FIELD OF THE INVENTION
[0001] This invention relates to an ink receptive material comprising a support material
containing at least one layer consisting essentailly of a mixture of inorganic particles;
specifically a mixture of colloidal (< 1 micron) and noncolloidal inorganic particulates.
BACKGROUND OF THE INVENTION
[0002] Ink receptive materials for inkjet printing or other liquid marking processes typically
employ layers comprising materials which are particularly receptive to the solvent
or carrier making up the ink. For example, when inks are based primarily on water,
as they are for most commercially available desk top inkjet printers, the ink receiving
layer could be comprised of a hydrophilic material so that the capacity of the receiving
layer to swell in the ink solvent allows the printed areas to become quickly apparently
dry and also prevents flooding of the ink on the surface. Alternatively, the ink receiving
layer could be comprised primarily of particulate materials so that the coated layer
is highly porous and is therefore able to carry the ink away from the printed surface
quickly. By "primarily particulate" material, it is meant that most (over 50%) of
the volume of the image receptive layer comprises distinct particles, either never
in solution or precipitated during the coating process. This alternative would also
give the impression of fast drying and would limit any flooding of the surface in
areas of high ink deposit.
[0003] For surfaces in which high gloss is not required, the porous coating approach is
preferred as it is inexpensive and easily applied by common coating methods such as
gravure coating. The particles which make up such a porous coating can be polymeric
or inorganic, and may have a hydrophilic character. Such particles, when used for
paper coatings, are typically referred to as pigments. In order for a coating made
from a particulate material to have sufficient cohesive strength to avoid crumbling
or flaking from the support, polymeric binders are added to the coating formulation.
They act like glue to help adhere the particles to each other and to the coated support.
Typically, these polymers are solution polymers such as polyvinyl alcohol or casein;
or latex polymers such as styrene-butadiene or acrylonitrile-styrene-butadiene. If
a latex polymer is preferred over a solution polymer as a binder, typically more latex
is necessary in order to obtain sufficient cohesive strength in the layer. A further
addition to such a coating formulation or an additional overcoat is typically a crosslinker
capable of cross linking the hydroxyl or carboxyl groups introduced by the polymeric
binder. This cross linking provides additional water resistance to the coating. Still
further, polymeric mordants are often added to such ink receiving layers in order
to impart waterfastness to the printing inks.
[0004] US 5,616,409 describes an inkjet recording medium comprising a paper of defined density
and Stockigt sizing degree over which an ink receptive layer has been coated. The
coated layers comprise 75% pigment, 20% binder and 5% cationic polymeric mordant.
The pigment consists of porous synthetic amorphous silica powder with particle sizes
over 1 micron, and the binder is either polyvinyl alcohol or silanol-modified vinyl
alcohol
[0005] EP Application 0 754 560 describes a color inkjet recording sheet which is coated
from an aqueous formulation containing a water-soluble crosslinkable polymeric binder,
an absorptive pigment, a zirconium crosslinking agent, and a cationically modified
polymer. Binder examples include water soluble polymers such as polyvinyl alcohol,
hydroxyethyl cellulose and rice starch. The binder concentration, as a percent of
total pigment+binder content, ranges from 12.7% to 30.8%. The pigment used is silica
with a particle size ranging from 1-10 microns. The total solids content of the coatable
formulations ranged from 12.6% to 17.9%.
[0006] US 4,460,637 describes an inkjet recording sheet having one or more layers; the top
layer shows a large pore radius, while the overall layer or layers shows an additional
pore radius which is much smaller. The dual pore radii can be obtained two ways. One
is by forming two separate layers, in which the layer closest to the free surface
contains pigment particles greater than 1 micron in diameter, while the bottom layer
contains colloidal particles in the submicron range. The other method is by coating
a single layer in which the pigment is formed by agglomerating colloidal particles
before coating, or by choosing commercial pigments which are porous in nature. In
either case, the pigment containing layer must be coated with a binder polymer such
as polyvinyl alcohol in order to prevent the dusting which originates from cohesive
failure of the coated layer.
