[0001] This invention relates to an ink jet recording element, more particularly to a porous
ink jet recording element and a 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] U.S. Patent 5,932,355 relates to an ink-jet recording sheet wherein the ink-receptive
composition contains a non-ionic silicone surfactant, from abot 14 to 93 % by weight
of a polymer and a small amount of particulates such that the coating is transparent.
However, there is a problem with this element in that it is not porous, so that it
has a poor dry time.
[0006] U.S. Patent 5,919,559 relates to an inkjet recording sheet comprising an ink absorbing
layer containing a predominant amount of water soluble resin or water dispersible
resin and an nonionic surfactant having an HLB number of 11 or more. However, there
is a problem with this element in that it is not porous, so that it will have a poor
dry time.
[0007] It is an object of this invention to provide an ink jet recording element that is
porous. It is another object of the invention to provide an ink jet recording element
that has a fast dry time and good image quality. Another object of the invention is
to provide a printing method using the above described element.
[0008] These and other objects are achieved in accordance with the invention which comprise
an ink jet recording element comprising a support having thereon a porous image-receiving
layer comprising at least 90% by weight of particles and less than 10% by weight of
a binder, the image-receiving layer also containing a nonionic surfactant having an
HLB number of less than 10 in an amount to substantially prevent foaming of the coating
composition which is used to coat the support with the image-receiving layer
[0009] By use of the invention, a porous ink jet recording element is obtained which has
a fast dry time and good image quality.
[0010] 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 described above;
C) loading the printer with an ink jet ink; and
D) printing on the porous image-receiving layer using the ink jet ink in response
to the digital data signals.
[0011] The presence of a binder in an image-receiving layer coating solution increases its
propensity to foam. The coating solution typically requires a large amount of agitation
to minimize the concentration gradients of the ingredients and thereby reduce variability.
This agitation, however, typically leads to entrainment of air, which leads to the
formation of excessive foam.
[0012] In accordance with the invention, certain non-ionic surfactants have been found to
be antifoaming agents. In addition, these materials do not themselves foam at low
concentrations.
[0013] As noted above, the non-ionic surfactants which are used in this invention have an
HLB number less than 10. The HLB number of a surfactant is used to specify the nature
of an oil/water dispersion that is formed in the presence of that surfactant. If the
HLB number is less than 7, the dispersed (or drop) phase will be water. If the HLB
number is above 12, the dispersed phase will be oil.
[0014] It has been found that the HLB number can also be used to predict the ability of
a nonionic surfactant to eliminate foam in a coating solution. If a surfactant has
an HLB number of 10 or greater, the surfactant may enhance the stability of the foam
instead of eliminating it.
[0015] The HLB number of surfactants can be measured or calculated. There are several methods
of measuring HLB, some of which are listed in "Nonionic Surfactants", Ed. M. Schick,
"Surfactant Science Series", Vol. 1, Marcel Deker Inc., New York, 1967.
[0016] There are several kinds of nonionic surfactants that can be used in the present invention.
There can be used, for example, ethoxylated alcohols having the formula R-O(CH
2CH
2O)
nH where R can be alkyl, aryl or aralkyl having from 2 to 30 carbon atoms and n can
vary from 2 to 20. The HLB number of an ethoxylated alcohol is related to the ratio
of the number of ethylene oxide groups to the number of carbon atoms in the R group.
Preferred ethoxylated alcohols useful in the invention include those where all or
some of the hydrogen atoms in the R group are substituted by fluorine atoms.
[0017] Another class of nonionic surfactants useful in the invention is the block copolymers
of ethylene oxide and propylene oxide. Examples of these are Pluronics ® (poloxamers)
which are triblock copolymers and Tetronics® (poloxamines), which are tetrafunctional
block copolymers derived from the sequential addition of propylene oxide and ethylene
oxide to ethylenediamine. The ratio of the amount of propylene oxide to ethylene oxide
is directly related to the HLB number of the surfactant.
[0018] Another class of nonionic surfactants useful in the invention is alkoxylated poly(dimethylsiloxanes)
(PDMS) or polyalkylene-modified PDMS materials, including those containing ethylene
oxide as well as ethylene oxide and propylene oxide and having an HLB number as described
above.
[0019] Another class of nonionic surfactants useful in the invention is based on derivatives
of mono and disaccharides, including sorbitol esters such as Spans®, and alkyl glucosides
and hydrophobic sucrose esters such as sucrose distearate.
[0020] Commercial examples of the above surfactants useful in the invention include:
- S-1
- Silwet® L7220 (Witcop Corp.)
- S-2
- Silwet® L7210 (Witcop Corp.)
- S-3
- Silwet ® L7602 (Witcop Corp.)
- S-4
- Pluronic ® L61 (BASF Corp.)
- S-5
- Tetronic® 90R4 (BASF Corp.)
