Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02312643 2000-06-27
Cft
C FO 9 318 -t-
- 1 -
- INK, INK-JET RECORDING METHOD, AND
INK-JET RECORDING APPARATUS
BACKGROUND OF THE INVENTION
Field of the invention
The present invention relates to an ink which
provides excellent color recording on plain paper such
as wood-free paper, medium-quality paper, bond paper,
and paper for copying. The present invention also
relates to an ink-jet recording method, and an ink-jet
recording apparatus employing the above ink.
Related Background Art
Personal computers including desk-top types,
lap-top types, and book types have come to employ a
color display unit in recent years. Software is also
directing to color representation. Consequently,
printers are changing from monocolor types to color
types.
Among recording methods employed by such
printers, ink-jet recording is attracting attention.
In the ink-jet recording, ink droplets are ejected and
are attached to a recording medium such as paper
sheets, converted paper sheets, plastic films, and
cloths without contact of a recording head with the
recording medium. The ink-jet recording method is
advantageous in that noise is not produced because of
non-contact of the recording head with the recording
CA 02312643 2000-06-27
medium, and high speed printing and color recording is
practicable.
In the ink-jet recording method, it is required
that (1) ink does not cause running of ink at the
recorded portion on the recording medium, (2) ink is
sufficiently stable during storage, and (3) the safety
is high. In color ink-jet recording, it is further
required that (4) mixing (or bleeding) of different
colors of inks caused by unfixed ink droplets does not
occur on contact of different color inks on a recording
medium, (5) a solid color portion is uniform in color,
and (6) failure of ink ejection does not occur after
interruption of ink ejection (first-ejection
difficulty), since limited colors of inks are more
frequently used in color printing unlike monocolor
printing.
However, conventional inks per se are not
usable as inks for color recording because they cause
serious bleeding and do not give high-quality images.
Presumably, the bleeding is caused by the fact that the
ink is dotted before the previously dotted different
color of ink has been sufficiently fixed. Coat paper,
which has high ink-absorbing ability, is used for color
recording in order to prevent the bleeding. Further,
for printing on plain paper such as paper for copying
and bond paper, a printing method reflecting upon the
fixing time of ink is proposed in which ink is dotted
CA 02312643 2000-06-27
- 3 -
after the previously dotted ink droplet has been fixed.
In such a printing method, speed of paper feed have to
be slowed down disadvantageously, thereby the printing
time becomes longer irrespectively of the ink-dotting
method. Therefore, high speed printing which is
characteristic of ink-jet recording cannot be practised
with such,a printing method.
To shorten the fixing time, Japanese Patent
Application Laid-Open No. 55-29546 discloses a method
in which a surfactant is incorporated into ink in a
larger amount than usual and thereby the ink seems to
become dry instantaneously owing to the increased
penetration power of ink afforded by the surfactant.
However, the simple addition of a surfactant in a
larger amount as above cannot prevent mixing of
different colors of inks at the border of colors even
though it improves the ink fixation. Moreover, it
augments penetration of ink toward the back face of the
paper, which lowers color density on the paper face, or
causes nonuniform dyeing of a fiber layer on the paper
surface, resulting in irregularity of color density in
solid printing area and deterioration of image quality.
Furthermore, feathering and ink fixation on a
plain paper are improved by use of strongly alkaline
ink (see Japanese Patent Application Laid-Open No. 56-
57862, etc.), or by use of a specific kind of ink (see
Japanese Patent Application Laid-Open No. 56-5871,
CA 02312643 2000-06-27
- 4 -
etc.). These inks, however, do not always prevent
bleeding satisfactorily, and even in the case where the
bleeding is relatively slight, the feathering is
conspicuous (not satisfying the aforementioned
requirement (1) of the prior art) or ejection failure
is liable to occur (not satisfying the aforementioned
requirement (6) of the prior art). As above, no color
ink has been obtained which satisfies all the above
requirements and gives high quality of an image with
high speed on plain paper.
SUMMARY OF THE INVENTION
The present invention intends to provide an ink
for ink-jet recording which is capable of forming a
color image of high quality at high and uniform color
density on a usual recording medium such as plain paper
without feathering or ink-bleeding, and especially
without mixing of different colors of inks at the color
border.
The present invention also intends to provide
an ink-jet recording method, and an ink-jet recording
apparatus employing the above ink.
According to a first aspect of the present
invention, there is provided an ink for ink-jet
recording which contains a dye and water, and further
comprises the components (a), (b), and (c) below:
(a) at least one surfactant selected from the group
consisting of higher alcohol-ethylene oxide adducts
CA 02312643 2000-06-27
- 5 -
represented by General Formula [1], alkylphenol-
ethylene oxide adducts represented by General Formula
[2], ethylene oxide-propylene oxide copolymers
represented by General Formula [3], and acetylene
glycol-ethylene oxide adducts represented by General
Formula [4], at a content of from 0.1 to 20 ~ by weight
based on the total weight of the ink;
R-O- ( CHZCH20 ) n-H [ 1 ]
where R is alkyl, and n is~an integer;
R ~ ~ O-~CHzCHzO~ H
[2]
where R is alkyl, and n is an integer;
CH3
HO- ( CHZCH20 ) n- ( CH ~CH20 ) i-R
where R is alkyl or hydrogen, and n and ~ are
respectively an integer;
CHs CHI CHs CHs
I I I I
CH~CHCHZC - C = C - C - CHZCHCH9
2o I t
O O
CH2 CHZ
I I
C HZ C HZ
I I
O ~O
I m I n
H H
where m and n are respectively an integer;
CA 02312643 2000-06-27
- 6 -
(b) thiodiglycol; and
(c) urea or an derivative thereof.
According to a second aspect of the present
invention, there is provided an ink-jet recording
method which conducts recording on a recording medium
with droplets of ink, which comprises dye, water, and
the aforementioned components (a), (b), and (c).
According to a third aspect another aspect of
the present invention, there is provided a color ink-
jet recording method which conducts recording by
ejecting droplets of inks of two or more colors to
adjacent or superposed positions on a recording medium,
using the ink comprising a dye, water and the
aforementioned components (a), (b), and (c).
According to a fourth aspect of the present
invention, there is provided an ink which comprises a
dye, a water-soluble organic solvent, water, and a
compound of the formula;
2o RZ R3
R 1- C-EC = C~ C - R4
0
CHZ CHZ
CH2 CH2 L 5 l
b b
~m ~ n
H H
where R1, RZ, R3, and R4 are respectively hydrogen, an
CA 02312643 2000-06-27
alkyl or alkenyl group of 1 to 4 carbon atoms, or a
substituted or unsubstituted phenyl group at a content of
from 0.1 to 20% by weight based on the total weight of
the ink; and m+n is ranging from 0 to 50; and ~ is a
number of 2 or more.
According to a fifth aspect of the present
invention, there is provided an ink-jet recording method
which conducts recording with droplets of ink on a
recording medium, using the ink comprising a dye, water-
soluable organic solvent, water, and a compound
represented by General Formula [5] above.
According to a sixth aspect of the present
invention, there is provided a color ink-jet recording
method which conducts recording by ejecting droplets of
ink of two or more colors to adjacent or superposed
positions on a recording medium, using the ink comprising
a dye, water and the aforementioned compound represented
by General Formula [5] above.
