount of solvent. The solvent, or carrier
liquid, typically is made up of water, an organic material such as a monohydric alcohol,
a polyhydric alcohol or mixtures thereof.
[0003] An ink jet recording element typically comprises a support having on at least one
surface thereof an ink-receiving or image-forming layer, and includes those intended
for reflection viewing, which have an opaque support, and those intended for viewing
by transmitted light, which have a transparent support.
[0004] It is well known that in order to achieve and maintain photographic-quality images
on such an image-recording element, an ink jet recording element must:
- Be readily wetted so there is no puddling, i.e., coalescence of adjacent ink dots,
which leads to non-uniform density
- Exhibit no image bleeding
- Exhibit the ability to absorb high concentrations of ink and dry quickly to avoid
elements blocking together when stacked against subsequent prints or other surfaces
- Exhibit no discontinuities or defects due to interactions between the support and/or
layer(s), such as cracking, repellencies, comb lines and the like
- Not allow unabsorbed dyes to aggregate at the free surface causing dye crystallization,
which results in bloom or bronzing effects in the imaged areas
- Have an optimized image fastness to avoid fade from contact with water or radiation
by daylight, tungsten light, or fluorescent light
[0005] An ink jet recording element that simultaneously provides an almost instantaneous
ink dry time and good image quality is desirable. However, given the wide range of
ink compositions and ink volumes that a recording element needs to accommodate, these
requirements of ink jet recording media are difficult to achieve simultaneously.
[0006] Ink jet recording elements are known that employ porous or non-porous single layer
or multilayer coatings that act as suitable image receiving layers on one or both
sides of a porous or non-porous support. Recording elements that use non-porous coatings
typically have good image quality but exhibit poor ink dry time. Recording elements
that use porous coatings typically contain colloidal particulates and have poorer
image quality but exhibit superior dry times.
[0007] While a wide variety of different types of porous image-recording elements for use
with ink jet printing are known, there are many unsolved problems in the art and many
deficiencies in the known products which have severely limited their commercial usefulness.
A major challenge in the design of a porous image-recording layer is to be able to
obtain good quality, crack-free coatings with as little non-particulate matter as
possible. If too much non-particulate matter is present, the image-recording layer
will not be porous and will exhibit poor ink dry times.
[0008] U.S. Patent 5,912,071 relates to a recording medium comprising a substrate and a
porous layer formed on the substrate wherein the porous layer comprises water-insoluble
resin particles preferably having a core/shell structure. However, there is no disclosure
in this reference of the use of a combination of water-insoluble, cationic, polymeric
particles and particles having a core/shell structure. An element with an image-receiving
layer that does not contain water-insoluble, cationic resin particles would not have
good image quality. An element with an image-receiving layer that does not contain
particles having a core/shell structure would exhibit cracking.
[0009] U.S. Patent 6,099,956 relates to a recording medium comprising a support with a receptive
layer coated thereon. The receptive layer comprises a water insoluble polymer, which
is preferably, a copolymer comprising a styrene core with an acrylic ester shell.
However, there is no disclosure in this reference of the use of a combination of water-insoluble,
cationic, polymeric particles and particles having a core/shell structure. An element
with an image-receiving layer that does not contain water-insoluble, cationic resin
particles would not have good image quality. An element with an image-receiving layer
that does not contain particles having a core/shell structure would exhibit cracking.
[0010] It is an object of this invention to provide a porous ink jet recording element that
has instant dry time when used in ink jet printing. It is another object of this invention
to provide a porous recording element that has good coating quality, especially reduced
cracking. It is another object of this invention to provide an ink jet recording element
that exhibits good image quality after printing. Still another object of the invention
is to provide a printing method using the above described element.
[0011] These and other objects are achieved in accordance with the invention, which comprises
an ink jet recording element comprising a substrate having thereon a porous image-receiving
layer comprising
a) organic particles encapsulated with an organic polymer having a Tg of less than
100°C; and
b) water-insoluble, cationic, polymeric particles.
[0012] The ink jet recording element of the invention has good coating and image quality
when used in ink jet printing.
[0013] Another embodiment of the invention relates to an ink jet printing method comprising
the steps of:
A) providing an ink jet printer that is responsive to digital data signals;
B) loading the printer with ink jet recording element described above;
C) loading the printer with an ink jet ink composition; and
D) printing on the image-receiving layer using the ink jet ink composition in response
to the digital data signals.