[0007] US 5,576,088 describes another two-layer ink receiving coating. The bottom layer
(layer closest to the support material) comprises a pigment and binder. The binder
is typically polyvinyl alcohol, and the pigment is a combination of large and colloidal
inorganic particles. Because of the presence of the polymeric binder, the solids content
of the base layer coating composition is 15%. The top layer also comprises pigment
and a synthetic polymeric binder. The pigment may be a combination of large and colloidal
particles (organic or inorganic), in which the content of colloidal-sized particles
is chosen to be high enough, preferably 90 to 100 weight per cent, to impart a particular
gloss. The binder content is kept low, so that coatings may be applied from higher
solids melts; from 20-40%.
[0008] It would be useful to have a coating formulation that is substantially free of organic
material as this would allow a substantial increase in coating composition solids.
SUMMARY OF THE INVENTION
[0009] The present invention discloses an inkjet recording medium comprising a substrate
coated on at least one surface with a coating composition comprising a mixture of
inorganic colloidal particles and non-colloidal pigments.
[0010] In another aspect of the invention there is disclosed an inkjet recording medium
comprising a substrate coated on at least one surface with a coating composition comprising
a mixture of inorganic colloidal particles and non-colloidal pigments.
[0011] The present inkjet recording medium provides superior liquid absorption through a
high level of porosity, resulting in fast ink drying and freedom from printed defects
which originate from ink flooding and coalescence. Further, it completely eliminates
the need for organic binders or fillers from the coating formulation used to produce
the ink receiving layer, so that viscosity buildup is minimized and coatings may be
acceptably deposited from very high solids melts. In this way, drying of the coated
film requires less energy due to less required water removal. Furthermore, without
polymeric binders porosity of the coating is enhanced. Such a composition provides
fast drying of printed inks. It also provides a low viscosity, high solids fraction
coating formulation which provides superior latitude in coating and drying processes
and reduced deformation of fibrous supports such as paper during the coating operation.
Furthermore, elimination of an organic species in the instant coatings allows for
higher temperature post processing operations such as high temperature calendaring
without the risk of polymer degradation.
DETAILED DESCRIPTION OF THE INVENTION
[0012] The present invention provides a coating composition in which solids content is maximized
and viscosity is minimized while providing a porous ink receiving layer demonstrating
excellent ink drying characteristics, good image quality, and excellent resistance
to ink smearing and bleeding in the presence of water or humidity.
[0013] Surprisingly, it was found that an efficient system could be provided which consists
solely of particulate species, more particularly, a mixture of colloidal and non-colloidal
particles. The inorganic colloidal particles provide rigidity and dusting-resistance
to the layer without causing increased viscosity or reduced water resistance which
polymeric binders cause. The larger particles, which can be organic or inorganic in
nature, provide ink absorption and porosity. Because of the higher solids content
which is coatable in the absence of polymeric additives, curl and cockle during the
coating and drying operation may be minimized.
[0014] Suitable support materials include conventional paper, calendared paper, paper coated
with extruded protective layers such as polyethylene, polypropylene or the like, and
opaque or nonopaque polymeric films. Examples of such polymeric film materials include
polyethylene terephthalate, polyethylene naphthalate, poly-1,4-cyclohexane dimethylene
terephthalate, polyvinyl chloride, polyimide, polycarbonate, polystyrene, cellulose
acetate, or cellulose acetate propionate.
[0015] The coating composition of the invention can be applied by any number of well-known
techniques, such as dip-coating, rod-coating, blade coating, air knife coating, gravure
coating and reverse roll coating, extrusion coating, slide coating, curtain coating,
and the like. After coating, the layer is generally dried by simple evaporation, which
may be accelerated by known techniques such as convection heating. Known coating and
drying methods are described in further detail in Research Disclosure No. 308119,
published Dec. 1989, pages 1007 to 1008.
[0016] The coating composition can be coated either from water or organic solvents, however
water is preferred for environmental reasons. The total solids content may range from
10% to 50% , but a preferred solids level is 40.
