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Description  |
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TECHNICAL FIELD
The present invention relates to ink compositions for ink-jet printers,
and, more particularly, to ink compositions in which the solubility of the
dye is increased by replacement of cations such as sodium and potassium.
BACKGROUND ART
The use of aqueous-based inks for ink-jet printers is well-known. Such
compositions are relatively inexpensive and easy to prepare; typically,
the ink comprises water and a glycol or glycol ether, usually diethylene
glycol (commonly referred to as the vehicle), and a dye. Typically, the
water and glycol ether are present in generally the same proportion and
the dye, for example, Food Black 2, is present up to about 6% of the total
composition, depending on the desired density of the print.
The prior art inks generally use existing commercial dye salts (cation plus
dye anion) as formed, which are simply dissolved in the vehicle and
filtered to prepare the ink. Such dyes, which generally contain a
plurality of sulfonate or carboxylate anion groups, are designed to form
solids in paper or cloth, employing cations such as sodium cations.
Consequently, the dyes do not easily remain liquid in the orifice of an
ink-jet printer.
Thus, a persistent problem associated with aqueous-based inks is their
propensity to crust over a period of time, eventually leading to plugging
of the orifice in the printer mechanism from which droplets of ink are
expelled in the printing operation. Crusting is the crystallization of the
ink around the orifice in the print head, causing partial or full blockage
of the orifice, leading to misdirection of the drop (partial blockage) or
prevention of drop ejection (full blockage). The crusting problem arises
from the evaporation of the water from the ink solvent (vehicle) and the
consequent precipitation of the dye salt which has become substantially
insoluble as a result of this water loss.
Attempts have been made to solve the crusting problem. Hygroscopic agents
have been added to reduce the rate of water evaporation by their ability
to pick up water vapor from the air. Exemplary of such hygroscopic agents
are water-soluble polymers, alkanol amines, amides and polyhydric
alcohols.
While some improvement has been realized with these hygroscopic agents, a
total solution to the crusting problems has not yet been achieved.
Further, apparently no methods are known to prevent crusting of the
anionic dyes in mildly acidic to mildly basic aqueous-based inks (pH 4 to
9). Such crusting is particularly exacerbated by the trend to fabricate
printheads with increasingly smaller orifices, on the order of 45 to 60
.mu.m in diameter.
Attempts are continuing to develop inks in which the dye solubility is
increased.
Other approaches include developing new dyes for inkjet inks. For example,
U.S. Pat. No. 4,557,761 discloses a variety of sulfonate-containing dyes
with cations such as sodium, potassium, lithium, ammonium and amine salt
cations.
However, as shown above, dyes with sodium cations have certain
deficiencies. Dyes with potassium cations also suffer from certain
deficiencies, notably evidencing crusting. Dyes with ammonium cations, on
the other hand, are not stable. Thus, the cations listed in U.S. Pat. No.
4,557,761 cannot be considered to be equivalent.
Finally, many cations are not suitable for dyes employed in inks used in
thermal ink-jet printing. In this instance, a problem known as kogation
may occur. Kogation is a coined term, unique to thermal ink-jet printing,
and describes the extent of decomposition of the ink on the resistors of
thermal ink-jet printers as a consequence of heating. Such heating is used
to form droplets of ink, which are propelled toward the substrate.
While sodium-containing dyes evidence crusting problems, they also evidence
superior kogation properties. Dyes containing other cations which evidence
improved crusting also often evidence poor kogation.
It is known to partially replace sodium cations with lithium cations; see,
e.g., Japanese Laid-Open 61-73772 (Applicant: Mitsubishi Kasei kagaku) and
Japanese Laid-Open 57-202358 (Applicant: Fujitsu). However, such partial
replacement has been found inadequate in dealing with the crusting
problem, especially for the smaller orifice sizes on the order of 45
.mu.m. Further, Japanese 57-202358 extols the use of a vehicle having
about 25 to 35% water, the balance glycol. Inks employing such vehicles,
however, are not suitable for printing on plain paper.
DISCLOSURE OF INVENTION
Accordingly, it is an advantage of the present invention to provide an ink
composition evidencing increased dye solubility in the vehicle.
It is an advantage of this invention to provide an ink in which the
crusting problem is minimal.
It is another advantage of this invention to provide an aqueous-based ink
for ink-jet printers in which kogation of the dye in the ink solvent
(vehicle) is not adversely affected by partial or total replacement of
sodium or other cations.
It is a further advantage of this invention to provide an aqueous-based ink
for ink-jet printers in which the solubility of anionic dyes in mildly
acidic to mildly basic media is increased.