[0014] Any organic particle may be used to prepare the encapsulated particles employed in
the invention. In a preferred embodiment, the organic particles are polymeric particles,
such as particles made from poly(methylmethacrylate), poly(styrene), poly(p-methylstyrene),
poly(t-butylacrylamide), poly(styrene-co-methylmethacrylate), poly(styrene-co-t-butylacrylamide),
poly(methylmethacrylate-co-t-butylacrylamide), and homopolymers derived from p-cyanophenyl
methacrylate, pentachlorophenyl acrylate, methacrylonitrile, isobornyl methacrylate,
phenyl methacrylate, acrylonitrile, isobornyl acrylate, p-cyanophenyl acrylate, 2-chloroethyl
acrylate, 2-chloroethyl methacrylate, 2-naphthyl acrylate, n-isopropyl acrylamide,
1-fluoromethyl methacrylate, isopropyl methacrylate, and 2-hydroxypropyl methacrylate.
In a preferred embodiment of the invention, the core polymer is derived from a styrene-containing
monomer or an acrylate-containing monomer, such as poly(methylmethacrylate), poly(styrene),
poly(p-methylstyrene), poly(t-butylacrylamide) or poly(styrene-co-methylmethacrylate).
In another preferred embodiment of the invention, the particle size of the inorganic
particles is from 5 nm to 1000 nm. In yet another preferred embodiment of the invention,
the Tg of the organic particle is at least 60°C, preferably from 60°C to 150°C.
[0015] The encapsulated particles used in the invention may be prepared in a preferred embodiment
by polymerizing one or more monomers in the presence of the organic particles. Useful
polymerization techniques can be found in "Emulsion Polymerization and Emulsion Polymers",
edited by P.A. Lovell and M.S. El-Aassar, John Wiley and Sons, 1997. Another embodiment
relates to preparing the encapsulated particles by adsorbing polymer onto the surface
of the organic particles. Another embodiment relates to preparing the encapsulated
particles by forming chemical bonds between the organic particles and the polymer
either before or after it is formed from the monomer.
[0016] The organic polymer used for encapsulation of the organic particles employed in the
invention has a Tg of less than 100°C, preferably from -50°C to 65°C. Methods for
determining Tg values of organic polymers are described in "Introduction to Physical
Polymer Science", 2nd Edition by L.H. Sperling, published by John Wiley & Sons, Inc.,
1992. For each of the organic polymers in Table 1 below, the Tg value was calculated
as the weighted sum of the Tg values for homopolymers derived from each of the individual
monomers,
i, that make up the polymer:

where
W is the weight percent of monomer
i in the organic polymer, and
X is the Tg value for the homopolymer derived from monomer
i. Tg values for the homopolymers were taken from "Polymer Handbook", 2nd Edition by
J. Brandrup and E.H. Immergut, Editors, published by John Wiley & Sons, Inc., 1975.
[0017] In a preferred embodiment of the invention, monomers used to prepare the organic
polymers of the encapsulated particles include acrylate and styrene monomers that
may have a cationic, anionic, or nonionic functionality such as quaternary ammonium,
pyridinium, imidazolium, sulfonate, carboxylate or phosphonate groups. Examples of
useful monomers include: n-butyl acrylate, n-ethylacrylate, 2-ethylhexylacrylate,
methoxyethylacrylate, methoxyethoxy-ethylacrylate, ethoxyethylacrylate, ethoxyethoxyethylacrylate,
2-ethylhexyl-methacrylate, n-propylacrylate, hydroxyethylacrylate, etc. and cationic
monomers such as a salt of trimethylammoniumethyl acrylate and trimethylammoniumethyl
methacrylate, a salt of triethylammoniumethyl acrylate and triethylammoniumethyl methacrylate,
a salt of dimethylbenzylammoniumethyl acrylate and dimethylbenzylammoniumethyl methacrylate,
a salt of dimethylbutylammoniumethyl acrylate and dimethylbutylammoniumethyl methacrylate,
a salt of dimethylhexylammoniumethyl acrylate and dimethylhexylammoniumethyl methacrylate,
a salt of dimethyloctylammoniumethyl acrylate and dimethyloctylammoniumethyl methacrylate,
a salt of dimethyldodeceylammoniumethyl acrylate and dimethyldocecylammoniumethyl
methacrylate, a salt of dimethyloctadecylammoniumethyl acrylate and dimethyloctadecylammoniumethyl
methacrylate, etc. Salts of these cationic monomers that can be used include chloride,
bromide, methylsulfate, triflate, etc.