According to a seventh aspect of the present
invention, there is provided a recording unit comprising
an ink container portion for holding ink and a head for
ejecting the ink as ink droplets, in which the ink is the
one specified in the above first or fourth aspect of the
present invention.
According to a eighth aspect of the present
invention, there is provided an ink cartridge comprising
an ink container portion for holding ink, in which the
ink is the one specified in the above first or fourth
aspect of the present invention.
CA 02312643 2000-06-27
_8_
According to ninth aspect of the present invention,
there is provided an ink-jet recording apparatus
comprising the recording unit of the seventh aspect of
the present invention, wherein the ink of the above first
or fourth aspect of the present invention is employed.
According to a tenth aspect of the present
invention, there is provided a ink-jet recording
apparatus, comprising an ink cartridge of the eighth
aspect of the present invention, and a recording head.
According to an eleventh aspect of the present
invention, there is provided a color ink-jet recording
method in which droplets of two or more color inks are
ejected in accordance of pulse signal to adjacent or
superposed positions on a recording medium, and in which
the ink comprises a nonionic surfactant in an amount of
from 1.0 to 20.0 o by weight based on the total weight of
the ink, the ink ejected for one pulse is in an amount of
from 10 to 70 p , and the feathering rate (A) defined by
Equation [I] is in the range of from 2.5 to 3.5:
A = B/C [I]
where B is a diameter (um) of a dot formed on plain
paper, and C is a diameter (um)of the ejected ink
droplet.
According to a twelfth aspect of the present
invention, there is provided color ink-jet recording
apparatus which conducts recording by ejecting droplets
CA 02312643 2000-06-27
_ g _
of two or more color inks onto adjacent or superposed
positions on a recording medium, said apparatus
comprises a recording means for conducting recording
mode, by use of an ink containing a nonionic surfactant
in an amount of from 1.0 to 20.0 ~ by weight, by
ejecting the ink for one pulse in an amount of from 10
to 70 p~ to form ink dots at the feathering rate (A)
defined by Equation [I] is in the range of from 2.5 to
3.5:
A = B/C [I]
where B is a diameter (um) of a dot formed on plain
paper, and C is a diameter (pm) of the ejected ink
droplet.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 shows an example of the pattern of
dotting of different color inks.
Fig. 2 shows another example of the pattern of
dotting of different color inks.
Fig. 3 is a longitudinal cross-sectional view
of a head portion of an ink-jet recording apparatus of
the present invention.
Fig. 4 is a transverse cross-sectional view of
a head portion of an ink-jet recording apparatus of the
present invention.
Fig. 5 is a perspective view of a head portion
of an ink-jet recording apparatus of the present
invention.
CA 02312643 2000-06-27
- 10 -
Fig. 6 is a perspective view of an ink-jet
recording apparatus of the present invention.
Fig. 7 is a longitudinal sectional view of an
ink cartridge of the present invention.
Fig. 8 is a perspective view of a recording
unit of the present invention.
Fig. 9 is a perspective view of a recording
portion in which a plurality of recording heads are
arranged and which was used in an example of the
present invention.
Fig. 10 is a perspective view of another
recording head used in the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The inventors of the present invention have
studied comprehensively a method of color image
formation which does not causes bleeding of ink and
gives a uniform color image without irregularity of
colors. As the result, it has been found as a first
invention that an ink containing the components (a),
(b), and (c) below is extremely effective:
(a) at least one surfactant selected from the group
consisting of higher alcohol-ethylene oxide adducts
represented by General Formula [1], alkylphenol-
ethylene oxide adducts represented by General Formula
[2], ethylene oxide-propylene oxide copolymers
represented by General Formula [3], and acetylene
glycol-ethylene oxide adducts represented by General
CA 02312643 2000-06-27
- 11 -
Formula [4], at a content of from 0.1 to 20 ~ by
weight;
R-O- ( CHzCHzO ) n-H [ 1 ]
where R is alkyl, and n is an integer;
~ O-fCH2CH20~- H
[2]
where R is alkyl, and n is an integer;
CH3
HO- ( CH2CH20 ) n- ( CH CHZO ) t-R [ 3 ]
Where R is alkyl or hydrogen, and n and ~.. are
respectively an integer;
CHs CHs CHs CHs
I I I I
CHsCHCH,x j - C = C - j - CHZCHCHs
O O
1 5 .I.
CHz CHZ
I I
CHZ CHZ
I I
O O
~m
H H
where m and n are respectively an integer;
(b) thiodiglycol; and
(c) urea or an derivative thereof.
As the further result of the study, it has been
found as a second invention that an ink comprising the
compound represented by General Formula (5) below is
extremely effective:
CA 02312643 2000-06-27
- 12 -
R2 R3
R1- C-EC---C~-C - R4
O O
~2 H2
1 1 [5]
CH2 CH2
b b
'~' n
H H
where Rl, Rz, R3, and R4 are respectively hydrogen, an
alkyl or alkenyl group of 1 to 4 carbon atoms, or a
substituted or unsubstituted phenyl group; and m+n is
ranging from 0 to 50; and ~ is a number of 2 or more.
The inks of the first invention and the second
invention are effective for formation of uniform images
without bleeding or color irregularity presumably from
the reasons below.
The most important factor which affects
prevention of ink bleeding and uniformity of color of
recorded images is considered to be the wettability of
a recording medium by the ink, or a wetting power of
the ink on the recording medium. Among the recording
media, plain paper especially has fibers exposed on the
recording surface, and the fiber density on the surface
is not uniform. At the portion where the fiber density
is high, the ink fixation is slow, whereby ink bleeds
or color of an image becomes irregular. The ink which
has a sufficient wetting power is considered to be
fixed uniformly irrespectively of the paper fiber
CA 02312643 2000-06-27
- 13 -
density, and to be free from bleeding and color
irregularity. Further, the ink which has excellent
wetting power is considered to form precisely circular
dots with uniformity of color, thereby providing images
of higher quality.
The first invention of the present invention
will be described in detail.
The wetting power of the ink relates closely to
the interaction between the ink and the recording
material at the interface. Addition of a surfactant
generally decreases the interfacial tension between the
ink and the recording medium, and improves the wetting
power of the ink. In particular, the nonionic
surfactant having ethylene oxide chain as the component
(a) of the first invention, when incorporated in the
ink, the hydrophilic ethylene oxide portion of the
surfactant presumably orients toward the recording
medium to give a specific uniform wettability. On the
contrary, an ionic surfactant, which has a hydrophilic
portion which has less affinity with the recording
medium than the nonionic surfactant, does not exhibit
such effect.
The ethylene oxide addition type nonionic
surfactant in the present first invention is preferably
added in an amount of from 0.1 to 20 ~, more preferably
from 0.1 to 5 ~ by weight based on the weight of the
ink. The wetting power is not sufficient at the amount
CA 02312643 2000-06-27
- 14 -
of the surfactant of less than 0.1 $ by weight, while,
addition of the surfactant in an amount exceeding 20
by weight does not improve more the wetting property
and is disadvantageous in production cost and ink
reliability.
The addition number of the ethylene oxide unit,
the hydrophilic portion, in the ethylene oxide addition
type nonionic surfactant in the present first invention
is preferably in the range of from 4 to 20, more
preferably from 4 to 10 in terms of "n" or "n+m" in
consideration of the affinity of the ethylene oxide
moiety with the recording medium and orientation
thereon. At the value of "n" or "n+m" of less than 4,
the solubility of the surfactant is not sufficient to
achieve the effect of the present invention, while at
the value of more than 20, the excessive ethylene oxide
is not necessarily effective and leads to slightly
unstable ink ejection.
