GOTOH AKIHIKO (JP)
NAMBA MICHIHIKO (JP)
NAGAI KIYOFUMI (JP)
MOROHOSHI NAOYA (JP)
OHSHIMA TOHRU (JP)
KOJIMA MARIKO (JP)
GOTOH AKIHIKO (JP)
NAMBA MICHIHIKO (JP)
NAGAI KIYOFUMI (JP)
MOROHOSHI NAOYA (JP)
OHSHIMA TOHRU (JP)
JPH09183224A | 1997-07-15 |
None
CLAIMS
1. A recording ink set comprising:
a black ink,
a cyan ink,
a magenta ink, and
a yellow ink, each of which comprises water, a
water-insoluble color, material, a water-soluble organic solvent,
and a surfactant,
wherein the black ink and at least one of the inks other
than the black ink respectively comprise a different
water-soluble organic solvent; and the surface tension of the
water-soluble organic solvent(s) used only for the inks other
than the black ink is higher than that of the water-soluble
organic solvent used only for the black ink.
2. The recording ink set according to claim 1, wherein
the contact angle between the each ink and a recording medium
when measured 100 ms after 2 μL of the each ink of the
recording ink set is dropped on a recording medium is 15
degrees to 35 degrees, the recording medium is provided with a
coating layer on at least one surface of a support and has a
transfer amount of pure water to the recording medium
measured by the use of a dynamic scanning absorptometer for a contact time of 100 ms is 3mL/m 2 to 15mL/m 2 .
3. The recording ink set according to any one of claims 1
to 2, wherein the surface tension of the each ink of the recording
ink set at a temperature of 25°C is 20 mN/m to 40 mN/m.
4. The recording ink set according to any one of claims 1
to 3, wherein the viscosity difference between at least one ink of
the recording ink set which comprises at least the black ink, the
cyan ink, the magenta ink, and the yellow ink, and the other
inks of the recording ink set is 0 mPa-s to 0.8 mPa-s.
5. The recording ink set according to any one of claims 1
to 4, wherein the viscosity of the each ink of the recording ink
set at a temperature of 25°C is 6 mPa-s to 20 mPa-s.
6. The recording ink set according to any one of claims 1
to 5, wherein the water content of the each ink is 40% by mass
to 60% by mass, and the content of each of the water-soluble
organic solvents in the each ink is 15% by mass to 40% by mass.
7. The recording ink set according to any one of claims 1
to 6, further comprising a penetrant which comprises a diol
compound having 7 to 11 carbon atoms.
8. The recording ink set according to any one of claims 1
to 7, wherein the surfactant is a fluorochemical surfactant, and the fluorochemical surfactant is represented by at least one selected from the following structural formulas (I), (II), and (III), CF 3 CF 2 (CF 2 CF 2 ^- CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
(where "m" is an integer of 0 to 10, and "n" is an integer
of 1 to 40),
OCH 2 - Rf OCH 2 -Rf
(where "Rf represents a fluorine-containing group, and "m", "n", and "p" are respectively an integer),
OCH 2 -Rf
(where "Rf represents a fluorine containing group; R 1 represents an anionic group; R2 represents a cationic group; and
"q" is an integer).
9. The recording ink set according to any one of claims 1 to 8, further comprising resin fine particles having a volume average particle diameter of 30 nm to 200 nm.
10. Recording inks comprising:
water,
a water-insoluble color material,
water-soluble organic solvents, and
a surfactant,
wherein the r.ecording inks comprise a black ink and at
least one selected from a cyan ink, a magenta ink, and a yellow
ink; the black ink and at least one of the inks other than the
black ink respectively comprise a different water-soluble organic
solvent; and the surface tension of the water-soluble organic
solvent(s) used only for the inks other than the black ink is
higher than that of the water-soluble organic solvent used only
for the black ink.
11. The recording inks according to claim 10, wherein
the contact angle between the each ink and a recording medium
when measured 100 ms after 2μL of the each ink of the recording
ink set is dropped on a recording medium is 15 degrees to 35
degrees, the recording medium is provided with a coating layer
on at least one surface of a support and has a transfer amount of
pure water to the recording medium measured by the use of a
dynamic scanning absorptometer for a contact time of 100 ms is 3mL/m 2 to 15mL/m 2 .
12. The recording inks according to any one of claims 10
to 11, wherein the surface tension of the each ink at a
temperature of 25°C is 20 mN/m to 40 mN/m.
13. The recording inks according to any one of claims 10
to 12, wherein the .viscosity difference between at least one
recording ink selected from the black ink, the cyan ink, the
magenta ink and the yellow ink, and the recording inks other
than the at least one recording ink is 0 mPa-s to 0.8 mPa-s.
14. The recording inks according to any one of claims 10
to 13, wherein the viscosity of the each ink at a temperature of
25°C is 6 mPa-s to 20 mPa-s.
15. The recording inks according to any one of claims 10
to 14, wherein the water content of the each ink is 40% by mass
to 60% by mass, and the content of each of the water-soluble
organic solvents in the each ink is 15% by mass to 40% by mass.
16. The recording inks according to any one of claims 10
to 15, further comprising a penetrant which comprises a diol
compound having 7 to 11 carbon atoms.
17. The recording inks according to any one of claims 10 to 16, wherein the surfactant is a fluorochemical surfactant, and the fluorochemical surfactant is represented by at least one
selected from the following structural formulas (I), (II), and (III), CF 3 CF 2 (CF 2 CF 2 X n -CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
(where "m" is , an integer of 0 to 10, and "n" is an integer
of 1 to 40),
OCH 2 -Rf OCH 2 -Rf
H-I-O-
(where "Rf represents a fluorine-containing group, and 'm", "n", and "p" are respectively an integer),
OCH 2 -Rf CH 2
R 2 R 1 0-CH 2 -C-CH 2 J-O- R 1 -R 2 + (III) CH-.
(where "Rf represents a fluorine-containing group; R 1
represents an anionic group, ' R2 represents a cationic group, ' and "q" is an integer).
18. The recording inks according to any one of claims 10 to 17, further comprising resin fine particles having a volume average particle diameter of 30 nm to 200 nm.
19. A recording method comprising:
recording an image on a recording medium which is
provided with a coating layer on at least one surface of a
support using a recording ink set according to any one of claims
1 to 9,
wherein the .transfer amount of pure water to the
recording medium measured by the use of a dynamic scanning
absorptometer for a contact time of 100 ms is 3mL/m 2 to
15mL/m 2 .
20. A recording method comprising:
recording an image on a recording medium which is
provided with a coating layer on at least one surface of a
support using recording inks according to claims 10 to 19,
wherein the transfer amount of pure water to the
recording medium measured by the use of a dynamic scanning
absorptometer for a contact time of 100 ms is 3mL/m 2 to
15mL/m 2 .
21. An inkjet recording apparatus comprising:
an ink drop discharge unit configured to discharge ink
drops to record an image by applying stimulation to each ink of a recording ink set according to any one of claims 1 to 9.