It is still another advantage of this invention to provide an aqueous-based
ink for thermal ink-jet printers for printing on plain papers.
Briefly, the ink composition of the invention comprises a vehicle and an
anionic dye containing a plurality of undesirable cations associated with
each dye molecule, substantially all of the cations being replaced by
lithium cations. The vehicle consists essentially of about 5 to 10% of at
least one glycol and/or glycol ether and the balance water.
The dye containing lithium cations evidences increased solubility and
reduced crusting in inks commonly used in ink-jet printing, yet shows no
tendency toward kogation in ink-jet printing. The low glycol ink is
suitably employed in thermal ink-jet printing on plain paper.
BEST MODES FOR CARRYING OUT THE lNVENTION
The ink compositions of the invention comprise an aqueous-based vehicle and
a dye. The pH of the ink may be maintained in both the mildly acidic and
mildly basic regions, ranging from about 4 to 9. In this connection, pH
buffers, biocides, and other components commonly found in ink-jet inks may
be employed in the practice of the invention.
The vehicle of the ink comprises water and at least one of the glycols and
glycol ethers commonly employed in the inks used in ink-jet printing.
Examples of such compounds include diethylene glycol, triethylene glycol
and polyethylene glycols. The glycol and/or glycol ether is present in an
amount ranging from about 5 to 10%, the balance being water. Preferably,
the vehicle comprises less than about 10% of the glycol and/or glycol
ether, and most preferably comprises about 5.5% a glycol ether such as
diethylene glycol and the balance water.
To the vehicle is added up to about 0.1 Molar of a dye, preferably an
anionic dye. The amount of the dye added is a function of choice, being
largely dependent upon the solubility of the dye in the vehicle (which
limits the upper range of dye concentration) and the desired density of
the print achieved with the ink (which limits the lower range of dye
concentration--typically about 0.005 Molar). Preferably, the concentration
of the dye in the ink composition is about 0.065 Molar. For Food Black 2,
a dye commonly employed in ink-jet inks, the corresponding concentration
in wt % ranges from about 0.5 to 10%, with about 6% being preferred.
The dye to which the invention is suitably applied is an organic molecule
having at least one negatively charged functional group per molecule.
Since sulfonate (SO.sub.3.sup.-), and carboxylate (CO.sub.3.sup.-), groups
are especially benefited from the practice of the invention, dyes having
such groups are preferred. An example of a preferred dye in this regard is
Food Black 2 (FB2), which has a mixture of two, three and four sulfonate
group per molecule. (The effective value is about 3.2 sulfonate groups per
molecule for commercially available FB2.)
In commercially-prepared dyes, the negative charge of the sulfonate group
in FB2 is most commonly balanced by the presence of positively charged
sodium (Na.sup.+). However, other cations, such as potassium, ammonium,
etc., may be present.
Other anionic dyes in addition to FB2 may also be suitably employed in the
practice of the invention, since, as will be discussed in further detail
below, the solubility of the anionic dyes is increased in acidic media by
employing the teachings of the invention. Examples of other anionic dyes
which may be employed in the ink composition disclosed herein include
Direct Red 9, Direct Red 227, Acid Yellow 23, Direct Yellow 86, Acid Blue
9, Direct Blue 86, Direct Blue 199 and Acid Blue 185.
In accordance with the invention, an ink composition suitable for use in
ink-jet printers is provided, comprising:
(a) a vehicle comprising about 5 to 10% at least one glycol and/or glycol
ether and the balance water; and
(b) a dye having at least one negatively charged functional group per
molecule, present in an amount up to about 0.1 Molar of the ink
composition, the dye having a plurality of anionic sites, originally
associated with undesirable cations, substantially all of the undesirable
cations being replaced with lithium cations.
While sodium and potassium are considered examples of such undesirable
cations, there may be other cations associated with the dye as obtained
from a dye manufacturer which may beneficially be replaced in accordance
with the teachings of this invention. All such replaceable cations are
considered herein to be undesirable cations.
The presence of lithium cations increases the solubility of the dye in the
vehicle without adversely affecting kogation in thermal ink-jet printers.
The presence of lithium also reduces crusting of the ink around the
orifices of the ink-jet printer, such crusting being caused by evaporation
of the water in the vehicle of the ink upon exposure to air.
The substantially complete replacement of undesirable cations by lithium
cations may be accomplished by a variety of methods, exemplary of which
are ion exchange and reverse osmosis.