[0018] Examples of the organic polymers which can be used in the invention to prepare the
encapsulated particles include poly(n-butylacrylate-covinylbenzyltrimethylammonium
chloride), poly(n-butylacrylate-covinylbenzyltrimethylammonium bromide), poly(n-butylacrylate-covinylbenzyldimethylbenzylammonium
chloride) and poly(n-butylacrylate-covinylbenzyldimethyloctadecylammonium chloride).
In a preferred embodiment of the invention, the polymer can be poly(n-butyl acrylate),
poly(2-ethylhexyl acrylate), poly(methoxyethylacrylate), poly(ethoxyethylacrylate),
poly(n-butylacrylate-co-trimethylammoniumethyl acrylate methylsulfate), poly(n-butylacrylate-co-trimethylammoniumethyl
methacrylate methylsulfate) or poly(n-butylacrylate-co-vinylbenzyltrimethylammonium
chloride).
[0019] Any weight ratio of organic particle to organic polymer in the encapsulated particles
may be used. In a preferred embodiment, the weight ratio is 0.2:1 to 20:1. In another
preferred embodiment, the weight ratio is 0.5:1 to 10:1.
[0020] Following are examples of organic particles encapsulated with an organic polymer
which can be used in the invention:
Table 1
Encapsulated Particle |
Organic Particle, A |
Organic Polymer, B |
Tg of B(°C) |
Ratio of A/B |
1 |
Poly(styrene) |
Poly(n-butyl methacrylate-co-ethyl methacrylate) (1:1) |
40 |
1:1 |
2 |
Poly(styrene) |
Poly(ethyl methacrylate) |
60 |
1:1 |
3 |
Poly(styrene) |
Poly(ethyl methacrylate-co-methyl methacrylate) (1:1) |
82 |
1:1 |
4 |
Poly(styrene) |
Poly(n-butylacrylate-co-trimethylammoniumethyl methacrylate methylsulfate) (1:1) |
12 |
1:1 |
5 |
Poly(methyl methacrylate) |
Poly(n-butylacrylate-co-trimethylammoniumethyl methacrylate methylsulfate) (2:1) |
1 |
10:1 |
6 |
Poly(methyl methacrylate) |
Poly(ethyl methacrylate-co-trimethylammoniumethyl methacrylate methylsulfate) (2:1) |
58 |
0.5:1 |
[0021] In a preferred embodiment of the invention, additional particles may be added to
the image-receiving layer such as inorganic particles, e.g., metal oxides or hydroxides,
such as alumina, boehmite, hydrated aluminum oxide, titanium oxide or zirconium oxide;
clay; calcium carbonate; calcined clay; inorganic silicates; or barium sulfate. Organic
particles such as polymeric beads may also be used. Examples of organic particles
useful in the invention are disclosed and claimed in U.S. Patent Application Serial
Numbers: 09/458,401, filed Dec. 10, 1999; 09/608,969, filed June 30, 2000; 09/607,417,
filed June 30, 2000; 09/608,466 filed June 30, 2000; 09/607,419, filed June 30, 2000;
and 09/822,731, filed March 30, 2001. In still yet another preferred embodiment, the
mean particle size of these additional particles is up to 5 µm.
[0022] The water insoluble, cationic, polymeric particles useful in the invention can be
in the form of a latex, water dispersible polymer, beads, or core/shell particles
wherein the core is organic or inorganic and the shell in either case is a cationic
polymer. Such particles can be products of addition or condensation polymerization,
or a combination of both. They can be linear, branched, hyper-branched, grafted, random,
blocked, or can have other polymer microstructures well known to those in the art.
They also can be partially crosslinked. Examples of core/shell particles useful in
the invention are disclosed and claimed in U.S. Patent Application Serial No. 09/772,097,
of Lawrence et al., Ink Jet Printing Method, filed January 26, 2001. Examples of water
dispersible particles useful in the invention are disclosed and claimed in U.S. Patent
Application Serial No. 09/770,128, of Lawrence et al., Ink Jet Printing Method, filed
January 26, 2001; and U.S. Patent Application Serial No.09/770,127, of Lawrence et
al., Ink Jet Printing Method, filed January 26, 2001. In a preferred embodiment, the
water insoluble, cationic, polymeric particles comprise at least 20 mole percent of
a cationic mordant moiety.