22. The inkjet recording apparatus according to claim 21,
wherein the stimulation is at least one selected from ' heat,
pressure, vibration and light.
23. The inkjet recording apparatus according to any one
of claims 21 to 22, wherein the size of discharged ink droplets is
3 pL to 40 pL; the recording speed is 5m/s to 20m/s> the
frequency of the applied stimulation is 1 kHz or more, ' and the
resolution is 300 dpi or more.
24. An inkjet recording apparatus comprising :
an ink drop discharge unit configured to discharge ink
drops to record an image by applying stimulation to the
recording inks according to any one of claims 10 to 19.
25. The inkjet recording apparatus according to claim 24,
wherein the stimulation is at least one selected from heat,
pressure, vibration and light.
26. The inkjet recording apparatus according to any one
of claims 24 to 25, wherein the size of discharged ink droplets is
3 pL to 40 pL, " the recording speed is 5m/s to 2Om/s5 the frequency of the applied stimulation is 1 kHz or more; and the
resolution is 300 dpi or more.
27. An ink record comprising:
an image recorded on a recording medium using the
recording ink set according to one of claims 1 to 9.
28. An ink re.cord comprising:
an image recorded on a recording medium using the
recording inks according to one of claims 10 to 19.
29. An ink cartridge comprising:
a recording ink set according to any one of claims 1 to 9,
wherein the recording ink set is contained in a container.
30. An ink cartridge comprising:
recording inks according to any one of claims 10 to 19,
wherein the recording inks are contained in a container. |
DESCRIPTION
RECORDING INK, RECORDING INK SET,
RECORDS, INK CARTRIDGE, RECORDING METHOD, AND
INKJET RECORDING APPARATUS
Technical Field
The present invention relates to an inkjet recording ink, a recording ink set, ink records, an ink cartridge, a recording method, and an inkjet recording apparatus.
Background Art
Conventionally, for colorants for inkjet recording ink, dyes have been used, however, dye inks have shortcomings in that they are poor in water resistance and weather resistance and easily bleeds on regular paper. To remedy these shortcomings, an ink using a pigment as a colorant is proposed.
For example, Patent Literature 1 proposes a method for alleviating color bleed using a self-dispersible carbon black, however, dyes are used for the color inks for the ink set demonstrated in the publication, and the color ink is inferior in water resistance and weather resistance. In addition, the color inks have a shortcoming in that they are inferior in feathering on regular paper to pigment inks. The method of alleviating color bleed proposed in the publication utilizes a quick
separation of solid contents from a solvent, however, it is difficult to prevent color bleed on media which are poor in
penetration.
Patent Literature 2 proposes an ink set containing inks having a difference in surface tension between the inks of 5 mN/m to 50mN/m.
Patent Literature 3 proposes an ink set having a
difference in viscosity between the inks of 0.7 mPa-s to 4 mPa-s. However, when there is a large difference in physical properties between inks, it is unfavorable because of difficulty of selecting members for ink nozzle and ink head peripherals and designing systems such as cleaning mechanism. Particularly when the ink viscosity differs between inks, the amount of discharged ink-drop varies at every discharge time, and the dot diameter differs between color inks to make it difficult to perform image processing. Thus, it is preferred that an ink set has smallest possible difference in physical properties between inks.
Patent Literature 4 proposes a method for reducing
occurrences of color bleed using water-soluble organic solvents having a difference in solubility parameter of 4 or more between
a black ink and color inks. However, with the ink compositions demonstrated in the present invention, namely, when an ink set
using an ink using a water-insoluble color material was used to record information on poorly ink absorbable coated paper, it was
impossible to prevent color bleed even when water-soluble
organic solvents having a difference in solubility parameter of 4
or more between color inks.
Patent Literature 5 proposes preventing color bleed by
defining the initial contact angle of ink with regular paper, the
difference in dynamic contact angle, and the rate of
dot-dimension change. The initial wet property of ink relative
to recording media affects color bleed, however, it is difficult to
prevent color bleed by only controlling the wet property of ink
relative to recording media.
Further, Patent Literature 6 defines the range of contact
angle between a first liquid and a second liquid, however,
similarly to Patent Literature 5, it is difficult to prevent color
bleed by only controlling the wet property of ink relative to
recording media. In addition, since the ink composition used in
Patent Literature 6 has a large water content, it easily causes a
phenomenon called cockling where the printed medium is
deformed like wavy paper.
Accordingly, an ink which excels in image water
resistance and image weather resistance and allows excellent
image formation without substantially causing color bleed not
only on regular paper but also on poorly water-absorbable
printing paper has not been realized yet. Here, poorly
water-absorbable paper means printing coated paper whose
surface is applied with an inorganic pigment such as calcium
carbonate and kaolin, and such paper is not generally recognized
as paper having inkjet suitability because it has a low r ^ ate of
ink absorption when printed with a water inkjet ink, and color
bleed easily occurs.
InkJet printing enables easy printing because of no need
of plate-making, and water inks have less environmental
burdens. For these reasons, it is desired to print images at a
quality as high as those seen in commercial printing such as
offset printing and gravure printing, using a water inkjet.
Patent Literature 1 Japanese Patent Application
Laid-Open (JP-A) No. 2004 352996
Patent Literature 2 Japanese Patent Application
Laid-Open (JP A) No. 2005- 154605
Patent Literature 3 Japanese Patent Application
Laid-Open (JP-A) No. 2005- 154607
Patent Literature 4 Japanese Patent Application
Laid-Open (JP-A) No. 2002-275402
Patent Literature 5 Japanese Patent Application
Laid-Open (JP A) No. 2003 321631
Patent Literature 6 Japanese Patent Application
Laid-Open (JP-A) No. 2004-338392
Disclosure of the Invention
The present invention aims to provide a recording ink
which is excellent in dry property, discharge stability, and
storage stability and allows excellent image formation not only
on regular paper but also on poorly water absorbable printing
coated paper whose surface is applied with an inorganic pigment,
without substantially causing color bleed, thereby forming
excellent printed matter having no paper cockling. The present
invention also aims to provide a recording ink set, ink records,
an ink cartridge, a recording method, and an inkjet recording
apparatus.
When an image is recorded on poorly water-absorbable
printing coated paper whose surface is applied with an inorganic
pigment, it takes some time to absorb water and a solvent
contained in the ink, and thus adjacent droplets easily cause
color bleeding. Particularly when a black droplet gravitates
toward a color droplet at the boundary portion between the color
ink and the black ink, the black ink moves toward the color ink,
and the black ink infiltrates into the color ink, and then color
bleed occurs on the ink-dry paper. In contrast, when a color
droplet gravitates toward a black droplet, the color ink moves
toward the black ink, and the color ink infiltrates into the black
ink, however, color bleeding is not observed on the ink-dry paper,
because the color ink is negated by the black ink, and color bleed
becomes less conspicuous.
Immediately after a color droplet makes contact with a black droplet, a fluid separating the two droplets is removed,
and the two liquids come to unite each other. At that point in time, it is found that a flow is induced from a liquid having a small surface tension toward a liquid having a large surface
tension.