[0017] The non-colloidal pigment may be any pigment commonly used in paper coatings, such
as clay, calcium carbonate, titanium dioxide, calcined clay, aluminosilicates, amorphous
silica and silicates, barium sulfate, satin white, or plastic pigments such as polystyrene
or nylon beads. Preferably, porous silica comprises the non-colloidal pigment, due
to its wide availability, innocuous handling, and freedom from environmental concerns.
While many types of amorphous and crystalline silica particles are manufactured by
various methods and are commercially available, it might be preferred to use some
porosity in order to accomplish faster ink drying in ink receiving layer. Synthetic
amorphous silicas are preferred, as they have a very porous nature. Such materials
can be successfully manufactured as either precipitated silica or silica gels. While
their porosity is helpful in the absorption of ink, noncolloidal particles with extremely
high levels of porosity are not as useful in the current invention as those with intermediate
levels of porosity. This is because very porous silica particles absorb too much of
the water used in the coating formulation, causing an unacceptable increase in viscosity,
necessitating a decrease in solids level to obtain a coatable formulation. Porosity
is commonly measured by oil absorption, in grams of oil per gram of silica. Preferred
levels range from 50-350g/g, preferably 100-240 g/g.
[0018] The colloidal particles are typically dispersed in water or solvent. They may include
but are not limited to silica, aluminum-modified silica, alumina, tin oxide, antimonate,
or (layered)coated oxides. The particle size is 1 nm to 1 micron, preferably 10 to
50 nm. The colloidal pigment may be chosen from the same set of ceramic materials
listed above. The primary characteristic of the colloidal particles is that they are
sufficiently small to exist in a dispersed state in a liquid (preferably water) and
have sufficient interparticle attractive forces to hold together, but not flow, under
typical coating and drying conditions. Colloidal materials are usually defined as
having a size range from 1 nm to 1 micron (Solid/Liquid Dispersions, Th. F. Thadros,
Ed., Academic Press, 1987, p.1). They may be spherical, ellipsoidal, acicular or fibrillar
in shape. Surfaces may be treated or polymer grafted in order to enhance dispersability.
While the surface charge of such particles may vary widely based on chemical composition,
any type may be used. Preferably, the charge at the surface of the particle should
be opposite that of the dyes in the marking inks, if dyes are used. In this way, mordanting
of the dyes may be facilitated, resulting in good bleed resistance and waterfastness.
For example, if dyes are anionic as for most commercial inkjet inks, a positively
charged colloidal particle is preferred; for example alumina (Dispal™, Condea Vista
Chemicals) or alumina-coated silica (Ludox™ CL, DuPont).
[0019] 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 per cent 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.
[0020] In one embodiment of the invention, it is optional to overcoat the dried composition
described above with an additional layer. While not essential to the invention, the
additional overcoat might be preferred for dot gain control, reduction in feathering
or bleed, or for gloss enhancement. Typically such a layer should be a thin polymeric
layer which may serve to control ink absorption rates. Many appropriate materials
are well known in the art and may be applied by a variety of methods. The use of film-forming
hydrophilic colloids as binders in ink receiving elements is well known. Examples
of hydrophilic materials which form excellent ink-receptive layers for aqueous inks
include but are not limited to polyvinyl alcohols and their derivatives, polyvinyl
pyrrolidone, sulfonated or phosphated polyesters, cellulose ethers and their derivatives,
poly(2-ethyl-2-oxazoline), gelatin, casein, zein, albumin, chitin, chitosan, dextran,
pectin, collagen derivatives, collodian, agar-agar, arrowroot, guar, carrageenan,
tragacanth, xanthan, rhamsan, sulfonated polystyrenes, acrylamides and their derivatives,
polyalkylene oxides and the like. Combinations of such materials may also be used.
The dry coverage of such a layer may range from 0.1 micrometer to 10 micrometers,
but preferably ranges from 0.5 micrometers to 5 micrometers, and even more preferably
ranges from 0.5 to 1.0 micrometers.
Examples
Examples 1-12 and Comparative Examples 13-22 demonstrate the advantage of this invention
over films cast entirely from either colloidal or noncolloidal particles.