[0023] In another preferred embodiment of the invention, the water insoluble, cationic,
polymeric particles which may be used in the invention are in the form of a latex
which contains a polymer having a quaternary ammonium salt moiety. In yet another
preferred embodiment, the water-insoluble, cationic, polymeric particles comprises
a mixture of latexes containing a polymer having a (vinylbenzyl)trimethyl quaternary
ammonium salt moiety and a polymer having a (vinylbenzyl)dimethylbenzyl quaternary
ammonium salt moiety.
[0024] The water insoluble, cationic, polymeric particles useful in the invention can be
derived from nonionic, anionic, or cationic monomers. In a preferred embodiment, combinations
of nonionic and cationic monomers are employed. In general, the amount of cationic
monomer employed in the combination is at least 20 mole percent.
[0025] The nonionic, anionic, or cationic monomers employed can include neutral, anionic
or cationic derivatives of addition polymerizable monomers such as styrenes, alpha-alkylstyrenes,
acrylate esters derived from alcohols or phenols, methacrylate esters, vinylimidazoles,
vinylpyridines, vinylpyrrolidinones, acrylamides, methacrylamides, vinyl esters derived
from straight chain and branched acids (e.g., vinyl acetate), vinyl ethers (e.g.,
vinyl methyl ether), vinyl nitriles, vinyl ketones, halogen-containing monomers such
as vinyl chloride, and olefins, such as butadiene.
[0026] The nonionic, anionic, or cationic monomers employed can also include neutral, anionic
or cationic derivatives of condensation polymerizable monomers such as those used
to prepare polyesters, polyethers, polycarbonates, polyureas and polyurethanes.
[0027] The water insoluble, cationic, polymeric particles employed in this invention can
be prepared using conventional polymerization techniques including, but not limited
to bulk, solution, emulsion, or suspension polymerization. In a preferred embodiment
of the invention, the water insoluble, cationic, polymeric particles employed have
a mean particle size of from 10 to 500 nm.
[0028] Examples of water insoluble, cationic, polymeric particles which may be used in the
invention include those described in U.S. Patent 3,958,995. Specific examples of these
polymers include:
Polymer A. Copolymer of (vinylbenzyl)trimethylammonium chloride and divinylbenzene
(87:13 molar ratio)
Polymer B. Terpolymer of styrene, (vinylbenzyl)dimethylbenzylamine and divinylbenzene
(49.5:49.5:1.0 molar ratio)
Polymer C. Terpolymer of butyl acrylate, 2-aminoethylmethacrylate hydrochloride and
hydroxyethylmethacrylate (50:20:30 molar ratio)
Polymer D. Copolymer of styrene, dimethylacrylamide, vinylbenzylimidazole and 1-vinylbenzyl-3-hydroxyethylimidazolium
chloride (40:30:10:20 molar ratio)
Polymer E. Copolymer of styrene, 4-vinylpyridine and N-(2-hydroxyethyl)-4-vinylpyridinium
chloride (30:38:32 molar ratio)
Polymer F. Copolymer of styrene, (vinylbenzyl)dimethyloctylammonium chloride), isobutoxymethyl
acrylamide and divinylbenzene (40:20:34:6 molar ratio)
[0029] In a preferred embodiment of the invention, the encapsulated organic particles comprise
up to 50 wt. % of the image-receiving layer.
[0030] The amount of water insoluble, cationic, polymeric particles used should be high
enough so that the images printed on the recording element will have a sufficiently
high density, but low enough so that the interconnected pore structure formed by the
aggregates is not filled. In a preferred embodiment of the invention, the water-insoluble,
cationic, polymeric particles are present in an amount of from 5 to 30 weight % of
the image-receiving layer.
[0031] The image-receiving layer employed in the invention may also contain a polymeric
binder in an amount insufficient to alter its porosity. In a preferred embodiment,
the polymeric binder is a hydrophilic polymer, such as poly(vinyl alcohol), poly(vinyl
pyrrolidone), gelatin, cellulose ethers, poly(oxazolines), poly(vinylacetamides),
partially hydrolyzed poly(vinyl acetate/vinyl alcohol), poly(acrylic acid), poly(acrylamide),
poly(alkylene oxide), sulfonated or phosphated polyesters and polystyrenes, casein,
zein, albumin, chitin, chitosan, dextran, pectin, collagen derivatives, collodian,
agar-agar, arrowroot, guar, carrageenan, tragacanth, xanthan, rhamsan and the like;
or a low Tg latex such as poly(styrene-co-butadiene), a polyurethane latex, a polyester
latex, poly(n-butyl acrylate), poly(n-butyl methacrylate), poly(2-ethylhexyl acrylate),
a copolymer of n-butylacrylate and ethylacrylate, a copolymer of vinylacetate and
n-butylacrylate, etc. The polymeric binder should be chosen so that it is compatible
with the aforementioned particles.