In the ion exchange reaction, the dye with undesirable cations, such as
sodium cations, is passed through an acid-loaded ion exchange resin. The
undesirable cations are replaced with hydrogen cations. The ion-exchanged
dye is then reacted with lithium hydroxide (LiOH). The lithium cations
replace the hydrogen cations, which react with the hydroxide anions to
form water.
Substantially all of the undesirable cations are replace by the lithium
cations in order to obtain substantial improvements in the properties
described. Specifically, the sodium concentration must be maintained below
about 500 ppm, and preferably below about 350 ppm, in order to avoid
crusting of the orifices during the lifetime of the printhead.
It has been observed that the more the lithium replacement for sodium, the
better the color density achievable.
The presence of lithium permits a concentration of dye up to about 0.1
Molar. Above this level, the viscosity of the ink is undesirably high. For
practical purposes and economy, the maximum amount of Li-dye is about
0.065 Molar; above this level, the color density increases only very
slowly.
An excess of lithium, about 5 to 10%, may be present in the ink to provide
the manufacturer with a margin when making the lithium form of the dye.
INDUSTRIAL APPLICABILITY
The Li-substituted dyes provided in accordance with the invention find use
in inks used in ink-jet printing, particularly in thermal ink-jet printing
.
EXAMPLES
Example 1
A series of dyes were prepared, employing food Black 2, which originally
had all anionic sites complexed with sodium cations. The vehicle comprised
diethylene glycol (DEG) and water in the concentrations given below. In
the inks listed in Table I below, the dye concentration is given in terms
of millimolarity (mM). Comparisons are made with substitutions of sodium
cations ranging from no replacement to full replacement by lithium (Li)
cations. For comparison, full replacement by ammonium cations (NH.sub.4)
and potassium cations (K) is also given.
TABLE I.
______________________________________
Sample
Cation % Na Replacement
Concentration, mM
______________________________________
1 Na -- 39
2 Li 100 39
3 Li 100 52
4 Li 100 65
5 NH.sub.4 100 39
6 K 100 39
______________________________________
The properties of solubility, crusting, kogation, storage and change in
color density (.DELTA.E) are listed in Table II below. The solubility is
shown for two vehicle concentrations: 50/50 DEG/H.sub.2 O and 90/10
DEG/H.sub.2 O.
Storage refers to the stability of chemical and physical properties during
storage.
.DELTA.E is a measure of color density. If the color is measured in CIELAB
coordinates, then .DELTA.E is given by
.DELTA.E=(L.sub.2 -L.sub.1).sup.2 +(a.sub.2 -a.sub.1).sup.2 +(b.sub.2
-b.sub.1).sup.2 ].sup.1/2
where L, a and b are coordinates of reference in CIELAB space and 1 refers
to the background media and 2 refers to the sample.
TABLE II.
______________________________________
Solubility
Sample
50/50 90/10 Crusting
Kogation
Storage
.DELTA.E
______________________________________
1 F F P G G F
2 E E E G G F
3 E E E E
4 E E E G E
5 P
5 P F
______________________________________
The foregoing relative observations were based on the following scale, with
the definitions of each observation for each property as follows:
E=Excellent
G=Good
F=Fair
P=Poor.
A perusal of Table II above shows that solubility is enhanced in both 50/50
DEG/H.sub.2 O and 90/10 DEG/H.sub.2 O for replacement of sodium cations by
lithium cations. Further, kogation is not adversely affected by such
replacement. Other properties of the inks containing Li-replaced dyes,
such as crusting, storage and print quality are seen to be at least
equivalent to those of inks containing sodium cations. Finally, comparison
with replacement by other cations (K and NH.sub.4 ) points up the
improvement achieved with the substitution of lithium for the undesirable
cations.
Example 2
Several pens were filled with inks containing 52 millimolar of one of the
following dyes: Food Black-2 Li2Na2, Food Black-2 Li3Nal, and Food Black-2
Li4. Each pen had 30 orifices, 47 .mu.m in diameter.
The pens were stored at 25.degree. C. and 50% RH and tested at 3, 12, and
85 days for crusting, annular rings, and wet spreading.
Crusting was defined as the crystallization of the ink around the orifice,
leading to misdirection of the drop (partial blockage) or to prevention of
drop ejection (full blockage). Annular rings were defined as
crystallization of ink around at least half of the orifice, but not
causing blockage of that orifice. Annular rings are considered to be a
problem, because they may eventually grow to block the nozzle. The results
are depicted in Table III, below.
TABLE III.
