[0001] The present invention relates to a porous ink jet recording element and printing
method using the element.
[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 and 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-receiving 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] An important characteristic of ink jet recording elements is their need to dry quickly
after printing. To this end, porous recording elements have been developed which provide
nearly instantaneous drying as long as they have sufficient thickness and pore volume
to effectively contain the liquid ink. For example, a porous recording element can
be manufactured by cast coating, in which a particulate-containing coating is applied
to a support and is dried in contact with a polished smooth surface.
[0005] When a porous recording element is manufactured, it is difficult to co-optimize the
image-receiving layer surface appearance and ink drying times. Good image-receiving
layer surface appearance is obtained when it is virtually crack-free. A crack-free
surface appearance can be obtained merely by adding more binder to the image-receiving
layer. However, adding more binder increases dry time since the binder fills the pores
in the image-receiving layer. Therefore, it is difficult to obtain an image-receiving
layer which has a crack-free surface yet is fast-drying.
[0006] Another problem encountered with a recording element is ink coalescence which occurs
when adjacent ink dots coalesce which leads to nonuniform density.
[0007] U.S. Patent 6,037,050 and EP 888,904 relate to an ink jet recording element wherein
an ink absorption layer comprises inorganic particles such as silica and a poly(vinyl
alcohol) binder that is crosslinked with a hardener. However, there is no disclosure
in these references that the crosslinker should be present in an amount greater than
10%, based on the binder.
[0008] It is an object of this invention to provide a porous ink jet recording element that
exhibits good overall appearance without cracking and has an excellent dry time and
reduced ink coalescence. It is another object of the invention to provide a printing
method using the above-described element.
[0009] These and other objects are achieved in accordance with the invention which comprises
an ink jet recording element comprising a support having thereon a porous image-receiving
layer comprising particles, a poly(vinyl alcohol) binder and a crosslinking agent,
the particles having a primary particle size of from 7 to 40 nm in diameter which
may be aggregated up to 300 nm, and the crosslinking agent being present in an amount
of at least 20 weight % of the poly(vinyl alcohol) binder.
[0010] By use of the invention, a porous ink jet recording element is obtained that exhibits
good overall appearance without cracking and has an excellent dry time and reduced
ink coalescence.
[0011] 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 an ink jet recording element as described above;
C) loading said printer with an ink jet ink composition; and
D) printing on said image-receiving layer using said ink jet ink composition in response
to said digital data signals.
[0012] Examples of particles useful in the invention include alumina, boehmite, clay, calcium
carbonate, titanium dioxide, calcined clay, aluminosilicates, silica, barium sulfate,
or polymeric beads. The particles may be porous or nonporous. In a preferred embodiment
of the invention, the particles are metallic oxides, preferably fumed. While many
types of inorganic and organic particles are manufactured by various methods and commercially
available for an image-receiving layer, porosity of the ink-receiving layer is necessary
in order to obtain very fast ink drying. The pores formed between the particles must
be sufficiently large and interconnected so that the printing ink passes quickly through
the layer and away from the outer surface to give the impression of fast drying. At
the same time, the particles must be arranged in such a way so that the pores formed
between them are sufficiently small that they do not scatter visible light.
[0013] The particles may be in the form of primary particles, or in the form of secondary
aggregated particles. The aggregates are comprised of smaller primary particles 7
to 40 nm in diameter, and being aggregated up to 300 nm in diameter. The pores in
a dried coating of such aggregates fall within the range necessary to ensure low optical
scatter yet sufficient ink solvent uptake.
[0014] Any fumed metallic oxide particles may be used in the invention. Examples of such
particles include fumed alumina, silica, titania, cationic silica, antimony(III) oxide,
chromium(III) oxide, iron(III) oxide, germanium(IV) oxide, vanadium(V) oxide, or tungsten(VI)
oxide. Preferred examples of fumed metallic oxides which may be used in the invention
include silica and alumina fumed oxides. Fumed oxides are available in dry form or
as dispersions of the aggregates mentioned above.
[0015] The process for fuming metallic oxides is well known in the art. For example, reference
may be made to Technical Bulletin Pigments, no. 56, Highly Dispersed Metallic Oxides
Produced by the AEROSIL ® Process, by DegussaAG., 1995.