[0032] The amount of binder used should be sufficient to impart cohesive strength to the
ink jet recording element, but should also be minimized so that the interconnected
pore structure formed by the aggregates is not filled in by the binder. In a preferred
embodiment of the invention, the weight ratio of the binder to the total amount of
particles is from 1:20 to 1:5.
[0033] In addition to the image-receiving layer, the recording element may also contain
a base layer, next to the support, the function of which is to absorb the solvent
from the ink. Materials useful for this layer include inorganic particles and polymeric
binder.
[0034] In addition to the image-receiving layer, the recording element may also contain
a layer on top of the image-receiving layer, the function of which is to provide gloss.
Materials useful for this layer include sub-micron inorganic particles and/or polymeric
binder.
[0035] The support for the ink jet recording element used in the invention can be any of
those usually used for ink jet receivers, such as resin-coated paper, paper, polyesters,
or microporous materials such as polyethylene polymer-containing material sold by
PPG Industries, Inc., Pittsburgh, Pennsylvania under the trade name of Teslin®, Tyvek®
synthetic paper (DuPont Corp.), impregnated paper such as Duraform®, and OPPalyte®
films (Mobil Chemical Co.) and other composite films listed in U.S. Patent 5,244,861.
Opaque supports include plain paper, coated paper, synthetic paper, photographic paper
support, melt-extrusion-coated paper, and laminated paper, such as biaxially oriented
support laminates. Biaxially oriented support laminates are described in U.S. Patents
5,853,965; 5,866,282; 5,874,205; 5,888,643; 5,888,681; 5,888,683; and 5,888,714. These
biaxially oriented supports include a paper base and a biaxially oriented polyolefin
sheet, typically polypropylene, laminated to one or both sides of the paper base.
Transparent supports include glass, cellulose derivatives, e.g., a cellulose ester,
cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose
acetate butyrate; polyesters, such as poly(ethylene terephthalate), poly(ethylene
naphthalate), poly(1,4-cyclohexanedimethylene terephthalate), poly(butylene terephthalate),
and copolymers thereof; polyimides; polyamides; polycarbonates; polystyrene; polyolefins,
such as polyethylene or polypropylene; polysulfones; polyacrylates; polyetherimides;
and mixtures thereof. The papers listed above include a broad range of papers, from
high end papers, such as photographic paper to low end papers, such as newsprint.
In a preferred embodiment, Ektacolor paper made by Eastman Kodak Co. is employed.
[0036] The support used in the invention may have a thickness of from 50 to 500 µm, preferably
from 75 to 300 µm. Antioxidants, antistatic agents, plasticizers and other known additives
may be incorporated into the support, if desired.
[0037] In order to improve the adhesion of the image-receiving layer to the support, the
surface of the support may be subjected to a corona-discharge treatment prior to applying
the image-receiving layer. The adhesion of the image-receiving layer to the support
may also be improved by coating a subbing layer on the support. Examples of materials
useful in a subbing layer include halogenated phenols and partially hydrolyzed vinyl
chloride-co-vinylacetate polymer.
[0038] The coating composition can be coated either from water or organic solvents, however
water is preferred. The total solids content should be selected to yield a useful
coating thickness in the most economical way, and for particulate coating formulations,
solids contents from 10-40 wt. % are typical.
[0039] Coating compositions employed in the invention may be applied by any number of well
known techniques, including dip-coating, wound-wire rod coating, doctor blade coating,
gravure and reverse-roll coating, slide coating, bead coating, extrusion coating,
curtain coating and the like. Known coating and drying methods are described in further
detail in Research Disclosure no. 308119, published Dec. 1989, pages 1007 to 1008.
Slide coating is preferred, in which the base layers and overcoat may be simultaneously
applied. After coating, the layers are generally dried by simple evaporation, which
may be accelerated by known techniques such as convection heating.