Here, the surface tension of liquid means the surface tensions of different water-soluble organic solvents contained in individual inks, not means the surface tension of the ink itself.
The surface tension of ink itself is controlled by the type and the added amount of surfactants and is a parameter primarily affecting the wet property relative to a base material. In other words, the surface tension of ink itself is adjusted to control the wet condition of a recording medium right after the ink is dropped on the recording medium and the wet condition of areas surrounding the ink-discharging nozzle.
Thus, the present inventors found that to control color bleed which is caused between a black ink and color inks, it is effective to use at least one different water-soluble organic solvent between a black ink and at least one of the inks other than the black ink and to make the surface tension of the water-soluble organic solvents used for the inks other than the black ink higher than that of the water-soluble organic solvent
used for the black ink.
At the same time, the present inventors also found that when the higher an ink infiltrates into paper right after the
dropping of the ink on the paper, i.e. the lower the contact angle between the ink and the paper right after the ink is dropped on the paper, the smaller the contact area between droplets, and
thus it is more advantageous in preventing color bleed.
The present invention is based on the findings by the present inventors, and the means for solving the problems are as follows.
< 1 > A recording ink set containing a black ink, a cyan ink, a magenta ink, and a yellow ink, each of which contains water, a water-insoluble color material, a water-soluble organic solvent, and a surfactant, wherein the black ink and at least one of the inks other than the black ink respectively contain a different water-soluble organic solvent, ' and the surface tension of the water-soluble organic solvent(s) used only for the inks other than the black ink is higher than that of the water-soluble
organic solvent used only for the black ink. < 2 > The recording ink set according to the item < 1>,
wherein the contact angle between the each ink and a recording medium when measured 100 ms after 2μL of the each ink of the recording ink set is dropped on a recording medium is 15
degrees to 35 degrees, the recording medium is provided with a
coating layer on at least one surface of a support and has a transfer amount of pure water to the recording medium measured by the use of a dynamic scanning absorptometer for a contact time of 100 ms is 3mL/m 2 to 15mL/m 2 . ' < 3 > The recording ink set according to any one of the items < 1 > to < 2 >, wherein the surface tension of the each ink of the recording ink set at a temperature of 25°C is 20 mN/m to 40 mN/m.
< 4 > The recording ink set according to any one of the items < 1 > to < 3 >, wherein the viscosity difference between at least one ink of the recording ink set which contains at least the black ink, the cyan ink, the magenta ink, and the yellow ink, and the other inks of the recording ink set is 0 mPa-s to 0.8 mPa-s. < 5 > The recording ink set according to any one of the items < 1 > to < 4 >, wherein the viscosity of the each ink of the recording ink set at a temperature of 25°C is 6 mPa-s to 20 mPa-s.
< 6 > The recording ink set according to any one of the items < 1 > to < 5 >, wherein the water content of the each ink is
40% by mass to 60% by mass, and the content of each of the water-soluble organic solvents in the each ink is 15% by mass to 40% by mass.
< 7 > The recording ink set according to any one of the
items < 1 > to < 6 >, further containing a penetrant which contains a diol compound having 7 to 11 carbon atoms.
8. The recording ink set according to any one of the items < 1 > to < 7 >, wherein the surfactant is a fluorochemical
surfactant, and the fluorochemical surfactant is represented by at least one selected from the following structural formulas (I),
(II), and (III), CF 3 CF 2 (CF 2 CF 2 ) Jn - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
(where "m" is an integer of 0 to 10, and "n" is an integer of 1 to 40),
OCB 2 - Rf OCH 2 -Rf
(where "Rf represents a fluorine-containing group, and
m , "n", and "p" are respectively an integer),
OCH 2 -Rf CH 2
R 2 R 1 - O-CH 2 -C-CH 2 -O- RfR 2 + (III)
CH,
(where "Rf represents a fluorine-containing group; R 1
represents an anionic group, ' R2 represents a cationic group! and "q" is an integer).
< 9 > The recording ink set according to any one of the items < 1 > to < 8 >, further containing resin fine particles
having a volume average particle diameter of 30 nm to 200 nm.
< 10 > Recording inks containing water, a water-insoluble
color material, water-soluble organic solvents, and a surfactant,
wherein the recording inks contains a black ink and at least one
selected from a cyan ink, a magenta ink, and a yellow ink; the
black ink and at least one of the inks other than the black ink
respectively contain a different water-soluble organic solvent;
and the surface tension of the water-soluble organic solvent(s)
used only for the inks other than the black ink is higher than
that of the water-soluble organic solvent used only for the black
ink.
< 11 > The recording inks according to the item < 10 >,
wherein the contact angle between the each ink and a recording
medium when measured 100 ms after 2μL of the each ink of the
recording ink set is dropped on a recording medium is 15
degrees to 35 degrees, the recording medium is provided with a
coating layer on at least one surface of a support and has a
transfer amount of pure water to the recording medium
measured by the use of a dynamic scanning absorptometer for a
contact time of 100 ms is 3mL/m 2 to 15mL/m 2 .
< 12 > The recording inks according to any one of the
items < 10 > to <11>, wherein the surface tension of the each
ink at a temperature of 25°C is 20 mN/m to 40 mN/m.
< 13 > The recording inks according to any one of the
items <10> to <12>, wherein the viscosity difference between at least one recording ink selected from the black ink, the cyan ink, the magenta ink and the yellow ink, and the recording inks other than the at least one recording ink is 0 mPa-s to 0.8 mPa-s.
< 14 > The recording inks according to any one of the items <10> to <13>, wherein the viscosity of the each ink at a temperature of 25°C .is 6 mPa-s to 20 mPa-s.
< 15 > The recording inks according to any one of the items <10> to <14>, wherein the water content of the each ink is
40% by mass to 60% by mass, and the content of each of the water-soluble organic solvents in the each ink is 15% by mass to 40% by mass.
< 16 > The recording inks according to any one of the items <10> to <15>, further containing a penetrant which contains a diol compound having 7 to 11 carbon atoms.
< 17 > The recording inks according to any one of the items <10> to <16>, wherein the surfactant is a fluorochemical surfactant, and the fluorochemical surfactant is represented by at least one selected from the following structural formulas (I), (II), and (III), CF 3 CF 2 (CF 2 CF 2 ) H1 - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
(where "m" is an integer of 0 to 10, and "n" is an integer of 1 to 40),
OCH 2 -Rf OCH 2 -Rf
(where "Rf represents a fluorine-containing group, and
"m", "n", and "p" are respectively an integer),
OCH 2 -Rf
represents an anionic group; R2 represents a cationic group; and
"q" is an integer).
< 18 > The recording inks according to any one of the
items <10> to <17>, further containing resin fine particles
having a volume average particle diameter of 30 nm to 200 nm.