[0021] Coating compositions were made by slowly adding a conventional porous non-colloidal
powder to a colloidal suspension of an oxide ceramic. The mixtures were stirred thoroughly
until they were free of agglomerates or obviously oversized particulates. The composition
was coated without further addition by the wound wire rod technique. The compositions
were coated on bare, untreated bond-grade paper and were allowed to dry in a conventional
lab oven at 70°C. The dried coatings were printed with blocks of solid colors (cyan,
magenta, yellow, black, red, green and blue) with a Canon BJC 610 or Canon BJC 620
inkjet printer at 360 dpi, special coated paper setting.
TABLE 1
Example |
Noncolloidal powder |
Colloidal species |
% solids |
Ratio of colloidal/non colloidal |
Dry coverage g/m2 |
Example 1 |
Silica IJ35 |
LudoxTM CL |
42 |
60/40 |
12 |
Example 2 |
Silica IJ35 |
Ludox™ AM |
42 |
60/40 |
12 |
Example 3 |
" |
LudoxTM SK |
38 |
56/44 |
11 |
Example 4 |
" |
LudoxTM TMA |
45 |
63/37 |
13 |
Example 5 |
" |
Nalco™ 1056 |
42 |
60/40 |
12 |
Example 6 |
" |
NalcoTM 1034A |
45 |
63/37 |
13 |
Example 7 |
" |
Nalco™ 8676 |
25 |
40/60 |
6.4 |
Example 8 |
" |
VistaTM 23N4-20 |
33 |
50/50 |
9 |
Example 9 |
Mica LVT-600 |
LudoxTM AM |
42 |
60/40 |
12 |
Example 10 |
Titania |
LudoxTM CL |
42 |
60/40 |
12 |
Example 11 |
Mizukasil |
LudoxTM CL |
42 |
60/40 |
12 |
Example 12 |
Nylon 12 |
LudoxTM CL |
42 |
60/40 |
12 |
Comparative Example 13 |
Silica IJ35 |
none |
40 |
0/100 |
uncoatable (too viscous) |
Comparative Example 14 |
" |
" |
20 |
0/100 |
8 |
Comparative Example 15 |
none |
LudoxTM CL |
30 |
100/0 |
13 |
Comparative Example 16 |
" |
LudoxTM AM |
30 |
100/0 |
13 |
Comparative Example 17 |
" |
LudoxTM SK |
30 |
100/0 |
10 |
Comparative Example 18 |
" |
LudoxTM TMA |
34 |
100/0 |
14 |
Comparative Example 19 |
" |
NalcoTM 1056 |
30 |
100/0 |
13 |
Comparative Example 20 |
" |
NalcoTM 1034A |
34 |
100/0 |
14 |
Comparative Example 21 |
" |
NalcoTM 8676 |
10 |
100/0 |
3.6 |
Comparative Example 22 |
" |
VistaTM 23N4-20 |
20 |
100/0 |
7.7 |
Materials
Noncolloidal particles:
[0022]
Silica IJ35 Gasil IJ35 noncolloidal porous silica, particle size 4.5 microns (Crosfield
Company)
Mica LVT-600: LVT-600 low viscosity talc, particle size 2.4 microns (Barretts Minerals,
Inc.)