[0040] The coating composition may be applied to one or both substrate surfaces through
conventional pre-metered or post-metered coating methods such as blade, air knife,
rod, roll coating, etc. The choice of coating process would be determined from the
economics of the operation and in turn, would determine the formulation specifications
such as coating solids, coating viscosity, and coating speed.
[0041] The image-receiving layer thickness may range from 1 to 60 µm, preferably from 5
to 40 µm.
[0042] After coating, the ink jet recording element may be subject to calendering or supercalendering
to enhance surface smoothness. In a preferred embodiment of the invention, the ink
jet recording element is subject to hot soft-nip calendering at a temperature of 65
° C and a pressure of 14000 kg/m at a speed of from 0.15 m/s to 0.3 m/s.
[0043] In order to impart mechanical durability to an ink jet recording element, crosslinkers
which act upon the binder discussed above may be added in small quantities. Such an
additive improves the cohesive strength of the layer. Crosslinkers such as carbodiimides,
polyfunctional aziridines, aldehydes, isocyanates, epoxides, polyvalent metal cations,
and the like may all be used.
[0044] To improve colorant fade, UV absorbers, radical quenchers or antioxidants may also
be added to the image-receiving layer as is well known in the art. Other additives
include pH modifiers, adhesion promoters, rheology modifiers, surfactants, biocides,
lubricants, dyes, optical brighteners, matte agents, antistatic agents, etc. In order
to obtain adequate coatability, additives known to those familiar with such art such
as surfactants, defoamers, alcohol and the like may be used. A common level for coating
aids is 0.01 to 0.30 wt. % active coating aid based on the total solution weight.
These coating aids can be nonionic, anionic, cationic or amphoteric. Specific examples
are described in MCCUTCHEON's Volume 1: Emulsifiers and Detergents, 1995, North American
Edition.
[0045] Ink jet inks used to image the recording elements of the present invention are well-known
in the art. The ink compositions used in ink jet printing typically are liquid compositions
comprising a solvent or carrier liquid, dyes or pigments, humectants, organic solvents,
detergents, thickeners, preservatives, and the like. The solvent or carrier liquid
can be solely water or can be water mixed with other water-miscible solvents such
as polyhydric alcohols. Inks in which organic materials such as polyhydric alcohols
are the predominant carrier or solvent liquid may also be used. Particularly useful
are mixed solvents of water and polyhydric alcohols. The dyes used in such compositions
are typically water-soluble direct or acid type dyes. Such liquid compositions have
been described extensively in the prior art including, for example, U.S. Patents 4,381,946;
4,239,543 and 4,781,758.
[0046] The following examples are provided to illustrate the invention.
Synthesis of Encapsulated Particle 1 Employed in the Invention
[0047] 200 g of deionized water and 2 g of cetyltrimethylammonium bromide (CTAB) were mixed
in a 2 L 3-neck round bottom flask equipped with a mechanical stirrer, condenser and
nitrogen inlet. The flask was immersed in a constant temperature bath at 80°C and
purged with nitrogen for 20 min. 0.5 g of 2,2'-azobis(2-methylpropionamidine) hydrochloride
(AMA) was then added.
[0048] A monomer emulsion comprising 200 g of styrene, 2 g of AMA, 20 g of CTAB and 200
g of deionized water was added over one hour with constant agitation. The reaction
mixture was stirred for an additional 30 minutes. A second monomer emulsion comprising
100 g of n-butyl methacrylate, 100 g of ethyl methacrylate, 2 g of AMA, 20 g of CTAB
and 200 g of deionized water was added over one hour. The reaction mixture was stirred
for an additional hour and then cooled to 60°C. 4 mL of 10 wt. % t-butyl hydroperoxide
and 10 wt. % formaldehyde-sulfite were added and the resulting reaction mixture stirred
for 30 minutes at 60°C. The reaction mixture was then cooled to room temperature and
filtered. The resulting dispersion was 40 wt. % solids and the particle size was 68
nm.
Synthesis of Encapsulated Particle 2 Employed in the Invention
[0049] 200 g of deionized water and 2 g of CTAB were mixed in a 2 L 3-neck round bottom
flask equipped with a mechanical stirrer, condenser and nitrogen inlet. The flask
was immersed in a constant temperature bath at 80 ° C and purged with nitrogen for
20 min. 0.5 g of AMA was then added.