< 19 > A recording method which includes recording
information on a recording medium which is provided with a
coating layer on at least one surface of a support using a
recording ink set according to any one of the items < 1 > to < 9 >,
wherein the transfer amount of pure water to the recording
medium measured by the use of a dynamic scanning
absorptometer for a contact time of 100 ms is 3mL/m 2 to
15mL/m 2 .
< 20 > A recording method including recording an image
on a recording medium which is provided with a coating layer on
at least one surface of a support using recording inks according
to the items < 10 > to <19>, wherein the transfer amount of pure
water to the recording medium measured by the use' of a
dynamic scanning absorptometer for a contact time of 100 ms is
3mL/m 2 to 15mL/m 2 .
< 21 > An inkjet recording apparatus including an ink
drop discharge unit .configured to discharge ink drops to record
an image by applying stimulation to each ink of a recording ink
set according to any one of the items < 1 > to <9>.
< 22 > The inkjet recording apparatus according to the
item <21>, wherein the stimulation is at least one selected from
heat, pressure, vibration and light.
< 23 > The inkjet recording apparatus according to any
one of the items <21> to <22>, wherein the size of discharged
ink droplets is 3 pL to 40 pL, " the recording speed is 5m/s to
20m/s> " the frequency of the applied stimulation is 1 kHz or
more! and the resolution is 300 dpi or more.
< 24 > An inkjet recording apparatus including an ink
drop discharge unit configured to discharge ink drops to record
an image by applying stimulation to the recording inks
according to any one of the items <10> to <19>.
< 25 > The inkjet recording apparatus according to the
item <24>, wherein the stimulation is at least one selected from
heat, pressure, vibration and light.
< 26 > The inkjet recording apparatus according to any
one of the items <24> to <25>, wherein the size of discharged
ink droplets is 3 pL to 40 pL; the recording speed is 5in/s to
20m/s> " the frequency of the applied stimulation is 1 kHz or
more; and the resolution is 300 dpi or more.
< 27> An ink record containing an image recorded on a
recording medium using the recording ink set according to one of
the items <1> to <9>.
< 28 > An ink record containing an image recorded on a
recording medium using the recording inks according to one of
the items <10> to <19>.
< 29 > An ink cartridge containing a recording ink set
according to any one of the items <1> to <9>, wherein the
recording ink set is contained in a container.
< 30 > An ink cartridge containing recording inks
according to any one of the items <10> to <19>, wherein the
recording inks are contained in a container.
Brief Description of Drawings
FIG. l is a schematic illustration showing an example of an
ink cartridge of the present invention.
FIG.2 is a schematic illustration showing the ink cartridge
shown in FIG. l including a case (exterior).
FIG.3 is a perspective view exemplarily explaining an inkjet
recording apparatus in the condition where the cover of the
cartridge mounting part thereof is opened.
FIG.4 is a schematic illustration exemplarily explaining the
entire structure of an inkjet recording apparatus.
FIG.5 is a schematic enlarged view showing an example of
an inkjet head suitably used in the present invention.
FIG.6 is an enlarged view exemplarily showing components
of an inkjet head suitably used in the present invention.
FIG.7 is an enlarged cross-sectional view exemplarily
showing the core part of the inkjet head in the inter-channel
direction, which is shown in FIG. 6.
Best Mode for Carrying Out the Invention
(Recording Ink)
The recording ink of the present invention contains at
least water, a water-insoluble color material, a water-soluble
organic solvent, and a surfactant, and the recording inks
contains at least a black ink, and one selected from a cyan ink, a
magenta ink, and a yellow ink, wherein at least one of the inks
other than the black ink contains a different water-soluble
organic solvent from that of the black ink, and the surface
tension of the water-soluble organic solvent(s) used only for the
inks other than the black ink is higher than that of the
water-soluble organic solvent used only for the black ink.
(Recording Ink Set)
The recording ink set of the present invention contains at
least a black ink, and one selected from a cyan ink, a magenta
ink, and a yellow ink, each of which contains at least water, a
water-insoluble color material, a water-soluble organic solvent,
and a surfactant, wherein at least one of the inks other than the
black ink contains a. different water-soluble organic solvent from
that of the black ink, and the surface tension of the
water-soluble organic solvent(s) used only for the inks other
than the black ink is higher than that of the water-soluble
organic solvent used only for the black ink.
The water-soluble organic solvent is not particularly
limited and may be suitably selected in accordance with the
necessity. Examples of the water-soluble organic solvent
include polyvalent alcohols such as ethylene glycol, diethylene
glycol, triethylene glycol, polyethylene glycol, polypropylene
glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol,
1,3-butanediol, 2,3-butanediol, 1,4-butanediol,
3-methyl- 1,3-butanediol, 1,5-pentanediol, tetraethylene glycol,
1,6-hexanediol, 3-methyl- 1,5-pentanediol,
2-methyl-2,4-pentanediol, polyethylene glycol, glycerol,
1,2,6-hexanetriol, 1,2,4'butanetriol, 1,2,3-butanetriol, and
petriol; polyvalent alcohol alkyl ethers such as ethylene glycol
monoethyl ether, ethylene glycol monobutyl ether, diethylene
glycol monomethyl ether, diethylene glycol monoethyl ether,
diethylene glycol monobutyl ether, tetraethylene glycol
monomethyl ether, and propylene glycol monoethyl ether;
polyvalent alcohol aryl ethers such as ethylene glycol
monophenyl ether and ethylene glycol monobenzyl ether;
nitrogen-containing heterocyclic compounds such as
N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone,
2-pyrrolidone, 1,3-dimethylimidazolidinone, and ε caprolactam;
amides such as formamide, N-methylformamide, formamide, and
N,N-dimethylformamide; amines such as monoethanolamine,
diethanolamine, triethanolamine, monoethylamine,
diethylamine, and triethylamine; sulfur-containing compounds
such as dimethylsulfoxide, sulfolane, and thiodiethanol;
propylene carbonate, and ethylene carbonate. Each of these
solvents can be used along with water individually or in
combination with two or more.
Of these water-soluble organic solvents, the following
ones are preferably used in terms that excellent effects can be
achieved for solubility and for preventing degradation of
injection properties caused by water evaporation. The
preferred water-soluble organic solvents are glycerin, ethylene
glycol, diethylene glycol, triethylene glycol, propylene glycol,
dipropylene glycol, tripropylene glycol, l,3 butanediol,
2,3-butanediol, 1,4-butanediol, 3-methyl-l,3-butanediol,
1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol,
3-methyl- l,5-pentanediol, 2-methyl-2,4-pentanediol,
3 methyl- 1,5-pentanediol, 2-methyl-2,4-pentariediol,
polyethyleneglycol, 1,2,4-butanetriol, 1,2,6-hexanetriol,
thiodiglycol, 2-pyrrolidone, N-methyl-2-pyrolidone, and
N-hydroxyethyl-2-pyrolidone.
Further, amo.ng these water-soluble organic solvents,
particularly preferable combinations of inks as an ink set
capable of preventing color bleed include the following ones.