Titania: Acicular titania FTL-300, (Ishihara Corporation USA) Dimensions: 5 microns
length x 0.3 microns width
Mizukasil: Mizukasil P-78D noncolloidal porous silica, particle size 7 microns (Mizusawa
Fine Chemicals)
Nylon 12: Orgasol ultrafine polyamide, particle size 4.7 microns (Elf Atochem ATO)
Colloidal particles:
[0023]
Ludox CL:TM Alumina-coated colloidal silica, 12 nm (DuPont Specialty Chemicals)
Ludox AM:™ Colloidal silica stabilized with sodium aluminate, 12 nm (DuPont)
Ludox SK: Combination of deionized colloidal silica with water soluble polymer, 12
nm (DuPont)
Ludox TMA: Deionized colloidal silica, 22 nm (DuPont)
Nalco 1056: Aluminum modified colloidal silica, 20 nm (Nalco Chemical Company)
Nalco 1034A:™ Colloidal silica 20 nm (Nalco Chemical Company)
Nalco 8676:™ Colloidal alumina, 2 nm (Nalco Chemical Company)
Vista 23N4-20:™ Dispal 23N4-20 alumina, 90 nm (Condea Vista Company)
[0024] The coatings were evaluated for the following attributes:
Bleed: (Measures the propensity of a printed area to spread beyond its intended or
specified boundaries)
1: No noticeable bleed between colors or into unprinted areas
2: Some bleed
3: Unacceptable (severe) bleed
Coalescence: (Nonuniformity of solid printed areas. Inks may puddle when absorption
is uneven, resulting in local nonuniformites of optical density)
1: No noticeable coalescence
2: Slight coalescence
3: Severe coalescence
Waterfastness:
1: Colors do not run when water is dripped on them
2: Colors run slightly
3: Colors run severely
TABLE 2
Example |
Comments- /Quality |
Printer Tested |
Bleed |
Coalescence |
Waterfastness |
No coating on paper |
|
Canon BJC-610 |
2 |
2 |
2 |
1 |
|
" |
1 |
1 |
1 |
2 |
|
" |
1 |
1 |
3 |
3 |
|
" |
1 |
1 |
3 |
4 |
|
" |
1 |
1 |
3 |
5 |
|
" |
1 |
2 |
2 |
6 |
|
" |
2 |
1 |
3 |
7 |
|
" |
1 |
1 |
2 |
8 |
|
" |
1 |
1 |
2 |
9 |
|
" |
3 |
3 |
2 |
10 |
|
Canon BJC-620 |
1 |
2 |
1 |
11 |
|
" |
1 |
1 |
1 |
12 |
|
" |
2 |
1 |
1 |
Comparative Examples: |
|
|
|
|
|
13 |
Could not coat |
|
|
|
|
14 |
Could not print (coating powdered off) |
|
|
|
|
15 |
Some bronzing in blue |
Canon BJC-610 |
2 |
2 |
1 |
16 |
|
" |
1 |
3 |
3 |
17 |
|
" |
2 |
3 |
3 |
18 |
|
" |
2 |
1 |
3 |
19 |
Bronzing in blue |
" |
2 |
2 |
2 |
20 |
|
" |
2 |
1 |
3 |
21 |
Bronzing effect in blue |
" |
2 |
2 |
3 |
22 |
Bronzing effect in blue |
" |
2 |
3 |
2 |
Examples 23-29 demonstrate preferred ratios of colloidal to noncolloidal particles.
[0025] The coating compositions were mixed as described above. In each case, the colloidal
particle was Ludox™ CL (DuPont Specialty Chemicals) and the noncolloidal particle
was Gasil™IJ35 (Crosfield). The coating solvent was water. The compositions were bead
coated on calendared raw photobase paper and dried at 55°C. Dry coverages ranged from
21 to 24 grains/meter 2.
[0026] Printed quality was evaluated for coalescence on the Canon BJC 4200 inkjet printer
using Photo Inks by evaluating a patch of solid cyan for nonuniformity.
[0027] Dry time was evaluated by printing solid strips of color on a Hewlett Packard 850C
inkjet printer at 80 per cent relative humidity. Immediately after printing, a sheet
of bond paper was pressed against the printed image and a heavy smooth metal roller
was passed over the combination. The sheets were separated. The dye offset to the
bond paper (cyan, magenta, yellow, red, green and blue) was inspected to identify
which color offset to the bond paper for the longest time after printing. In each
case, this was the blue ink. The spot on the offset sheet at which no more blue ink
was visible was measured with respect to the spot at which zero time had passed (point
of heaviest offset) between printing and applying the bond paper. This length was
converted to time.
[0028] Dot size was measured by printing low density patches of cyan ink from a Hewlett
Packard 690C inkjet printer using standard inks. Diameter was measured directly using
an optical microscope at 290X magnification.