[0050] A monomer emulsion comprising 200 g of styrene, 2 g of AMA, 20 g of CTAB and 200
g of deionized water was added over one hour with constant agitation. The reaction
mixture was stirred for an additional 30 minutes. A second monomer emulsion comprising
200 g of ethyl methacrylate, 2 g of AMA, 20 g of CTAB and 200 g of deionized water
was added over one hour. The reaction mixture was stirred for an additional hour and
then cooled to 60 °C. 4 mL of 10 wt. % t-butyl hydroperoxide and 10 wt. % formaldehyde-sulfite
were added and the resulting reaction mixture stirred for 30 minutes at 60 ° C. The
reaction mixture was then cooled to room temperature and filtered. The resulting dispersion
was 41 wt. % solids and the particle size was 72 nm.
Synthesis of Encapsulated Particle 3 Employed in the Invention
[0051] 200 g of deionized water and 2 g of CTAB were mixed in a 2 L 3-neck round bottom
flask equipped with a mechanical stirrer, condenser and nitrogen inlet. The flask
was immersed in a constant temperature bath at 80 ° C and purged with nitrogen for
20 min. 0.5 g of AMA was then added.
[0052] A monomer emulsion comprising 200 g of styrene, 2 g of AMA, 20 g of CTAB and 200
g of deionized water was added over one hour with constant agitation. The reaction
mixture was stirred for an additional 30 minutes. A second monomer emulsion comprising
100 g of ethyl methacrylate, 100 g of methyl methacrylate, 2 g of AMA, 20 g of CTAB
and 200 g of deionized water was added over one hour. The reaction mixture was stirred
for an additional hour and then cooled to 60 ° C. 4 mL of 10 wt. % t-butyl hydroperoxide
and 10 wt. % formaldehyde-sulfite were added and the resulting reaction mixture stirred
for 30 minutes at 60°C. The reaction mixture was then cooled to room temperature and
filtered. The resulting dispersion was 39 wt. % solids and the particle size was 70
nm.
Element 1 of the Invention
[0053] A coating solution for a base layer was prepared by mixing 254 dry g of precipitated
calcium carbonate Albagloss-s® (Specialty Minerals Inc.) as a 70% solution, 22 dry
g of silica gel Gasil® 23F (Crosfield Ltd.), 2.6 dry g of poly(vinyl alcohol) Airvol®
125 (Air Products) as a 10% solution, 21 dry g of styrene-butadiene latex CP692NA®
(Dow Chemical Co.) as a 50% solution and 0.8 g of Alcogum® L-229 (Alco Chemical Co.).
The solids of the coating solution was adjusted to 35 wt. % by adding water. The base
layer coating solution was bead-coated at 25 ° C on Ektacolor Edge Paper (Eastman
Kodak Co.) and dried by forced air at 60 ° C. The thickness of the base layer was
25 µm or 27 g/m
2.
[0054] A coating solution for the image receiving layer was prepared by mixing 15.0 dry
g of alumina Dispal® 14N4-80 (Condea Vista) as a 20 wt. % solution, 2.4 dry g of fumed
alumina Cab-O-Sperse® PG003 (Cabot Corp.) as a 40 wt. % solution, 0.6 dry g of poly(vinyl
alcohol) Gohsenol® GH-17 (Nippon Gohsei Co. Ltd.) as a 10 wt. % solution, 1.2 dry
g of Polymer A as a 20 wt. % solution, 1.2 dry g of Polymer B as a 20 wt. % solution,
0.9 dry g of Encapsulated Particles 1 as a 40 wt. % solution, 0.1 g of Silwet® L-7602
(Witco. Corp.), 0.2 g of Silwet® L-7230 (Witco. Corp.) and water to total 153 g.
[0055] The image-receiving layer coating solution was bead-coated at 25 ° C on top of the
base layer described above. The recording element was then dried by forced air at
60°C for 80 seconds followed by 38°C for 8 minutes. The thickness of the image-receiving
layer was 8 µm or 8.6 g/m
2.
Element 2 of the Invention
[0056] This element was prepared the same as Element 1 except that 0.9 dry g of Encapsulated
Particles 2 as a 41 wt. % solution was used instead of Encapsulated Particles 1.
Element 3 of the Invention
[0057] This element was prepared the same as Element 1 except that 0.9 dry g of Encapsulated
Particles 3 as a 39 wt. % solution was used instead of Encapsulated Particles 1.
Synthesis of Comparative Encapsulated Particles 1 (Tg of encapsulating polymer is
greater than 100° C.)