A combination of a color ink containing diethylene glycol
(surface tension = 48.5 mN/m) with a black ink containing
1,4-butanediol (surface tension = 45.3 mN/m) or triethylene
glycol (surface tension = 45.2 mN/m) or 1.5-pentanediol (surface
tension = 43.2 mN/m) or N-methylpyrrolidone (surface tension =
41 mN/m) or 1,3-butanediol (surface tension = 37.8 mN/m) or
3-methyl- l,5-pentanediol (surface tension = 37.5 mN/m) or
propylene glycol (surface tension = 36 mN/m) or tripropylene
glycol (surface tension = 34 mN/m) or 2,3-butanediol (surface
tension = 33.8 mN/m) or 3-methyl- 1,3-butanediol (surface
tension = 32.8 mN/m) or dipropylene glycol (surface tension = 32
mN/m) or 2-methyl-2,4-pentanediol (surface tension = 27 mN/m).
A combination of a color ink containing ethylene glycol
(surface tension = 46.5 mN/m) with a black ink containing
1,4-butanediol (surface tension = 45.3 mN/m) or triethylene
glycol (surface tension = 45.2 mN/m) or 1,5-pentanediol (surface
tension = 43.2 mN/m) or N-methylpyrrolidone (surface
tension = 41 mN/m), 1,3-butanediol (surface tension — 37.8
mN/m) or 3-methyl- 1,5-pentanediol (surface tension = 37.5
mN/m) or propylene glycol (surface tension = 36 mN/m) or
tripropylene glycol (surface tension = 34 mN/m) or
2,3-butanediol (surface tension = 33.8 mN/m) or
3-methyl- l,3-butanediol (surface tension = 32.8 mN/m) or
dipropylene glycol (surface tension = 32 mN/m) or
2-methyl-2,4-pentanediol (surface tension = 27 mN/m).
A combination of a color ink containing 1,4'butanediol
with a black ink containing 1,5-pentanediol (surface tension =
43.2 mN/m) or N-methylpyrrolidone (surface tension = 41 mN/m)
or 1,3-butanediol (surface tension = 37.8 mN/m) or
3-methyl- l,5-pentanediol (surface tension = 37.5 mN/m) or
propylene glycol (surface tension = 36 mN/m) or tripropylene
glycol (surface tension = 34 mN/m) or 2,3-butanediol (surface
tension = 33.8 mN/m) or 3-methyl- l,3-butanediol (surface
tension = 32.8 mN/m) or dipropylene glycol (surface tension = 32
mN/m) or 2-methyl-2,4-pentanediol (surface tension = 27 mN/m).
A combination of a color ink containing 1,3-butanediol
with a black ink containing 3-methyl- 1,5-pentanediol (surface
tension = 37.5 mN/m) or propylene glycol (surface tension = 36
mN/m) or tripropylene glycol (surface tension = 34 mN/m) or
2,3-butanediol (surface tension = 33.8 mN/m) or
3-methyl- l,3-butanediol (surface tension = 32.8 mN/m) or
dipropylene glycol (surface tension = 32 mN/m) or
2-methyl-2,4-pentanediol (surface tension = 27 mN/m).
A combination of a color ink containing triethylene glycol
with a black ink containing 1,5-pentanediol (surface tension =
43.2 mN/m) or N methylpyrrolidone (surface tension = 41 mN/m)
or 1,3-butanediol (surface tension = 37.8 mN/m) or
3-methyl- l,5-pentanediol (surface tension =- 37.5 mN/m) or
propylene glycol (surface tension = 36 mN/m) or tripropylene
glycol (surface tension = 34 mN/m) or 2,3-butanediol (surface
tension = 33.8 mN/m) or 3-methyl- l,3-butanediol (surface
tension = 32.8 mN/m) or dipropylene glycol (surface tension = 32
mN/m) or 2-methyl-2,4-pentanediol (surface tension = 27 mN/m).
A combination of a color ink containing 1,5-pentanediol
with a black ink containing 1,3-butanediol (surface tension =
37.8 mN/m) or 3-methyl- l,5-pentanediol (surface tension = 37.5
mN/m) or propylene glycol (surface tension = 36 mN/m) or
tripropylene glycol (surface tension = 34 mN/m) or
2,3-butanediol (surface tension = 33.8 mN/m) or
3-methyl- l,3'butanediol (surface tension = 32.8 mN/m) or
dipropylene glycol (surface tension = 32 mN/m) or
2-methyl-2,4-pentanediol (surface tension = 27 mN/m).
A combination of a color ink containing 1,3-butanediol
with a black ink containing propylene glycol (surface tension =
36 mN/m) or tripropylene glycol (surface tension = 34 mN/m) or
2,3-butanediol (surface tension = 33.8 mN/m) or
3-rαethyl- l,3-butanediol (surface tension = 32.8 mN/m) or
dipropylene glycol (surface tension = 32 mN/m) or
2τnethyl-2,4-pentanediol (surface tension = 27 mN/m).
A combination of a color ink containing propylene glycol
with a black ink containing tripropylene glycol (surface tension
= 34 mN/m) or 2,3-butanediol (surface tension = 33.8 mN/in) or
3-methyl- l,3-butanediol (surface tension = 32.8 mN/m) or
dipropylene glycol (surface tension = 32 mN/m) or
2-methyl-2,4-pentanediol (surface tension = 27 mN/m).
A combination of a color ink containing tripropylene
glycol with a black ink containing 3-methyl- l,3-butanediol
(surface tension = 32.8 mN/m) or dipropylene glycol (surface
tension = 32 mN/m) or 2-methyl-2,4 pentanediol (surface tension
= 27 mN/m).
A combination of a color ink containing 2,3-butanediol
with a black ink containing 3-methyl- l,3-butanediol (surface
tension = 32.8 mN/m) or dipropylene glycol (surface tension = 32
mN/m) or 2-methyl-2,4 pentanediol (surface tension = 27mN/m).
A combination of a color ink containing
3-methyl- l,3-butanediol with a black ink containing dipropylene
glycol (surface tension = 32 mN/m) or 2-methyl-2,4-pentanediol
(surface tension = 27mN/m).
Further, a combination of a color ink containing
dipropylene glycol with a black ink containing
2-methyl-2,4-pentanediol (surface tension = 27mN/m).
In addition, glycerin serves as a moisturizing agent and
can be used in both color ink and black ink.
The content of the water-soluble organic solvent in the
recording ink is preferably 15% by mass to 40% by mass, and
more preferably 20% by mass to 35% by mass. With an
excessively small content of the water-soluble organic solvent,
the ink is easily dried in the nozzle, and droplets may not be
smoothly discharged. With an excessively large content of the
water-soluble organic solvent, the ink viscosity may be increased,
and it may exceed the appropriate viscosity limit.
For the surfactant, one selected from anionic surfactants,
cationic surfactants, nonionic surfactants, ampholytic
surfactants, and fluorochemical surfactants can be used alone,
or two or more selected therefrom can be mixed for use.