The medium for the aforementioned ethylene
oxide addition type nonionic surfactant is described
below.
Generally, the ethylene oxide addition type
nonionic surfactant is inconvenient for stabilization
of ink ejection because of its relatively high
viscosity in consideration of ejection stabilization.
Therefore, an additional water-soluble organic solvent
is studied to improve the ink ejection without
CA 02312643 2000-06-27
- 15 -
impairing the effects of the present invention.
Consequently, thiodiglycol has been found to be
satisfactory. The failure of ink ejection is caused
generally by rise of viscosity resulting from
vaporization of water at the nozzle. The use of
thiodiglycol is considered to reduce more the rise of
the viscosity than other solvents, thereby improving
the ejection property. However, single use of
thiodiglycol is not sufficiently effective yet for
ejection stabilization. After comprehensive study, it
has been found that combined use of thiodiglycol and
urea or a derivative of urea improves greatly the ink
ejection property. Presumably, the interaction between
the thiodiglycol and urea or a urea derivative
suppresses the rise of the viscosity specifically, and
the dissolution of a dye is improved. The thiodiglycol
and a urea derivative-thiourea derivative are used
respectively in an amount of from 1 to 30 % by weight.
The amount of water used in the present first
invention is preferably in the range of from 50 to 85
%, more preferably from 55 to 75 % by weight. If the
amount of water is less than 50 %, the viscosity of the
ink is relatively high, and the ejection stability
tends to be relatively lower, even when thiodiglycol or
urea or derivative thereof is used concurrently. If
the amount of water is more than 85 %, the ethylene
oxide portion, which is the hydrophilic portion of the
CA 02312643 2000-06-27
- 16 -
ethylene oxide addition type nonionic surfactant, is
relatively free, resulting in less orientation thereof
and less uniformity.
The water-soluble organic solvents constituting
the ink of the present first invention include
polyalkylene glycols such as polyethylene glycol, and
polypropylene glycol; alkylene glycols having 2 to 6
carbon atoms such as ethylene glycol, propylene glycol,
butylene glycol, triethylene glycol, hexylene glycol,
and diethylene glycol; glycerin; 1,2,6-hexanetriol;
lower alkyl ether of polyhydric alcohols such as
ethylene glycol methyl ether, diethylene glycol methyl
(or ethyl) ether, and triethylene glycol monomethyl (or
ethyl) ether; alcohols such as methyl alcohol, ethyl
alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl
alcohol, sec-butyl alcohol, t-butyl alcohol, isobutyl
alcohol, benzyl alcohol, and cyclohexanol; amides such
as dimethylformamide, and dimethylacetamide; ketones
and ketone alcohols such as acetone, and diacetone
alcohol; ethers such as tetrahydrofuran, and dioxane;
and nitrogen-containing heterocyclic ketones such as N-
methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-
imidazolidinone.
The water-soluble organic solvent may be
incorporated in such an amount that the ink-bleeding is
not caused and the ejection property is not impaired.
Among the above solvents, preferred are ethylene
CA 02312643 2000-06-27
- 17 -
glycol, triethylene glycol, hexylene glycol, diethylene
glycol, glycerin, ethyl alcohol, isopropyl alcohol,
cyclohexanol, and so forth. The solvent preferably is
contained in an amount of from 1 to 15 % by weight
based on the total weight of the ink.
The dyes employed in the present invention
include direct dyes, acid dyes, reactive dyes, disperse
dyes, vat dyes, and the like. The content of the dye
is decided depending on the kinds of the liquid medium
components and the required properties of the ink, and
is generally in the range of from 0.5 to 15 $,
preferably from 1 to 7 % by wight based on the total
weight of the ink.
The main constituents of the ink of the present
first invention are described above. Other additives
may be incorporated provided that the objects of the
invention are achievable. The additive includes
viscosity-adjusting agents such as polyvinyl alcohol,
celluloses, and water-soluble resins; pH-controlling
agents such as diethanolamine, triethanolamine, and
buffer solutions; fungicides; and so forth. To the ink
of electrically chargeable type used for ink-jet
recording in which the ink droplets are charged, a
resistivity-adjusting agent is added such as lithium
chloride, ammonium chloride, and sodium chloride.
The second invention will be described in
detail.
CA 02312643 2000-06-27
- 18 -
Generally, inks which contain a compound having
one triple bond in the molecule give uniform color.
However, the ink of the present second invention
provides much more excellent uniformity of color than
the above ink containing a compound having one triple
bond.
Presumably, the compound which is represented
by General Formula [5] having two or more triple bonds
and contained in the ink of the present second
invention has high electron density in the molecule and
has rigid hydrophobic portion (triple bond-containing
portion), causing little a free change in structure in
comparison with the compound having one triple bond,
whereby the compound of General Formula [5] orients
regularly to the surface of the ink, and interacts
effectively with the recording medium at the interface
to exhibit high wettability.
The ink of the present second invention
contains the compound of General Formula [5] below in
an amount of preferably from 0.001 to 20 ~, more
preferably from 0.001 to 5 $ by weight based on the
total weight of the ink, and the number of m+n in the
formula is in the range of from 0 to 50.
CA 02312643 2000-06-27
- 19 -
R2 R3
R 1- C-EC = C~ C - R4
O O
"1"2 C1 2 L 5 7
CH2 CHZ
b d
~m ~ n
H H
Specific examples of the compound of General
Formula [5] are shown below without limiting the
compound thereto in any way.
No.l
O-C-C=C-C=C-C-
O O
CH2 ~HZ
~H2 CHI
d d
~m ~f'n
H H
2o No.2 C2H5 C2H5
C2H5-CHZ-O-C-C=C-C=C-C-0-CH2-C2H5
O
CH2 CH2
~H2 CH2
b 'O
Im In
H H
CA 02312643 2000-06-27
- 20 -
1
No.3
CH3 CHg CHg CHg
CH3=CH-CHZ-C-C=C-C_--C-C-CH2-CH-CHg
I I
O O
CH2 C i2
CHZ CHZ
O
~m ~n
H H
to
No.4
CHg CH3
C2 H5-0-C-C-C-C-C°-C-C-C2H5
O
H2 H2
CH2 CH2
is O O
~m 'f'n
H H
No.S
C2H5 CHg
I I
2o CZHS- C=C-C=C-C-O-C2H5
-C=C-
~
O
C
i2 C I2
CHZ CH2
~m 'I'n
H H
a
CA 02312643 2000-06-27
- 2z -
The liquid medium constituting the ink of the
present second invention may be an plain water-soluble
organic solvent. The water-soluble solvents include
polyalkylene glycols such as polyethylene glycol, and
polypropylene glycol; alkylene glycols having 2 to 6
carbon atoms such as ethylene glycol, propylene glycol,
butylene glycol, triethylene glycol, hexylene glycol,
diethylene glycol, and thiodiglycol; glycerin; 1,2,6-
hexanetriol; lower alkyl ether of polyhydric alcohols
such as ethylene glycol methyl ether, diethylene glycol
methyl (or ethyl) ether, and triethylene glycol
monomethyl (or ethyl) ether; alcohols such as methyl
alcohol, ethyl alcohol, n-propyl alcohol, isopropyl
alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl
alcohol, isobutyl alcohol, benzyl alcohol, and
cyclohexanol; amides such as dimethylformamide, and
dimethylacetamide; ketones and ketone alcohols such as
acetone, and diacetone alcohol; ethers such as
tetrahydrofuran, and dioxane; and nitrogen-containing
heterocyclic ketones such as N-methyl-2-pyrrolidone, 2-
pyrrolidone, 1,3-dimethyl-2-imidazolidinone.