- S-6
- Tetronic® 701 (BASF Corp.)
- S-7
- Tetronic® 150R1 (BASF Corp.)
- S-8
- Fluorad® FC171 ( 3M Corp.)
- S-9
- Brij ® 30 (ICI Chemicals)
- S-10
- Brij ® 93 (ICI Chemicals)
[0021] The surfactants used in the present invention are typically used in relatively small
amounts. Based on their HLB numbers, these surfactants have limited solubility in
coating solutions. These surfactants have a cloud point, which is the highest temperature
at which the surfactant is soluble in water.
Coating operations typically take place between 25 and 30°C. Therefore, these surfactants
are usually used at levels below their solubility limit at the operating temperature.
In general, the surfactants may be used in an amount of at least 0.05 % by weight
of the coating solution, preferably from 0.05 % to 1.0 % by weight.
[0022] 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 inorganic such as alumina, silica, fumed alumina
or fumed silica. Such particles are preferred for ink jet recording elements because
they possess positively charged surfaces, which are capable of binding anionic ink
jet printing dyes, rendering printed images resistant to dye migration due to water
and high humidity conditions.
[0023] As noted above, the porous image-receiving layer comprises at least 90% by weight
of particles. This amount of particles will insure that the layer is porous, i.e.,
have interconnecting voids so that the solvent in the ink can travel through the layer
to a support or base layer if one is present. In a preferred embodiment, the porous
image-receiving layer comprises at least 90-95% by weight of particles.
[0024] In general, any binder may be used in the invention. In a preferred embodiment, the
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. In still another preferred
embodiment of the invention, the hydrophilic polymer is poly(vinyl alcohol), hydroxypropyl
cellulose, hydroxypropyl methyl cellulose, gelatin, or a poly(alkylene oxide). In
yet still another preferred embodiment, the hydrophilic binder is poly(vinyl alcohol).
The polymeric binder should be chosen so that it is compatible with the aforementioned
particles.
[0025] The amount of binder used in the invention 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 particles is not filled in by the binder.
In a preferred embodiment of the invention, the amount of binder employed is less
than 10% by weight, preferably 5-10 % by weight.
[0026] The thickness of the image-receiving layer may range from 5 to 40 µm, preferably
from 10 to 20 µm. The coating thickness required is determined through the need for
the coating to act as a sump for absorption of ink solvent and the need to hold the
ink near the coating surface. The coating may be applied in a single layer or in multiple
layers so the functionality of each coating layer may be specified. For example, a
two-layer structure can be created wherein the base layer functions as a sump for
absorption of ink solvent while the top layer holds the ink. In that case, the nonionic
surfactant and particles are used in both layers, i.e., the base layer contains at
least 90% by weight of particles and less than 10% by weight of a binder, and the
base layer also contains a nonionic surfactant having an HLB number of less than 10
in an amount to substantially prevent foaming of the coating composition which is
used to coat the support with the base layer.
[0027] 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, softnip calendering at a temperature of 65°C
and pressure of 14000 kg/m at a speed of from 0.15 m/s to 0.3 m/s.
[0028] 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 resincoated 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.
[0029] 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.
[0030] 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.
[0031] 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.
[0032] 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 adhesion promoters, rheology modifiers, biocides, lubricants, dyes, optical
brighteners, matte agents, antistatic agents, etc.
[0033] The coating composition can be coated so that the total solids content will yield
a useful coating thickness, and for particulate coating formulations, solids contents
from 10-60% are typical.
[0034] Ink jet inks which can be 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.
[0035] The following examples further illustrate the invention.
Example 1-Surfactant in Image-receiving Layer Coating Solution
[0036] Coating solution 1 was prepared by mixing 100 dry g of Dispal® 14N4-80 alumina (Condea
Vista Co.) as a 20% solution with 4 dry g of poly(vinyl alcohol) GH-17® (Nippon Gohsei
Co. Ltd.) as a 10% solution and 0.1 dry g of 2,3-dihydroxy-1,4-dioxane (Clariant Corp).
The solids of the coating solution was adjusted to 20% by adding water.
[0037] The nonionic surfactants S-1 through S-10 described above were compared to the performance
of control surfactants C-1 through C-4, identified below, whose HLB numbers are outside
the range of this invention. All surfactants were added to the coating solution at
a level of 0.5 % by weight.
- C-1
- Silwet ® L7500 (Witco Corp.)
- C-2
- Pluronic® F108 (BASF Corp.)
- C-3
- Tetronic® 904 (BASF Corp.)
- C-4
- Triton ® X-45 (Union Carbide Corp.)
[0038] The HLB numbers of all surfactants employed are based on the values reported by the
respective manufacturer, except where noted.
[0039] About 20 ml of the coating solution was placed in a 50 ml graduated cylinder which
had a diameter of 1 cm. It was then manually shaken until the foam height remained
constant. After the shaking was stopped, the initial foam volume (total volume of
the coating solution and associated foam) was noted. The volume of the foam was noted
again after 30 minutes.