Examples of the anionic surfactant include alkylallyl,
alkylnaphthalenesulfonate, alkylphosphate, alkylsulfate,
alkylsulfonate, alkylethersulfate, alkylsulfosuccinate,
alkylester sulfate, alkylbenzene sulfonate,
alkyldiphenyletherdisulfonate, alkylaryletherphosphate,
alkylarylethersulfate, alkylaryletherestersulfate, olefinsulfonate,
alkaneolefinsulfonate, polyoxyethylenealkyletherphosphate,
polyoxyethylenealkylethersulfic ester salt, ethercarboxylate,
sulfosuccinate, α-sulfo fatty acid ester, fatty acid ' salt,
condensates of higher fatty acid and amino acid, and
naphthenate.
Examples of the nonionic surfactant include acetylene
glycol surfactants, polyoxyethylenealkylether,
polyoxyethylenealkylphenylether, polyoxyethylenealkyl ester,
and polyoxyethylene sorbitan fatty acid ester.
Examples of the cationic surfactant include alkyl amine
salt, dialkyl amin salt, aliphatic amine salt, benzalkonium salt,
quaternary ammonium salt, alkylpyridinium salt, imidazolium
salt, sulfonium salt, and phosphonium salt.
Examples of the amphoteric surfactant include
imidazoline derivatives such as imidazolium betaineJ
dimethylalkyllauryl betaine, alkylglycine,
alkyldi(aminoethyl) glycine.
For the fluorochemical surfactant, those represented by
the following Structural Formula (I) to (III) can be preferably
used.
CF 3 CF 2 (CF 2 CF 2 ^ 1 -CH 2 CH 2 O(CH 2 CH 2 O) n H - • - ( I )
(In the Structural Formula (I), " m" is an integer of 0 to
10, and " n" is an integer of 1 to 40.)
OCH 2 -Rf OCH 2 -Rf
H-I-O-CH 2
-
(In the Structural Formula (II), "Rf" represents a
fluorine-containing group, and "m" , "n" and "p" are
respectively an integer.)
OCH 2 -Rf
(In the Structural Formula (III), "Rf" represents a
fluorine containing group, "R 1 " represents an anionic group,
and "R2" represents a cationic group, and "q" is an integer.)
Examples of commercially available fluorochemical
surfactants include Surflon S-Hl, S-112, S-113, S 121, S-131,
S-132, S-141, and S-145 (available from Asahi Glass Co., Ltd.);
Fluorad FC-93, FC 95, FC-98, FC-129, FC 135, FC-170C, FC 430,
FC-431, and FC4430 (available from Sumitomo 3M Limited);
Megafack F-470, F- 1405, and F-474 available from Dainippon
Ink & Chemicals Inc.); Zonyl FS 300, FSN, FSN-IOO, and FSO
(available from DuPont Kabushiki Kaisha); EFTOP EF-351,
EF-352, EF-801, and EF-802 (available from JEMCO Inc).
Nonionic surfactants and fluorochemical surfactants are
particularly preferably used.
Examples of the colorant include dyes such as oiLsoluble
dyes and disperse dyes; and pigments. In the present invention,
pigments that excel in water resistance and weather resistance
were used.
Examples of the pigments to be used in the present
invention include, carbon black as a black pigment; and include
color pigments such as anthraquinone, phthalocyanine blue,
phthalocyanine green, diazo, monoazo, pyranthron, perylene,
heterocyclic yellow, quinacridone, and (thio)indigoid. Examples
of typical phthalocyanine blue include copper phthalocyanine
blue and derivatives thereof (CI. Pigment Blue 15). Examples
of typical quinacridone include C.I. Pigment Orange 48, C.I.
Pigment Orange 49, C.I. Pigment Red 122, C.I. Pigment Red 192,
CL Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment 206,
C.I. Pigment Red 207, C.I. Pigment Red 209, C.I. Pigment Violet
19, and C.I. Pigment Violet 42. Examples of typical
anthraquinone include C.I. Pigment Red 43, C.I. Pigment Red
194 (Perylene Red), C.I. Pigment Red 216 (brominated
Pyranthron Red) and C.I. Pigment Red 226 (Pyranthron Red).
Examples of typical perylene include C.I. Pigment Red 123
(Vermillion), CL Pigment Red 149 (scarlet), CL Pigment Red
179 (maroon), CL Pigment Red 190 (red), CL Pigment Violet,
CL Pigment Red 189 (yellow shade red), and Pigment Red 224.
Examples of typical thioindigoid include CL Pigment Red 86,
C.I. Pigment Red 87, C.I. Pigment Red 88, C.I. Pigment Red 181,
C.I. Pigment Red 198, C.I. Pigment Violet 36, and C.I. Pigment
Violet 38. Examples of heterocyclic yellow include C.I. Pigment
Yellow 117, and C.I. Pigment Yellow 138. Examples of the other
appropriate color pigments are described in "The Colour Index,
3 rd edition (The Society of Dyers and Colourists, 1982)".
Further, in the present invention, it is possible to use a
pigment obtained b.y dispersing it in a water-based medium
using a dispersing agent. For the dispersing agent, those
known in the art used for conventionally known pigment
dispersions can be preferably used.
Examples of preferable dispersion agents include
polyacrylic acid, polymethacrylic acid, acrylic acid-acrylonitrile
copolymers, vinyl acetate-acrylic acid ester copolymers, acrylic
acid-acrylic acid alkylester copolymers, styrene-acrylic acid
copolymers, styrene-methacrylic acid copolymers, styrene-acrylic
acid-acrylic acid alkyl ester copolymers, styrene-methacrylic
acid-acrylic acid alkyl ester copolymers,
styrene-crmethylstyrene-acrylic acid copolymers,
styrene-crmethylstyrene-acrylic acid copolymer-acrylic acid
alkyl ester copolymers, styrene-maleic acid copolymers,
vinylnaphthalene-maleic acid copolymers, vinylacetate-ethylene
copolymers, vinylacetate -fatty acid vinylethylene copolymers,
vinylacetate-maleic acid ester copolymers, vinylacetate-crotonic
acid copolymers, and vinylacetate ^ acrylic acid copolymers.
The mass average molecular mass of these copolymers is
preferably 3,000 to 50,000, more preferably 5,000 to 30,000, and
most preferably 7,000 to 15,000. For the added amount of the
dispersing agent, the dispersing agent may be suitably added
within such a range that the pigment can be stably dispersed
and other effects of the present invention cannot be eliminated.
The dispersing agent is preferably added to the pigment at a
ratio of l ; 0.06 to 1.3, and more preferably added at a ratio of
i:0.125 to 1 :3.
For colorants to be used in the present invention, a
pigment that at least one hydrophilic group is combined to the
surface thereof can be used. As the result, like conventional
inks, the pigment can be stably dispersed without using a
dispersing agent for dispersing pigments. When such a
pigment having a hydrophilic group on the surface thereof and
needing no dispersing agent is used, it is possible to provide a
highly reliable ink which excels in long-term storage stability, is
resoluble to water even when moisture is evaporated, and causes
no nozzle clogging due to dried pigment in the nozzle when used
in a printer.