TABLE 3
Example |
Colloidal/Non -colloidal particles |
Per cent solids in formulation |
Printed Quality: Coalescence in Cyan (Canon BJC 4200 Photo Inks) |
Time to dry HP 850 inks |
Dot size HP 690 Standard Inks Cyan |
23 |
40/60 |
50 |
Could not coat (powdery) |
Not tested |
Not tested |
24 |
50/50 |
45 |
Poor coated quality |
Not tested |
Not tested |
25 |
60/40 |
42 |
poor coated quality |
Not tested |
Not tested |
26 |
65/35 |
40 |
good |
instant |
90 microns |
27 |
70/30 |
38 |
good |
instant |
100 microns |
28 |
80/20 |
35 |
fair |
52 seconds |
130 microns |
29 |
90/10 |
32 |
poor |
1 min 23 seconds |
130 microns |
[0029] These examples show the balance between coatability, coating quality, dry time and
dot gain which show the advantage of intermediate compositions of colloidal:noncolloidal
particulate ratios.
[0030] The following examples show the effect of overcoating the coating of Example 26 with
a polymeric layer designed to control (i.e. slow) the absorption of ink into the porous
particulate layer. This layer was slide coated (simultaneously from another slot during
bead coating) over the coating composition used to form Example 26. The composition
of the overcoat was an 80/20 (weight) mixture of cationically modified hydroxyethyl
cellulose (Quatrisoft LM200, Amerchol) and methyl cellulose (Methocel A4M, Dow Chemical)
in water. The per cent solids of the overcoat was 1.75%. The coatings were dried as
described for examples 23-29.
TABLE 4
Example |
Dry coverage of overcoat, g/m2 |
Bleed in Canon 4200 with Photo Inks |
Bleed in HP 690 with standard inks |
26 |
0 |
severe |
excellent |
30 |
0.27 |
poor |
excellent |
31 |
0.54 |
fair |
excellent |
32 |
0.81 |
good |
excellent |
33 |
1.08 |
good |
excellent |
[0031] This data clearly shows that depending upon the ink set tested, a thin absorption
control overcoat may be preferred.
Example 34
[0032] A coating was made which was identical to Example 1, except that it was coated directly
on polyethylene-coated paper. The polyethylene surface was treated with a corona discharge
prior to applying the coating formulation in order to aid in welling and adhesion.
The coating was continuous and did not powder or flake from the support material.
This demonstrates the wide range of support materials which may be successfully coated
with the current invention.
1. An inkjet recording medium comprising a substrate coated on at least one surface with
a coating composition comprising a mixture of inorganic colloidal particles and non-colloidal
pigments.
2. An inkjet recording medium comprising a substrate having disposed on a surface thereof,
a coating composition that is free of an organic species.
3. The inkjet recording medium of claim 1, 2, or 3 wherein the coating composition has
a solids content of 10-70 weight % of the coating composition.
4. The inkjet recording medium of claim 1 or 2, wherein the noncolloidal pigment in the
coating composition is selected from clay, calcium carbonate, titanium dioxide, calcined
clay, aluminosilicates, amorphous silica and silicates, barium sulfate, satin white
and plastic pigments porous silica.
5. The inkjet recording medium of claim 6, wherein the noncolloidal pigment is porous
silica.
6. The inkjet recording medium of claim 1 or 2, wherein the noncolloidal pigment in the
coating composition has an oil absorption capacity between 100-240 grams of oil per
grams of silica.
7. The inkjet recording medium of claim 1 or 2, wherein the colloidal particle in the
coating composition is selected from silica, aluminum-modified silica, alumina, tin
oxide, antimonate, and coated oxides.
8. The inkjet recording medium of claim 1 or 2, wherein the colloidal particles in the
coating composition has a particle size between 1nm and 1 micron.
9. The inkjet recording medium of claim 1, 2, or 3, wherein the coating composition further
comprises coating aids.
10. The inkjet recording medium of claim 12 wherein the amount of coating aids is between
0.01 and 0.30 weight percent based on the total solution.