Among the above water-soluble solvents,
preferred are ethylene glycol, triethylene glycol,
hexylene glycol, diethylene glycol, glycerin,
thiodiglycol, ethyl alcohol, isopropyl alcohol,
cyclohexanol, and so forth. The solvent is preferably
contained at a content of from 1 to 35 $ based on the
CA 02312643 2000-06-27
- 22 -
total weight of the ink.
The dyes employed in the present invention
include direct dyes, acid dyes, basic dyes, reactive
dyes, disperse dyes, vat dyes, and the like. The
content of the dye is decided depending on the kinds of
the liquid medium components and the required
properties of the ink, and is generally in the range of
from 0.5 to 15 %, preferably from 1 to 7 % by weight
based on the total weight of the ink.
The main constituents of the ink of the present
second invention are described above. Other additives
may be added provided that the objects of the invention
are achievable. The additives include clogging-
preventing agents such as urea and its derivatives;
viscosity-adjusting agents such as polyvinyl alcohol,
celluloses, and water-soluble resins; pH-controlling
agents such as diethanolamine, triethanolamine, and
buffer solutions; fungicides; surfactants, and so
forth. To the ink of electrically chargeable type used
for ink-jet recording in which the ink droplets are
charged, an resistivity-adjusting agent is preferably
incorporated such as lithium chloride, ammonium
chloride, and sodium chloride.
The inks of the first invention and the second
invention are suitable for ink-jet recording in which
the ink droplets are ejected by action of thermal
energy. However, the inks are naturally useful also
CA 02312643 2000-06-27
- 23 -
for other types of ink-jet recording and for general
writing implements.
The recording apparatus suitable for recording
with the ink of the present first invention and the
present second invention includes those in which
thermal energy is given to the ink in a chamber in a
recording head in correspondence with recording signals
and thereby ink droplets are formed.
The third invention will be described in
detail.
The inventors of the present invention have
noticed the necessary conditions shown below for
forming color images in high quality on plain paper.
When different color inks are dotted in a
pattern as shown in Fig. l, the different color inks
are less liable to be mixed at the boundaries of the
dotted colors, even if the adjacent color is dotted
subsequently in a short time. In this case, however,
disadvantages may be caused such that the central
portion surrounded by dots becomes blank, which may
cause decrease of color density, and a slight shift of
the ejected ink droplet from the aimed impact point may
increase the area of the blank portion.
On the contrary, if the ink is dotted as shown
in Fig. 2 by satisfying the Equation [II] below, the
above disadvantage is significantly reduced, and
excellent images are obtained:
CA 02312643 2000-06-27
- 24 -
B >_ ~x 103 x 1/D [II]
where B is a dot diameter (pm) formed on plain paper,
and D is a recording density (dots/mm). In this method
of dotting, however, different color inks are
necessarily mixed as shown by the shadowed portions in
Fig. 2, and thereby mixing of the different color inks
is liable to occur.
In Figs. 1 and 2, C, M and Y means a droplet of
cyan ink, magenta ink and yellow ink, respectively.
The inventors have investigated the method of
preventing the mixing of different color inks at the
color boundaries with the high quality of image being
maintained regarding the case where the inks are dotted
according to Equation [II]. As the result, it has been
found that the above problem is solved by adjusting the
feathering rate (A) shown by Equation [I] below on
plain paper to be in the range of from 2.5 to 3.5.
A = B/C [I]
where B is a dot diameter (um) formed on plain paper,
and C is a diameter (um) of the elected ink droplet.
At the feathering rate of less than 2.5,
the ink droplet attached on paper surface spreads less
and the ink layer does not become thin, thereby
different colors of inks coming to be mixed at the
boundaries of colors when inks are dotted under the
conditions shown in Fig. 2. On the contrary, at the
feathering rate of more than 3.5, the ink droplet
CA 02312643 2000-06-27
- 25 -
spreads excessively and the edge of the dot becomes
unclear, thus providing images of low quality.
In order to control the feathering ratio in the
range of from 2.5 to 3.5, nonionic surfactant is
incorporated into the ink in an amount of from 1 to 20
$, more preferably from 3 to 10 $ by weight. With the
amount of.the nonionic surfactant of less than 1 $ by
weight, the feathering ratio becomes less than 2.5,
thus causing color ink mixing at the color border,
while with the amount of the nonionic surfactant of
more than 20 % by weight, the feathering rate becomes
more than 3.5, thus the image quality liable to become
low.
Simple use of surfactant in a large amount
gives rise to disadvantages of lowering of color
density and image quality caused by excessive
penetration of ink droplets toward the back face of the
paper sheet, and of nonuniformity of color density in a
solid print portion caused by nonuniform dyeing of the
fiber layer at the paper surface. The inventors of the
present invention have found that color image recording
with high quality is practicable when a nonionic
surfactant is used as the surfactant and when printing
is carried out using the ink containing it in an amount
of from 1 to 20 $ by weight with controlling the amount
of ink ejection in the range of from 10 to 70 p:2,
preferably from 20 to 50 pR per one nozzle for one
CA 02312643 2000-06-27
- 26 -
pulse. The present third invention has been
accomplished on the basis of the above two findings.
The nonionic surfactant does not have selective
affinity to a fiber layer on the surface of paper,
whereby uniform dyeing is achievable and nonuniformity
of color density is avoided. The ink for the color
recording method of the present invention contains a
surfactant in a large amount. Therefore, if the ink
droplets are elected in an amount of more than 70 p~
per one nozzle for one pulse, the amount of the ink
exceeds the absorbable and fixable limit of the fiber
layer on the paper surface, causing penetration of ink
into a pore layer under the fiber layer owing to the
penetrating power of the surfactant, thus resulting in
deterioration of image quality owing to lowered color
density and irregular feathering. Accordingly the
amount of the ink ejection has to be controlled to be
in the range of from 10 to 70 p~2 per pulse.
The nonionic surfactants employed in the
present third invention include polyoxyethylene alkyl
ethers, polyoxyethylene phenyl ethers, polyoxyethylene-
polyoxypropylene glycols, polyoxyethylene-
polyoxypropylene alkyl ethers, polyethylene oxide
adducts of acetylene glycol, etc. Of these, preferred
are nonylphenyl ether-ethylene oxide adducts, ethylene
oxide-propylene oxide copolymer (EO-PO adducts),
acetylene glycol-polyethylene oxide adducts;
CA 02312643 2000-06-27
- 27 -
particularly preferred are acetylene glycol-
polyethylene oxide adducts (acetylene glycol-EO
adducts) represented by the structural formula below.
CHs CHa CHa CHa
I
CHa-CH-CHz-C-C=C- i -CHz-CH-CHa
O O
CHz CHa
I I
i Ha j Hz
O n O as
H H
where m + n = 10.