For carbon black having at least one hydrophilic group on
the surface thereof to be used in the present invention, those
having ionicity are preferable, and anionically charged carbon
black or cationically charged carbon black is suitably used.
For the carbon black, it is possible to use those produced
by a known method for producing a carbon black such as channel
method, oil furnace method, furnace method, acetylene black
method, and thermal black method.
For a carbon black to be used for a black pigment, such a
carbon black is preferable that is produced by furnace method or
channel method and has a primary particle diameter of 15 nm to
40 nm, a specific surface area based on the BET method of 50
m 2 /g to 300 m 2 /g, a DBP oil absorption of 40 mL/lOOg to ' 150
mL/100g, and a pH value of 2 to 9.
For the preferred carbon black, it is possible to use #2700,
#2650, #2600, #2450B, #2400B, #2350, #230, #1000, #990, #980,
#970, #960, #950, #900, #850, #750B, MCF88, #650B, MA600,
MA77, MA7, MA8, MAIl, MAlOO, MAlOOR, MAlOOS, MA220,
MA230, MA200RB, MA14, #52, #50, #47, #45, #45L, #44, #40,
#33, #32, #30, #25, #20, #10, #5, #95, #85, CF9, and #260
(available from Mitsubishi Chemical Corporation); Raven 700,
Raven 5750, Raven 5250, Raven 5000, Raven 3500, and Raven
1255 (available from Columbia Company); Regal 400R, Regal
330R, Regal 660R, Mogul L, Monarch 700, Monarch 800,
Monarch 880, Monarch 900, Monarch 1000, Monarch 1100,
Monarch 1300, and Monarch 1400 (available from Cabot Corp.);
Color Black FWl, Color Black FW2, Color Black FW2V, Color
Black FW18, Color Black FW200, Color Black FWS150, Color
Black FWS160, Color Black FWS170, Printex 35, Printex U,
Printex V, Printex 140 U, Printex 140 V, Special Black 6, Special
Black 5, Special Black 4A, and Special Black 4 (available from
Degsa. Co.); Tokai Black #8500, Tokai Black #8300, Tokai Black
#7550, Tokai Black #7400, Tokai Black #7360, Tokai Black #7350,
Tokai Black #7270, and Tokai Black #7100 (available from
TOKAI CARBON CO., LTD.); Show Black NIlO, Show Black
N220, Show Black N234, Show Black N339, Show Black N330,
Show Black N326, Show Black N330T, Show Black MAF, " and
Show Black N550 (available from Showa Cabot K. K.), however,
the carbon black is not limited to those described above.
The carbon black to be used in the present invention is a
carbon black having a surface which is subjected to a
modification treatment and to which at least one hydrophilic
group is directly bound or is bound through another atomic
group, and the carbon black can be stably dispersed without
using a dispersing agent.
Examples of the method for modifying the surface of a
carbon black include a method in which a carbon black is added
to an oxidizing agent aqueous solution, for example, an
alkali-metal salt such as hypochlorite, chlorite, chlorate,
persulfate, perborate, and percarbonate; or an ammonium salt to
thereby subject the carbon black to an oxidization treatment; a
method of subjecting a carbon black to an oxidizing plasma
treatment at low-temperature! and a method of oxidizing a
carbon black using ozone.
Examples of the hydrophilic group include -COOM,
SO 3 M, PO 3 HM, -PO 3 M 2 , SO 2 NH 2 , and -SO 2 NHCOR (where M
represents a hydrogen atom, an alkali metal, ammonium or
organic ammonium, ' and R represents an alkyl group having 1 to
12 carbon atoms, a .phenyl group that can have a substituent
group, or a naphthyl group that can have a substituent group).
Of these, it is preferable to use a carbon black having a surface
to which -COOM or -SO3M is bound. Examples of the alkali
metal which is represented by M in the hydrophilic group
include lithium, sodium, and potassium. Examples of the
organic ammonium include monomethyl ammonium, trimethyl
ammonium, monomethanol ammonium, and trimethanol
ammonium.
In addition, it is possible to bind N-ethylpyridyl group
represented by the following Structural Formula with a carbon
black by subjecting the carbon black to a treatment using
3-amino-N-ethylpyridium bromide, and it is also possible to
introduce a cationic hydrophilic group into a carbon black by
reacting diazonium salt to the carbon black. For the cationic
hydrophilic group, a quaternary ammonium group is preferably
used, and quaternary ammonium groups described below are
more preferably used. A carbon black pigment of which any one of these quaternary ammonium groups is bound to the surface is
suitably used as a color material.
- NH 3 X - NR 3 s
The added amount of pigment as colorant is preferably 4%
by mass to 15% by mass, and more preferably 5% by mass to 12% by mass. When the added amount is more than 12% by mass, it
easily adversely affect the fixing ability, discharging stability, and reliabilities of clogging prevention, and the like. When the added amount is less than 3% by mass, a sufficient image
density may not be obtained.
To the ink of the present invention, resin fine particles can be added. The resin fine particles are fine particles in
which a water-insoluble resin is dispersed in water, and have an effect that when the solvent is evaporated, resin fine particles are fused to each other to form a film then to make a colorant fixed on a medium. Further, when the solvent is evaporated, resin fine particles come to have a property of thickening and flocculating each o.ther to prevent infiltration of colorant
components to recording media, thereby obtaining a high-image density. An effect of preventing occurrences of strike-through
can also be obtained.
Examples of the resin components include acrylic resins,
vinyl acetate resins, styrene-butadiene resins, vinylchloride resins, acryl-styrene resins, acrylic silicone resins, butadiene resins, styrene resins, urethane resins, and acrylic urethane resins. For the added amount of the resin emulsion, it is
preferably adjusted to a content of 0.1% by mass to 40% by mass relative to the ink content, and more preferably adjusted to a content of 1% by mass to 25% by mass relative to the ink content. When the content of resin fine particles is less than 0.1% by mass, a sufficient fixing ability may not be obtained, and when the content thereof is more than 40% by mass, there may be
cases where the storage stability may be degraded because of the composition with high solids content and less solvent; and
the discharging stability may be degraded because the resin fine
particles are easily dried and solidified in the nozzle.
The resin fine particles preferably have a particle
diameter of 30 nm to 200 nm.
In the present invention, a diol compound having 7 to 11
carbon atoms can be used as a penetrant. When the number of
carbon atoms is less than 7, the diol compound cannot be
sufficiently infiltrated into a recording medium, the recording
medium is contaminated at the time of duplex printing, and the
pixel density is scarce due to insufficient ink-widening on a
recording medium, which may degrade font character quality
and image density. When the number of carbon atoms is more
than 11, the storage stability may be degraded.
Preferred examples of the diol compound include
2-ethyl- l,3-hexanediol, and 2,2,4-trimethyl- l,3-pentanediol.