[0040] If the foam height had reduced to about 20 ml, the surfactant is deemed effective.
If the foam height remained high even after 30 minutes, the surfactant is considered
to be ineffective. The results are shown in Table 1 below.
Table 1
| Surfactant |
HLB |
Initial foam volume |
Volume after 30 minutes |
Effectiveness |
| None |
N/A |
41 |
40 |
N/A |
| S-1 |
5-8 |
23 |
21 |
Yes |
| S-2 |
5-8 |
23 |
21 |
Yes |
| S-3 |
5-8 |
24 |
20 |
Yes |
| S-4 |
3 |
20 |
20 |
Yes |
| S-5 |
7 |
25 |
21 |
Yes |
| S-6 |
3 |
25 |
20 |
Yes |
| S-7 |
1 |
26 |
21 |
Yes |
| S-8 |
2.8* |
22 |
21 |
Yes |
| S-9 |
9.7 |
27 |
21 |
Yes |
| S-10 |
4.9 |
21 |
21 |
Yes |
| C-1 |
13 |
37 |
37 |
No |
| C-2 |
27 |
46 |
46 |
No |
| C-3 |
15 |
40 |
38 |
No |
| C-4 |
10.4 |
44 |
40 |
No |
[0041] The above results show that the non-ionic surfactants of the invention were effective
in reducing foam as compared to the surfactants whose HLB number is above the number
described in the invention
Example 2-Surfactant in Base Layer Coating Solution
[0042] Coating solution 2 was prepared by mixing 100 dry g of Albagloss-s® precipitated
calcium carbonate (Speciality Minerals Inc.) as a 70% solution with 5 dry g of poly(vinyl
alcohol) GH-17® (Nippon Gohsei Co., Ltd.) as a 10% solution and 0.1 dry g of 2,3-dihydroxy-1,4-dioxane
(Clariant Corp). The solids of the coating solution was adjusted to 35% by adding
water.
[0043] The same surfactants were added to the base coating composition and tested as in
Example I and the results are shown in Table 2 below:
Table 2
| Surfactant |
HLB |
Initial foam volume |
Volume after 30 minutes |
Effectiveness |
| None |
N/A |
36 |
36 |
N/A |
| S-1 |
5-8 |
26 |
21 |
Yes |
| S-2 |
5-8 |
25 |
23 |
Yes |
| S-3 |
5-8 |
28 |
26 |
Yes |
| S-4 |
3 |
29 |
26 |
Yes |
| S-5 |
7 |
25 |
21 |
Yes |
| S-6 |
3 |
32 |
25 |
Yes |
| S-7 |
1 |
27 |
22 |
Yes |
| S-8 |
2.8* |
30 |
26 |
Yes |
| S-9 |
9.7 |
27 |
21 |
Yes |
| S-10 |
4.9 |
21 |
21 |
Yes |
| C-1 |
13 |
39 |
37 |
No |
| C-2 |
27 |
43 |
46 |
No |
| C-3 |
15 |
42 |
38 |
No |
| C-4 |
10.4 |
43 |
40 |
No |
[0044] The above results show that the non-ionic surfactants of the invention were effective
in reducing foam as compared to the surfactants whose HLB number is above the number
described in the invention
Example 3- Printing on Recording Element
[0045] The base layer coating solution from Example 2 was bead-coated at 25 ° C on a base
paper and dried at 60°C by forced air. The base paper used was Nekoosa Solutions Smooth
® (Georgia Pacific), Grade 5128 (Carrara White ®, Color 9220), basis weight 150 g/m
2. The image-receiving layer coating solution of Example 1 was coated on top of this
base layer. The recording element was then dried at 60 ° C by forced air to yield
a two-layer recording element in which the thicknesses of the bottom and topmost layers
were 25 µm (27 g/m
2) and 8 µm (8.6 g/m
2), respectively.
[0046] Test images of cyan, magenta, yellow, red, green and blue patches at 100% ink laydown
were printed on the above recording element using an Epson Stylus® Color 740 using
inks with catalogue number S020191. 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 transferred
image 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.
[0047] After drying for 24 hours at ambient temperature and humidity, the Status A D-max
densities were measured using an X-Rite® 820 densitometer as follows (for each of
the red, green and blue densities, the two component color densities were measured
and averaged). The results are shown in table 3.
Table 3
| Dry Time |
Status A D-max Density |
| (cm) |
Cyan |
Magenta |
Yellow |
Red |
Green |
Blue |
| 0 |
2.28 |
1.99 |
1.79 |
1.96 |
2.13 |
2.31 |
[0048] The above results show that the ink jet recording element of the invention has good
image optical density and an apparent instant dry time (No ink was transferred to
the bond paper immediately after printing).