[0016] Any poly(vinyl alcohol) may be used in the invention. In a preferred embodiment,
the poly(vinyl alcohol) has an average viscosity greater than 20 cp when employed
in a 4% aqueous solids solution at 20°C. Specific examples of such poly(vinyl alcohols)
which may be used in the invention include the following:
Table 1
|
Poly(vinyl alcohol) |
Average Viscosity @ 4% (cp) |
PVA-A |
Gohsenol® GH-17 |
301 |
PVA-B |
Gohsenol® GH-23 |
521 |
PVA-C |
Gohsenol® N300 |
27.51 |
PVA-D |
Elvanol® 52-22 |
23.52 |
1Trade publication, Nippon Gohsei Co., Ltd. |
2Trade publication, DuPont Corp. |
[0017] The amount of poly(vinyl alcohol) binder used should be sufficient to impart cohesive
strength to the image-receiving layer, but as small as possible 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 particles is from
1:20 to 1:5.
[0018] The image-receiving layer may also contain a mordant. Examples of mordants which
may be used include water-soluble cationic polymers, metal salts, water-insoluble
cationic polymeric particles 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 of even date herewith,
Docket 81894HEC. 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 of even date herewith, Docket 81815HEC; and
U.S. Patent Application Serial No. 09/70,127, of Lawrence et al., Ink Jet Printing
Method, filed of even date herewith, Docket 81817HEC.
[0019] Examples of crosslinkers which may be used in the invention include carbodiimides,
polyfunctional aziridines, aldehydes, isocyanates, epoxides, polyvalent metal cations,
acetals, ketals, etc. In a preferred embodiment of the invention, the crosslinker
is an aldehyde, an acetal or a ketal. In a more preferred embodiment, the crosslinker
is 2,3-dihydroxy-1,4-dioxane.
[0020] As noted above, the amount of crosslinking agent is present in an amount of at least
20 weight % of the poly(vinyl alcohol) binder. This amount is far beyond a typical
amount of crosslinking agent for poly(vinyl alcohol). For example, in Paper Coating
Additives, Robert J. Kane, TAPPI PRESS, Atlanta Ga., 1995, page 96, it is disclosed
that a typical aldehyde crosslinker, glyoxal, is used at 10% by weight relative to
the poly(vinyl alcohol). In a preferred embodiment of the invention, the crosslinking
agent is present in an amount of at least 40 weight %, more preferably 50 weight %,
of the poly(vinyl alcohol) binder.
[0021] Since the image-receiving layer is a porous layer comprising particles, the void
volume must be sufficient to absorb all of the printing ink. For example, if a porous
layer has 60 volume % open pores, in order to instantly absorb 32 cc/m
2 of ink, it must have a physical thickness of at least 54 µm.
[0022] 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.), 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, polyethylene-coated paper is employed.
[0023] 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.
[0024] In order to improve the adhesion of the ink-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.
[0025] 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.
[0026] 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% 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.
[0027] 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% are typical.
[0028] 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.
[0029] The following example is provided to illustrate the invention.
EXAMPLE
Element 1 of the Invention
[0030] A coating solution was prepared by combining fumed alumina (Cab-O-Sperse® PG003,
Cabot Corp.), PVA-B and crosslinker 2,3-dihydroxy-1,4-dioxane (Clariant Corp.) in
a ratio of 88:10:2 to give an aqueous coating formulation of 30% solids by weight,
so that the crosslinking agent is present in an amount of 20 weight % of the poly(vinyl
alcohol) binder.
[0031] The layer was bead-coated at 40°C on polyethylene-coated paper base which had been
previously subjected to corona discharge treatment. The coating was then dried at
60°C by forced air to yield a recording element with a thickness of 40 µm.
Element 2 of the Invention
[0032] This element was prepared the same as Element 1 except that the ratio of components
was 87:10:3 to give an aqueous coating formulation of 30% solids by weight, so that
the crosslinking agent is present in an amount of 30 weight % of the poly(vinyl alcohol)
binder.
Element 3 of the Invention
[0033] This element was prepared the same as Element 1 except that the ratio of components
was 86:10:4 to give an aqueous coating formulation of 30% solids by weight, so that
the crosslinking agent is present in an amount of 40 weight % of the poly(vinyl alcohol)
binder.