The water-soluble organic solvents employed in
addition to the nonionic surfactant in the present
third invention include amides such as
dimethylformamide, and dimethylacetamide; ketones such
as acetone; ethers such as tetrahydrofuran, and
dioxane; polyalkylene glycols such as polyethylene
glycol, and polypropylene glycol; alkylene glycols
having 2 to 6 carbon atoms such as ethylene glycol,
propylene glycol, butylene glycol, triethylene glycol,
thiodiglycol, hexylene glycol, and diethylene glycol;
glycerin; 1,2,6-hexanetriol; lower alkyl ether of
polyhydric alcohols such as ethylene glycol methyl (or
ethyl) ether, diethylene glycol methyl (or ethyl)
ether, and triethylene glycol monomethyl (or ethyl)
ether; N-methyl-2-pyrrolidone, 1,3-dimethyl-2-
CA 02312643 2000-06-27
- 28 -
imidazolidinone, triethanolamine, sulfolane,
dimethylsulfoxide, and so forth.
The clogging-preventing agents include urea and
derivatives of urea, sulfonamides, and the like.
The dyes employed in the present invention
include direct dyes, acid dyes, reactive dyes, disperse
dyes, vat,dyes, and the like. The content of the dye
is decided depending on kinds of the liquid medium
components and the required properties of the ink, and
is generally in the range of from 0.5 to 15 %,
preferably from 1 to 7 % by weight based on the total
weight of the ink.
The main constituents of the ink of the present
third invention are described above. Other additives
may be added provided that the objects of the invention
are achievable. The additives include viscosity-
adjusting agents such as polyvinyl alcohol, celluloses,
and water-soluble resins; pH-controlling agents such as
diethanolamine, triethanolamine, and buffer solutions;
fungicides; and so forth. To formulate the ink of
electrically chargeable type used for ink-jet recording
in which the ink droplets are charged, an resistivity-
adjusting agent is preferably added such as lithium
chloride, ammonium chloride, and sodium chloride.
The recording method of the present third
invention is particularly suitable for ink-jet
recording in which ink droplets are ejected by the
CA 02312643 2000-06-27
- 29 -
action of thermal energy, but is also applicable to
other ink-jet recording methods.
A recording apparatus is described below which
produces ink droplets by thermal energy and is suitable
for practising the recording of the present first
invention, the present second invention, and the
present third invention. The present invention is
suitable for the recording system in which recording
signal is applied to a recording ink in a recording
head and ink droplets are ejected by the action of the
generated thermal energy. The construction of the
recording head, which is the main portion of the
apparatus, is shown in Figs. 3, 4, and 5.
A head 13 is constructed by bonding a plate of
glass, ceramics, or plastics having an ink flow path to
a heat-generating head 15. (The the head is shown in
the drawing, but the invention is not limited to this.)
The heat-generating head 15 is constituted of a
protection layer 16 formed of silicon oxide or the
like, aluminum electrodes 17-1 and 17-2, a heat-
generating resistance layer 18 formed of nichrome or
the like, a heat accumulation layer 19, and a substrate
plate 20 made of aluminum or the like having a high
heat-radiating property.
Ink 21 reaches the ejection orifice 22, forming
a meniscus 23 by action of pressure P not shown in the
drawing.
CA 02312643 2000-06-27
- 30 -
On application of an electric signal to the
electrodes 17-1 and 17-2, the region designated by a
symbol "n" on the heat-generating head 15 generates
abruptly heat to form a bubble in the portion of the
ink 21 contacting therewith. The pressure generated by
the bubble pushes out the meniscus 23 and ejects the
ink 21 from the orifice 22 in a form of ink droplets
24, and the ink droplets are ejected to a recording
medium 25. Fig. 5 shows a rough sketch of a multiple
recording head constructed by juxtaposing a
multiplicity of heads shown in Fig. 3. The recording
head is prepared by bonding a glass plate 27 having a
plurality of flow paths to a heat-generating head 28
similar to the one shown in Fig. 3.
Incidentally, Fig. 3 is a cross-sectional view
of the head 13 along an ink flow path, and Fig. 4 is a
cross-sectional view of the head at the line A-B in
Fig. 3.
Fig. 6 illustrates an example of the ink-jet
recording apparatus having such a head mounted therein.
In Fig. 6, a blade 61 as a wiping member is
held at one end by a blade-holding member, forming a
fixed end in a shape of a cantilever. The blade 61 is
placed at a position adjacent to the recording region
of the recording head, and is constituted such that it
moves in the direction perpendicular to the moving
direction of the recording head to come into contact
CA 02312643 2000-06-27
- 31 -
with the ejection nozzle face to cap the nozzles. An
ink absorption member 63 is provided at a position
adjacent to the blade 61, and is held so as to protrude
into the moving path of the recording head in a manner
similar to that of the blade 61. The aforementioned
blade 61, the cap 62, and the absorption member 63
constitute an ejection-recovery section 64. The blade
61 and the absorption member 63 remove water, dust, and
the like from the ink ejecting nozzle face.
A recording head 65 has an ejection energy-
generating means for ejection, and conducts recording
by ejecting ink onto a recording medium opposing to the
ejection nozzle face. A carriage 66 is provided for
supporting and moving the recording head 65. The
carriage 66 is engaged slideably with a guide rod 67.
A portion of the carriage 66 is connected (not shown in
the drawing) to a belt 69 driven by a motor 68, so that
the carriage 66 is movable along the guide rod 67 to
the recording region of the recording head 65 and the
adjacent region thereto.
A paper delivery portion 51 for delivery of a
recording medium and a paper delivery roller 52 driven
by a motor (not shown in the drawing) delivers the
recording medium to the position opposing to the
ejecting nozzle face of the recording head, and the
recording medium is discharged with the progress of the
recording to a paper discharge portion provided with
CA 02312643 2000-06-27
4
- 32 -
paper-discharging rollers 53.
In the above constitution, when the recording
head 65 returns to a home position at the completion of
the recording or other timing, the cap 62 of the
ejection-recovery portion 64 is positioned out of the
moving path of the recording head 65, and the blade 61
is made to protrude into the moving path. Therefore,
the ejecting nozzle face of the recording head 65 is
wiped therewith. The cap 62 moves to protrude toward
the moving path of the recording head when the cap 62
comes into contact with the ejecting nozzle face of the
recording head for capping.
At the time when the recording head 65 moves
from the home position to the record-starting position.,
the cap 62 and the blade 61 are at the same position as
in the above-mentioned wiping time, so that the
ejection nozzle face of the recording head is wiped
also in this movement.
The recording head moves to the home position
not only at the end of the recording and at the time of
ejection recovery, but also at a predetermined interval
during movement for recording in the recording region.
Hy such movement, the wiping is conducted.
Fig. 7 illustrates an example of the ink
cartridge 95 that contains ink to be supplied through an
ink supplying member such as a tube. The ink container
portion 40, for example an ink bag, contains an ink to
CA 02312643 2000-06-27
- 33 -
be supplied, and has a rubber plug 42 at the tip. By
inserting a needle (not shown in the drawing) into the
plug 42, the ink in the ink bag 40 becomes suppliable.
An ink absorption member 44 absorbs waste ink.
The ink container portion has preferably a
liquid-contacting surface made of polyolefin,
particularly preferably made of polyethylene.
The ink-jet recording apparatus used in the
present invention is not limited to the above-mentioned
one which has separately a head and an ink cartridge.