[0058] 200 g of deionized water and 2 g of CTAB were mixed in a 2 L 3-neck round bottom
flask equipped with a mechanical stirrer, condenser and nitrogen inlet. The flask
was immersed in a constant temperature bath at 80 ° C and purged with nitrogen for
20 min. 0.5 g of AMA was then added.
[0059] A monomer emulsion comprising 200 g of styrene, 2 g of AMA, 20 g of CTAB and 200
g of deionized water was added over one hour with constant agitation. The reaction
mixture was stirred for an additional 30 minutes. A second monomer emulsion comprising
200 g of methyl methacrylate, 2 g of AMA, 20 g of CTAB and 200 g of deionized water
was added over one hour. The reaction mixture was stirred for an additional hour and
then cooled to 60 °C. 4 mL of 10 wt. % t-butyl hydroperoxide and 10 wt. % formaldehyde-sulfite
were added and the resulting reaction mixture stirred for 30 minutes at 60°C. The
reaction mixture was then cooled to room temperature and filtered. The resulting dispersion
was 40 wt. % solids and the particle size was 70 nm. The Tg of the encapsulating organic
polymer is 105°C.
Synthesis of Comparative Encapsulated Particles 2 (Tg of encapsulating polymer is
greater than 100° C.)
[0060] 200 g of deionized water and 2 g of CTAB were mixed in a 2 L 3-neck round bottom
flask equipped with a mechanical stirrer, condenser and nitrogen inlet. The flask
was immersed in a constant temperature bath at 80°C and purged with nitrogen for 20
min. 0.5 g of AMA was then added.
[0061] A monomer emulsion comprising 200 g of styrene, 2 g of AMA, 20 g of CTAB and 200
g of deionized water was added over one hour with constant agitation. The reaction
mixture was stirred for an additional 30 minutes. A second monomer emulsion comprising
190 g of methyl methacrylate, 10 g of ethylene glycol dimethacrylate, 2 g of AMA,
20 g of CTAB and 200 g of deionized water was added over one hour. The reaction mixture
was stirred for an additional hour and then cooled to 60°C. 4 mL of 10 wt. % t-butyl
hydroperoxide and 10 wt. % formaldehyde-sulfite were added and the resulting reaction
mixture stirred for 30 minutes at 60°C. The reaction mixture was then cooled to room
temperature and filtered. The resulting dispersion was 40 wt. % solids and the particle
size was 76 nm.
[0062] The Tg of the encapsulating organic polymer is 110°C. The presence of a small amount
of the ethyleneglycol dimethacrylate increases the Tg value of the homopolymer derived
from methyl methacrylate by 5 °C.
Comparative Element 1
[0063] This element was prepared the same as Element 1 except that 0.9 dry g of Comparative
Encapsulated Particles 1 as a 40 wt. % solution was used instead of Encapsulated Particles
1.
Comparative Element 2
[0064] This element was prepared the same as Element 1 except that 0.9 dry g of Comparative
Encapsulated Particles 2 as a 40 wt. % solution was used instead of Encapsulated Particles
1.
Coating Quality
[0065] The above dried coatings for visually evaluated for cracking defects. Results are
tabulated in Table 2 below.
Image Quality & Dry Time
[0066] An Epson Stylus Color 740 printer for dye-based inks using Color Ink Cartridge S020191/IC3CL01
was used to print on the above recording elements. The image consisted of adjacent
patches of cyan, magenta, yellow, black, green, red and blue patches, each patch being
in the form of a rectangle 0.4 cm in width and 1.0 cm in length. Bleed between adjacent
color patches was qualitatively assessed. A second image was printed, and immediately
after ejection from the printer, the image was wiped with a soft cloth. The dry time
was rated as 1 if no ink and was smudged on the image. The dry time was rated as 2
if some ink smudged, and 3 if a lot of ink smudged. Results are shown in Table 2 as
follows:
Table 2
Recording Element |
Coating Quality |
Image Quality |
Dry Time |
1 |
No cracking |
Little bleeding |
1 |
2 |
No cracking |
Little bleeding |
1 |
3 |
No cracking |
Little bleeding |
1 |
Comparative 1 |
Cracking |
Severe Bleeding |
2 |
Comparative 2 |
Cracking |
Severe Bleeding |
2 |
[0067] The above table shows that the recording elements of the invention have good coating
quality, image quality and instant dry time as compared to the comparative recording
elements.