Comparative Element C-1
[0034] This element was prepared the same as Element 1 except that PVA-D was used instead
of PVA-B, and the ratio of components was 84:15:1 to give an aqueous coating formulation
of 30% solids by weight, so that the crosslinking agent is present in an amount of
6.6 weight % of the poly(vinyl alcohol) binder.
Comparative Element C-2
[0035] This element was prepared the same as Element 1 except that PVA-D was used instead
of PVA-B, and the ratio of components was 86.5:12.5:1 to give an aqueous coating formulation
of 30% solids by weight, so that the crosslinking agent is present in an amount of
8 weight % of the poly(vinyl alcohol) binder.
Comparative Element C-3
[0036] This element was prepared the same as Element 1 except that PVA-D was used instead
of PVA-B, and the ratio of components was 89:10:1 to give an aqueous coating formulation
of 30% solids by weight, so that the crosslinking agent is present in an amount of
10 weight % of the poly(vinyl alcohol) binder.
Coating Quality
[0037] The above dried coatings were visually evaluated for cracking with the following
results:
Table 2
Recording Element |
Cracking |
1 |
None |
2 |
None |
3 |
None |
C-1 |
None |
C-2 |
None |
C-3 |
Some |
[0038] The above results show that neither any of the recording elements of the invention
nor two comparative elements exhibited any cracking.
Dry Time
[0039] Test images of cyan, magenta, yellow, red, green, blue and black bars, each 1.1 cm
by 13.5 cm, were printed on the above elements using an Epson Stylus® Photo 870 using
inks with catalogue number T008201. Immediately after ejection from the printer, a
piece of bond paper was placed over the printed image and rolled with a smooth, heavy
weight. Then the bond paper was separated from the printed image. Ink transferred
to the bond paper if the recording element was not dry. The length of the bar imaged
on the bond paper was measured and is proportional to the dry time. Dry times corresponding
to a length of about 40 cm or less are acceptable.
Table 3
Recording Element |
Proportional Dry Time (cm) |
1 |
6 |
2 |
2 |
3 |
6 |
C-1 |
91 |
C-2 |
91 |
C-3 |
65 |
[0040] The above results show that the elements of the invention had much better dry times
than all the comparative elements.
Coalescence
[0041] A test image of a green patch was printed on each of the above elements using an
Epson Stylus® Photo 870 using inks with catalogue number T008201. Coalescence of the
ink on the patches was visually rated as follows:
1 = None
2 = Slight
3 = Moderate
4 = Severe
[0042] The following results were obtained:
Table 4
Recording Element |
Coalescence |
1 |
3 |
2 |
2 |
3 |
1 |
C-1 |
4 |
C-2 |
4 |
C-3 |
4 |
[0043] The above results show that the recording elements of the invention had much less
coalescence than the comparative elements.
1. An ink jet recording element comprising a support having thereon a porous image-receiving
layer comprising particles, a poly(vinyl alcohol) binder and a crosslinking agent,
said particles having a primary particle size of from 7 to 40 nm in diameter which
may be aggregated up to 300 nm, and said crosslinking agent being present in an amount
of at least 20 weight % of said poly(vinyl alcohol) binder.
2. The recording element of Claim 1 wherein said crosslinking agent is present in an
amount of at least 40 weight % of said poly(vinyl alcohol) binder.
3. The recording element of Claim 1 wherein said crosslinking agent is present in an
amount of at least 50 weight % of said poly(vinyl alcohol) binder.
4. The recording element of Claim 1 wherein said crosslinker is an aldehyde, an acetal
or a ketal.
5. The recording element of Claim 1 wherein said crosslinker is 2,3-dihydroxy-1,4-dioxane.
6. The recording element of Claim 1 wherein said support is polyethylene-coated paper.
7. The recording element of Claim 1 wherein said image-receiving layer also contains
a mordant.
8. The recording element of Claim 1 wherein the weight ratio of said binder to said particles
is from 1:20 to 1:5.
9. The recording element of Claim 1 wherein said particles are metallic oxides.
10. An ink jet printing method comprising the steps of:
A) providing an ink jet printer that is responsive to digital data signals;
B) loading said printer with an ink jet recording element as described in claim 1;
C) loading said printer with an ink jet ink composition; and
D) printing on said image-receiving layer using said ink jet ink composition in response
to said digital data signals.