__________________________________________________________________________
[Na]
[Li]
Day 3 Day 12 Day 85
Ink ppm
ppm
WS C AR WS C AR WS C AR
__________________________________________________________________________
FB2Li2Na2
2386
746
0 87
99 0 79
123
FB2Li3Na1
1109
1086
0 0 47 0 12
38 0 30
41
FB2Li4 218
1430
1 0 8 0 0 8 0 0 12
__________________________________________________________________________
Notes:
WS = # of pens (12 total) with wet spreading
C = # of nozzles with crusting
AR = # of nozzles with annular rings
A plot of the foregoing data reveals that up to about 500 ppm of sodium
cations may be tolerated without adversely affecting crusting. However,
greater than about 500 ppm of sodium results in crusting of orifices,
leading to partial or full blockage of the orifices. Crusting is
substantially completely eliminated by maintaining the concentration of
sodium ions below about 350 ppm.
Example 3
A similar test was performed as in Example 2, but filling pens with the
following dyes: Food Black-2 Na4 (12 pens) and Food Black-2 Li4 (11 pens).
The pens were tested at 1, 4, 6, 11, and 14 days for crusting and annular
rings. The results are depicted in Table IV, below.
TABLE IV.
__________________________________________________________________________
[Na] [Li]
Day 1
Day 4
Day 6
Day 11
Day 14
Ink ppm
ppm
C AR C AR C AR C AR C AR
__________________________________________________________________________
FB2Na4
4800
0
5 28 66
6 89
7 74
38 94
25
FB2Li4
218
1430
0 0 0
0 0
0 0
0 0
0
__________________________________________________________________________
The superiority of inks containing substantially complete replacement of
sodium ions by lithium ions is evident.
Example 4--Black Ink
A composition comprising 5.5 wt. % diethylene glycol (DEG), 2.3 wt %
lithium-substituted Food Black 2 dye (at least about 75% substitution of
Na.), 0.01 wt % ICI Proxel CRL biocide, 0.08 wt % sodium borate, and the
balance deionized water was prepared. This ink produced laser printer
quality print having a dry time of less than 20 seconds and the ability to
remain in an uncapped pen for a minimum of 20 days without crusting. No
bacterial growth was observed in the ink.
Example 5--Magenta Ink
A composition comprising 5.5 wt. % DEG, 2 wt % Direct Red 227 dye, 0.3 wt %
Nuodex Co. Nuosept 95 biocide, 0.08 wt % sodium borate, and the balance
deionized water was prepared. This ink gave the same results as observed
in Example 4.
Example 6--Cyan Ink
A composition comprising 5.5 wt. % DEG, 2 wt % Direct Blue 199 dye, 0.3 wt
% Nuodex Co. Nuosept 95 biocide, 0.08 wt % sodium borate, and the balance
deionized water was prepared. This ink gave the same results as observed
in Example 4.
Example 7--Yellow Ink
A composition comprising 5.5 wt. % DEG, 1 wt % Direct Yellow 86 dye, 0.3 wt
% Nuodex Co. Nuosept 95 biocide, 0.08 wt % sodium borate, and the balance
deionized water was prepared. This ink gave the same results as observed
in Example 4.
Example 8--Black Ink
A composition comprising 10 wt. % DEG, 2.3 wt % lithium-substituted Food
Black 2 dye, 0.08 wt % sodium borate, and the balance deionized water was
prepared. This ink produced laser quality print on bond papers and good
(letter quality print on most photocopy paper. Bacterial growth was
observed in the ink after storage.
Example 9--Black Ink
For comparison, a composition comprising 12 wt. % DEG, 2.3 wt %
lithium-substituted Food Black 2 dye, 0.08 wt % sodium borate, and the
balance deionized water was prepared. This ink produced laser quality
print on bond papers and unacceptable (less than letter quality) print on
photocopy paper.
Example 10--Black Ink
For comparison, a composition comprising 15 wt. % DEG, 2.3 wt %
lithium-substituted Food Black 2 dye, 0.08 wt % sodium borate, and the
balance deionized water was prepared. This ink produced good (letter
quality) print on bond papers and unacceptable (less than letter quality)
print on photocopy paper. The dry time was slower than that of inks
containing lower amounts of DEG.
Example 11--Black Ink
for comparison, a composition comprising 50 wt. % DEG, 2.3 wt %
lithium-substituted Food Black 2 dye, 0.08 wt % sodium borate, and the
balance deionized water was prepared. This ink produced unacceptable (less
than letter quality) print on most media, except custom-coated paper.
Thus, an ink composition for ink-jet printers has been provided. The ink
comprises an anionic dye in which at least a portion of the associated
cations are replaced with lithium cations. Various changes and
modifications will be readily apparent to those of ordinary skill in the
art, and all such changes and modifications are considered to be within
the scope of this invention.
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