Integration thereof as shown in Fig. 8 may suitably be
used.
In Fig. 8, a recording unit 70 houses an ink
container portion such as an ink absorption member, and
the ink in the ink absorption member is ejected from a
head 71 having a plurality of orifices. The ink
absorption member may be made of a material such as
polyurethane. An air-communication opening 72 is
provided to communicate interior of the cartridge with
the open air. The recording unit 70 may be used in
place of the recording head shown in Fig. 6, and is
readily mountable to and demountable from the carriage
66.
An ink-jet recording apparatus which ejects ink
droplets by action of thermal energy to the ink is
exemplified above. The present invention, however, is
applicable also to other ink-jet recording apparatuses
CA 02312643 2000-06-27
- 34 -
such as the one of piezo type which employs a
piezoelectric element.
For practising the recording according to the
present invention, a recording apparatus, for example,
is used which has four in number of recording heads
shown in Fig. 5 juxtaposed on a carriage. Fig. 9 shows
an example of the apparatus. Recording heads 81, 82,
83, and 84 are recording heads ejecting respectively
recording inks of yellow, magenta, cyan, and black.
The heads are mounted on the aforementioned recording
apparatus, and eject respective color inks in
accordance with recording signals. The apparatus in
Fig. 9 employs four recording heads, but the present
invention is not limited thereto. One recording head
may be constructed to ejects all of the yellow,
magenta, cyan, and black inks as shown in Fig. 10.
The present invention is described in more
detail by reference to Examples and Comparative
Examples. In the description, the terms "parts" and
"~" are based on weight unless otherwise mentioned.
Hereinafter, the ethylene oxide adduct is simply
referred to as "E0 adduct".
The dyes and liquid medium in an amount (parts)
shown below are employed in the Example and Comparative
Example to provide each 100 parts of inks,
respectively.
Example 1
CA 02312643 2000-06-27
- 35 -
(Dyes)
Black: C.I. Food Black 2 2 parts
Dye A of Formula below 1.2 parts
Dye B of Formula below 0.8 part
Yellow: C.I. Direct Yellow 86 2.5 parts
Cyan: C.I. Direct Blue 199 3.5 parts
Magenta: Dye C of Formula below 3.5 parts
(Liquid medium)
Thiodiglycol 7.5 parts
Urea 7.5 parts
Glycerin 7.5 parts
Higher alcohol-EO adduct (n=15)* 1 part
Pure water balance
* Higher alcohol-EO adduct: BO-15TX trade-mark of Nikko
Chemicals K.K.) is used.
Dye A OH
O O ~ ~ ~ ~ ~ ~N~ .
' S03Li
S03Li
S03Li
S03Li
Dye B
OCH3 OH
~'OON~~
~ ~ SO3Li
S03Li CH3 S03Li
Dye C
S03Na OH
CH3~C~~1 ~ ~ NH-C0~
S03Na S03Na
CA 02312643 2000-06-27
- 36 -
Each of the four color compositions was stirred
sufficiently, and was filtered under pressure through a
Fluoropore Filter (trade-mark of Sumitomo
Electric Industries, Ltd.) having a pore diameter. of
0.22 um to prepare the ink of the present invention.
The respective inks were introduced into a color ink-
bet printer BJC-820J (trade-mark of Canon K.K.)
which conducts recording by forming ink droplets by
applying thermal energy to the inks in the recording
heads, and recording was conducted on commercial paper
.
sheets for copying (Canon~NP Dry SK), and bond paper
sheets (Plover Bond Paper PB).
Evaluation was made as described below. The
results are shown in Table 1.
(1) Bleeding:
Color samples were prepared by printing such
that different colors are adjacent to each other, and
the occurrence of bleeding was evaluated by the
standard below. The evaluation was made for seven
colors: black, yellow, cyan, and magenta; and red,
green, and blue formed by dotting in superposition of
two colors taken from the colors of yellow, cyan, and
magenta.
o . No bleeding is observed at every boundary.
a . Bleeding is remarkable at the boundaries of red,
green, and blue where a larger amount of ink is
applied.
* trade-marks
CA 02312643 2000-06-27
- 37 -
x . Bleeding is remarkable at nearly all the
boundaries.
(2) Color uniformity:
Uniformity at solid color print portions are
examined visually.
o . Solid color print is completely uniform without
irregularity.
a . Nonuniformity is remarkable at the portion where
fiber density is high.
x . Color irregularity is much more remarkable.
(3) Occurrence of feathering:
Three hundred dots are printed continuously on
a commercial paper sheet for copying and a commercial
bond paper sheet such that the dots are not brought
into contact with each other. The dotted ink are dried
in the air for 24 hours at room temperature. Irregular
shape and irregular feathering of dots are counted
under microscope. The evaluation is made by the
percentage of the counted dot number according to the
standard below:
not more than 10 $
o . 11 $ to 30 $
a . 31 $ to 50 $
x . not less than 51 $
(4) Ejection property:
The ink to be tested is filled to the printer,
and alphabet and numeral letters are printed
CA 02312643 2000-06-27
- 38 -
continuously for 10 minutes with the printer.
Thereafter, printer is left standing without capping of
the nozzles. After 10 minutes of intermission of the
printing, the printing is started again. The ejection
property is evaluated from scratches and unsharped
edges in printed letters after restarting the printing.
o . No scratch and no unsharped edge is observed from
the first letter.
a . A part of the first letter is scratched or
unsharped.
x . The first letter cannot be printed.
(5) Storage stability:
The ink is placed in an amount of 100 m~ in a
heat-resistant glass bottle, stoppered tightly, and
stored in a thermostatic chamber at 60°C. After 2
months of storage, the ink is used for printing, and
evaluated.
o . No abnormality is observed.
x . Failure of discharge, or irregularity or
discoloration of printed letters is observed.
(6) Anti-Clogging (crusting recovery):
The ink to be tested is filled to the printer,
and alphabet and numeral letters are printed
continuously for 10 minutes with the printer.
Thereafter, printer is left standing without capping of
the nozzles. After one month of intermission of the
printing, ejection recovery operation was conducted.
CA 02312643 2000-06-27
- 39 -
The evaluation was made by counting the required number
of times of the ejection recovery operations for
carrying out normal printing.
o . Printing is normal after 1 to 5 times of ejection
recovery operation.
a . Printing is normal after 6 to 10 times of eje ction
recovery operation.
x . Printing is normal after 11 or more times of
ejection recovery operation.
Examples 2 to 5
In respective Examples, the kind and the amount
of the dyes used were as below:
(Dyes for Examples 2 to 4)
Black: C.I. Food Black 2 2 arts
p
Dye A 1.2 parts
Dye B 0.8 part
Yellow: C.I. Direct Yellow 86 2.5 parts
Cyan: C.I. Direct Blue 199 3.5 parts
Magenta: Dye C 3.5 parts
(Dyes for Example 5)
Black: C.I. Food Black 2 2
parts
Dye A 1.2 parts
Dye B 0.8 part
Yellow: C.I. Direct Yellow 86 2.5 parts
Cyan: C.I. Acid Blue 9 3.0 parts
Magenta: Dye C 3.5 parts
The liquid mediums used in respective Examples
were as
CA 02312643 2000-06-27
- 40 -
below:
(Liquid medium for Example 2)
Thiodiglycol 7.5 parts
Urea 7.5 parts
Glycerin 7.5 parts
Nonylphenyl ether-EO adduct
(n =9 to 10) 5 part
Pure water balance
(Liquid medium for Example 3)
Thiodiglycol 7.5 parts
Thiourea 7.5 parts
Glycerin 7.5 parts
Ethylene oxide-propylene oxide
copolymer (n=10 "Q=7) 15 parts
Pure water balance
(Liquid medium for Example 4)
Thiodiglycol 7.5 parts
Urea 7.5 parts
Glycerin 7.5 parts
Acetylene glycol-EO adduct
(n+m = 10) 5 parts
Pure water balance
(Liquid medium for Example 5)
Thiodiglycol 7.5 parts
Urea 7.5 parts
Glycerin 7.5 parts
Acetylene glycol-EO adduct
CA 02312643 2000-06-27
- 41 -
(n+m = 4) 1 parts
Pure water balance
In the above, as acetylene glycol-EO adduct. Acetylenol
(trade-mark of Kawaken Fine Chemical K.K.) as the
nonylphenyl ether-EO adduct, Emulgen 909 (trade-mark of Kao
Corporation), and as the ethylene oxide-propylene oxide
copolymer, Karpole MH-50 (trade-mark of Asahi Denka Kogyo
K.K.) are used, respectively.
The respective inks were prepared with the dye
and the liquid medium shown above in the same manner as
in Example 1. Printing properties, ejection
properties, and the storage stability of the inks were
evaluated in the same manner as in Example 1. The
results are shown in Table 1.
Comparative Examples 1 to 5
In respective Comparative Examples, the kind
and the amount of the dyes were are as below:
(Dyes for Comparative Examples 1 to 5)
Black: C.I. Food Black 2 2 parts
Dye A 1.2 parts
Dye B 0.8 part
Yellow: C.I. Direct Yellow 86 2.5 parts
Cyan: C.I. Direct Blue 199 3.5 parts
Magenta: Dye C 3.5 parts
The liquid mediums used in respective Comparative
Examples were as below:
(Liquid medium for Comparative Example 1)
CA 02312643 2000-06-27
- 42 -
Thiodiglycol 7.5 parts
Urea 7.5 parts
Glycerin 7.5 parts
Pure water balance
(Liquid medium for Comparative Example 2)
Thiodiglycol 15 parts
Glycerin 7.5 parts
Acetylene glycol-EO adduct
(n+m = 10) 5 parts
Pure water balance
(Liquid medium for Comparative Example 3)
Urea 10 parts
Glycerin 12.5 parts
Acetylene glycol-EO adduct
(n+m = 10) 5 arts
P
Pure water balance
(Liquid medium for Comparative Example 4)
Thiodiglycol 7.5 parts
Urea 7.5 parts
Glycerin 7.5 parts
Anionic surfactant (Neopelex 25,
made by Kao Corporation) 7 parts
Pure water balance
(Liquid medium for Comparative Example 5)
Thiodiglycol 7.5 parts
Urea 7.5 parts
Glycerin 7.5 parts
CA 02312643 2000-06-27
- 43 -
Cationic surfactant (Cation DDC-50,
made by Sanyo Chemical
Industries, Ltd.) 5 parts
Pure water balance
The respective inks were prepared with the dye
and the liquid medium shown above in the same manner as
in Example 1. Printing properties, ejection
properties, and the storage stability of the inks were
evaluated in the same manner as in Example 1. The
results are shown in Table 1.
Table 1
Evaluation (1) (2) (3) (4) (5) (6)
item
SK PB SK PB SK PB
Examples
1 0 0 0 0 0 0 0 0 0
2 0 0 0 0 0 0 0 0 0
3 0 0 0 0 0 0 0 0 0
4 0 0 0 0 ~ m o 0 0
5 0 0 0 0 ~ 0 0 0 0
Comparative examples
1 x x x x o 0 0 0 0
2 0 0 0 0 0 o a o x
3 0 0 0 0 0 o x o a
4 0 o a x x x x x a
5 a x a x a a x x x
CA 02312643 2000-06-27
- 44 -
SK: Commercial paper for copying
PB: Plover Bond paper
Examples 6 to 10 and Comparative Example 6
The dyes of black, cyan, magenta, and yellow,
and the amount thereof used in respective Examples and
Comparative Example are as shown below:
(Dyes)
Black: C.I. Food Black 2 2 parts
Dye A 1.2 parts
Dye B 0.8 part
Yellow: C.I. Direct Yellow 86 2.5 parts
Cyan: C.I. Acid Blue 9 3.5 parts
Magenta: Dye C 3.5 parts
Example 6
Dye (black, yellow, cyan, or magenta)
in an amount as shown above
Glycerin 8 parts
Urea 5 parts
Thiodiglycol 8 parts
Compound No.l 1 part
Pure water balance
The above ink compositions were respectively
stirred sufficiently, and filtered through a Fluoropore
Filter (pore diameter 0.22 um, trade name, made by
Sumitomo Electric Industries, Ltd.) to prepare
inks of
this Example.
Example 7
CA 02312643 2000-06-27
- 45 -
Dye (black, yellow, cyan, or magenta)
in an amount as shown above
Glycerin 8 parts
Urea 5 parts
Thiodiglycol 8 parts
Compound No.2 16 part
Pure water balance
The above ink compositions were prepared in the
same manner as in Example 6 to prepare inks of this
Example.
Example 8
Dye (black, yellow, cyan, or magenta)
in an amount as shown above
Glycerin 8 parts
Urea 5 parts
Thiodiglycol 8 parts
Compound No.3 0.5 part
Cyclohexanol 1 part
Pure water balance
The above ink compositions were prepared in the
same manner as in Example 6 to prepare inks of this
Example.
Example 9
Dye (black, yellow, cyan, or magenta)
in an amount as shown above
Glycerin 8 parts
Urea 5 parts
CA 02312643 2000-06-27
- 46 -
Thiodiglycol 8 parts
Compound No.4 10 parts
Pure water balance
The above ink compositions were
prepared in the
same manner as in Example 6 to prepare inks of this
Example.
Example 10
Dye (black, yellow, cyan, or magenta)
in an amount as shown above
Glycerin 8 parts
Urea 5 parts
Thiodiglycol 8 parts
Compound No.5 5 parts
Pure water balance
The above ink compositions were
prepared in the
same manner as in Example 6 to prepare inks of this
Example.
Comparative Example 6
Dye (black, yellow, cyan, or magenta)
in an amount as shown above
Glycerin 5 parts
Urea 5 parts
Thiodiglycol 6 parts
Pure water balance
The above ink compositions were
prepared in the
same manner as in Example 6 to prepare inks of this
Comparative Example.
CA 02312643 2000-06-27
- 47 -
< Evaluation >
The obtained inks of Examples 6 to 10 and
Comparative Example 6 were used for printing on
commercial paper sheets for copying (Canon NP dry SK,
and Prober bond paper PB). The recording apparatus
employed was similar to the one shown in Fig. 6. A
color image was formed by use of four recording heads
shown in Fig. 9. The recording heads were the same as
the ones used in the ink-bet printer HJC-820J (trade
name, made by Canon K.K.). The recording heads were
driven under the driving conditions (or current-flowing
conditions) of the applied voltage of 28 V, the pulse
width of 3.2 usec, and the drive frequency of 5 kHz.
The inks were evaluated regarding the
evaluation items below. The results are shown in Table
2.
(1) Bleeding:
Evaluated in the same manner as in Example 1.
(2) Uniformity of color:
Evaluated in the same manner as in Example 1.
(3) Rate of occurrence of feathering:
Three hundred dots are printed continuously on
a commercial paper sheet for copying and a commercial
bond paper sheet such that the dots are not brought
into contact with each other. The dotted ink are dried
in the air for 24 hours at room temperature. Irregular
shape and irregular feathering of dots are counted
CA 02312643 2000-06-27
- 48 -
under microscope. The evaluation is made by the
percentage of the counted dot number according to the
standard below:
o . not more than 10 $
a . 10 ~ to 20 $
x . not less than 21 $
(4) Storage stability:
Evaluated in the same manner as in Example 1.
(5) Anti-Clogging (crusting recovery):
Evaluated in the same manner as in Example 1.
Table 2
Evaluation (1) (2) (3) (4) (5)
item
Example 6 0 0 0 0 0
Example 7 0 0 0 0 0
Example 8 0 0 0 0 0
Example 9 0 0 0 0 0
Example 10 0 0 0 0 0
Comparative x x o 0 0
example 6
Examples 11 to 18 and Comparative Examples 7 to 10
A color ink-jet recording apparatus which has
four heads of the same recording density for yellow
magenta, cyan, and black colors and conducts recording
by generation of ink droplets upon applying thermal
CA 02312643 2000-06-27
- 49 -
energy to the inks in the recording head was employed.
Three kinds of multiple-nozzle On-Demand type heads of
recording densities of 300 dpi (11.8 dots/mm), 360 dpi
(14.2 dots/mm); and 400 dpi (15.7 dots/mm) were used.
The color inks (yellow, magenta, cyan, and
black) for respective Examples were prepared by
stirring sufficiently the composition shown below and
filtering the mixture through Fluoropore Filter (pore
diameter of 0.22 um, trade name, made by Sumitomo
Electric Industries, Ltd.) under pressure.
(Dyes)
Black: C.I. Food Black 2 2 parts
Dye A 1.2 parts
Dye H 0.8 part
Yellow: C.I. Direct Yellow 86 2.5 parts
Cyan: C.I. Direct Hlue 199 3.5 parts
Magenta: Dye C 3.5 parts
(Liquid medium)
Thiodiglycol 7.5 parts
Urea 7.5 parts
Glycerin 7.5 parts
Surfactant (as shown in Table
3)
Pure water balance
With the recording apparatus having the heads
of recording density shown in Table 3 mounte d thereon,
recording was conducted at the ejection rate shown on
commercial paper for copying (Canon NP dry S K, and
CA 02312643 2000-06-27
- 50 -
Xerox 4024), and commercial bond paper (Plover bond
paper sheet PB), and the recorded matter was evaluated.
The printed dot diameters and the feathering
rates derived from the dot diameter are shown in Table
3. The evaluation results are shown in Table 4.
Recording was carried out under environmental
conditions of the temperature of 25~2°C and the
humidity of from 50 to 70 ~ RH, and the printed samples
were evaluated after they were left for one day from
the time they were printed.
The dot diameter ("B" in Equation [I]) in the
present invention was derived by image processing of
printed dots by means of a CCD camera to measure the
area of the dot and conversion of the area to a
diameter of precise circle. The ink droplet diameter
("C" in Equation [I]) was calculated from the equation
below:
V = (4/3)n(C/2)3 x 10-3
where V is the volume of a droplet (p~L) ejected per one
pulse.
The evaluation items:
(1) Bleeding,
(2) Uniformity of color, and
(3) rate of feathering
were evaluated in the same manner as in Example 1.
(4) Optical density:
The optical density of the printed matter was
* trade-mark
CA 02312643 2000-06-27
-51-
measured by MacBeth Refractodensitometer RD-915 (trade-
mark of MacBeth Co.). The average O.D. values of yellow,
magenta, cyan, and black were evaluated according to the
standard below:
0 . not less than 1.0
p . 0.9 to 1.o
X . not more than 0.9
CA 02312643 2000-06-27
- 52 -
t~
I -r~
x a ~0 00 ,~ d~ ~ C~ L~ ~ M L~ L~ N
+~
~
H ~ N N M M N N N N N N
N"
N
M N
G
+~
O
~ w ~ wo d~ c W O O ~
4i
of
~ ~ O ~
d di '~, M N d~ d~ t~ d~ d,
N
a
~ ~ d~ d~ t~ 00 0o w n
~
x 1~
.. d d~ d~ N M d~ M d~ d~ lM d~ d~
H 'O
N
O d~ N d~ 00 tn O N In N r-I 00 ~--I
1-~ d~ M l0 .-1vG r-1 L~ O r-1 M N o0
O
~
~
O ~
al
r-I N O d~ t0 Ov
A H .-il
v
~ r e-I.-i .-I ,-i .-I ,~
b
~
~i
N fl) N N N L~ N 00 l~ a0 N 00 N L~
O
O ~ 'd~ 'd~d~ In 'd~r-I lm --I d~ r-I 'd~In
+''
ri r-1r-1 r-Ir-Ii-1 ~-Iv--I .-1 r-I r-Ir-i
I
~~ ~
+~ : m n
-
C"Id ~-I In tn LIBO In t~ In O lf) N In
Id
.,
O
N
U
+~
N
U U U 0
4
b ~ ~ ~ -11
-I
r
b ~ ~ b ~ ro ~1
U b b b W
N c b ~ ~ O
~0
O
O
W W W W W w W W W
W N
S-I 1
I 1 O
H H O
U U U U ~ U ~ ~ O O O .4
~ ~ ~ ~ ~ ~
N r- r- r- r- r- r- ~ O ~ ~' ~ U
I 1 I 1 1 I
O b~ b~ O b~ O ~ ~ r- . r- O
~ ~ 1
~ O
H O N N N O O p ~r ,
t~
1~ f~ G G O G , O ~ ~ G O b
O
O N N N O O O .C c11O O O
~r ~r ~r ~ ~ ~ W
r r O ?~ ~r 5r
N N a' P ~
~ N ~ ~ , + +~ +~
a a a a a ~ z ~ U U U O
, ~ - a a a
,
M O ~'
c
H C
O N
cd
r-1 N M 'd~ll7~ t~ 00 ~ O
~ 0
x O
W
U
CA 02312643 2000-06-27
- 53 -
1
+~
.r.,
N
cu
0 0 0 0 0 0 0 o a o o x
~ a~
o N
O
Ca ~~
U -~i
O O O a O O O O a x x x
G1~ N
O 'Lf
G
O
O O a O O a O O x x x x
c~
N
w
O
b
a O O O O O O O O x O O x
G4
E
c~
x
w
a~
d' N r-1 N M d~ In t0 L~ CO b l~ op Ov
r-I r-I e~ rW -i r~ ri e-I r1 O
O cd
E
6
O
U
CA 02312643 2000-06-27
- 54 -
As described above, the present invention gives
color images of high quality formed by dots of
precisely circle shape with excellent color density
without causing feathering, bleeding, and color
nonuniformity even on plain paper.
Furthermore, the present invention enables
excellent recording without failure of ejection after
intermission of printing with stability and without
nozzle clogging.
15
25