The added amount of the diol compound is preferably
0.1% by mass to, 20% by mass, and more preferably 0.5% by mass
to 10% by mass. When the added amount of the diol compound
is excessively small, the infiltration property of the ink relative
to paper may be degraded, resulting in contamination of the
paper when the paper is conveyed and rubbed with a roller,
and/or it may make the ink adhere on a conveying belt, resulting
in contamination of a recording medium when the recorded
surface of the recording medium is flipped for printing both
sides of the recording medium. Therefore, it may not be able to
effectively achieve high-speed printing and duplex printing.
When the added amount of the diol compound is excessively
large, the printing dot diameter may be increased to broaden the
character line width and/or to degrade the image sharpness.
In the present invention, an aminopropanediol compound
can be added to materials of the recording ink. An
aminopropanediol cpmpound is a water-soluble base compound
and can keep an ink alkaline pH thereby preventing the ink
from eating away members which make contact with the ink for
a long term and can also control flocculation of colorants caused
by moisture evaporation, thereby maintaining stable ink
discharging property.
Aminopropanediol derivatives are not particularly limited,
may be suitably selected in accordance with the intended use,
and examples thereof include l-amino-2,3-propanediol,
l-methylamino-2, 3 -propanediol,
2-amino-2-methyl- 1,3 -propane diol, and
2-amino-2-ethyl- l,3'propanediol. Of these,
2-amino-2-ethyl l, 3-propanediol is particularly preferable.
The added amount of the aminopropanediol compound in
the recording ink is preferably 0.01% by mass to 10% by mass,
more preferably 0.1% by mass to 5.0% by mass, and still more
preferably 0.1% by mass to 2.0% by mass. When the added
amount of the aminopropanediol compound is excessively large, it may cause disadvantages that the pH value of the recording ink is increased to increase the viscosity of the recording ink.
The other components are not particularly limited, may
be suitably selected in accordance with the necessity, and examples thereof include a pH adjustor, an antiseptic and mildewproofing agent, an anti-corrosive agent, an antioxidant, an ultraviolet abso.rber, an oxygen absorbent, and a light stabilizer.
[0048]
Examples of the antiseptic and mildewproofing agent include l,2-benzisothiazoline-3-on, sodium dehydroacetate, sodium sorbate, 2-pyridinethiol- l-oxide sodium, sodium benzoate, and pentachlorophenol sodium. The pH adjustor is not particularly limited, and an
arbitrarily selected material can be used, provided that it allows adjusting the pH to 7 or more without adversely affecting the compounded ink.
Examples of the pH adjustor include amines such as diethanolamine, and triethanolamine> " hydroxides of alkali-metal
elements such as lithium hydroxide, sodium hydroxide, and potassium hydroxide! ammonium hydroxide; quaternary ammonium hydroxide! quaternary phosphonium hydroxide, ' and
alkali-metal carbonates such as lithium carbonate, sodium
carbonate, and potassium carbonate.
Examples of the anti-corrosive agent include acidic
sulphite salt, sodium thiosulfate, ammonium thiodiglycolate,
diisopropylammonium nitrite, pentaerythritol tetranitrate, and
dicyclohexylammonium nitrite.
Examples of the antioxidant include phenol antioxidant
agents (including hindered phenol antioxidants), amine
antioxidants, sulfur .antioxidants, and phosphorous
antioxidants.
Examples of the phenol antioxidant (including hindered
phenol antioxidants) include butylated hydroxyanisol,
2,6-di-tert-butyl-4-ethylphenol,
stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate,
2,2'-methylenebis (4-methyl-6-tert-butylphenol),
2,2'-methylenebis (4-ethyl-6-tert'butylphenol),
4,4'-butylidenebis (3 methyl-6 tert butylphenol),
3,9-bis[l, l-dimethyl-2- [β-(3-tert-butyl-4-hydroxy-5-methylphenyl
) propionyloxy]ethyl]2,4,8, 10 tetraixaspiro[5,5]undecane,
1, 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl)butane,
l,3,5-trimethyl-2,4,6-tris(3, 5-di-tert-butyl-4-hydroxybenzyl)ben-
zene, tetrakis[methylene-3-(3',5'-di tert-butyl-4'-hydroxyphenyl)
propionate] methane.
The amine antioxidant include phenyl β-naphthylamine,
α-naphthylamine, N, N'-di-sec-butyl p phenylenediamine,
phenothiazine, N, N'-diphenyl ~ p"phenylenediamine,
2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butyl-phenol, butylhydroxyanisol,
2,2'-methylenebis (4-methyl-6-tert-butylphenol), ' 4,4'-butylidenebis (3-methyl-6 tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), tetrakis [methylene -3(3, 5 -di-tert-butyl- 4- dihydroxyphenyl)
propionate] methane, and l, l,3-tris(2 methyl-4-hyroxy5-tert-butylphenyl) butane. Examples of the sulfur antioxidant include dilauryl
3,3'-thiodipropyonate, distearylthiodipropyonate, laurylstearylthiodipropyonate, dimyristyl 3,3'-thiodipropyonate,
distearyl β,β' thiodipropyonate, 2-mercaptobenzoimidazol, and dilauryl sulfide. Examples of the phosphorous antioxidant include triphenylphosphite, octadecylphosphite, triisodecylphosphite, trilauryltrithiophosphite, and trinonylphenylphosphite.
Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet
absorbers, salicylate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, and nickel complex salt ultraviolet
absorbers.
Examples of the benzophenone ultraviolet absorbers
include 2-hydroxy4-n-octoxybenzophenone,
2 -hydroxy 4-n-dodecyloxybenzophenone,
2,4-dihydroxybenzophenone, 2-hydroxy4-methoxybenzophenone,
and 2,2',4,4'-tetrahydroxybenzophenone.
Examples of the benzotriazole ultraviolet absorber '
include 2-(2' hydroxy5'-tert-octylphenyl)benzotriazole,
2-(2'-hydroxy5'-tert-octylphenyl)benzotriazole,
2-(2'-hydroxy5'-methylphenyl)benzotriazole,
2-(2'-hydroxy4'-octoxyphenyl)benzotriazole, and
2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-
chlorobenzotriazole.
Examples of the salicylate ultraviolet absorber include
phenylsalicylate, p-tert-butylphenylsalicylate, and
p -octylphenylsalicy late .
Examples of the cyanoacrylate ultraviolet absorber
include ethyl-2-cyano-3,3'-diphenylacrylate,
methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate,
butyl-2-cyano-3-methyl-3-(p-methoxyphenyl) aery late.
Examples of the nickel complex salt ultraviolet absorber
include nickelbis(octylphenyl) sulfide,
2,2'-thiobis(4-tert-octylphenolate)-n butylamineNickel (II),
2,2'-thiobis(4-tert-octylphenolate)-2-ethylhexylamineNick el (II),
and 2,2'-thiobis(4-tert-octylphenolate)triethanolamineNickel
(II).
The recording ink of the present invention can be
produced by dispersing or dissolving at least water, a colorant, a
water-soluble organic solvent, and a surfactant in a water-based
medium, and further dispersing or dissolving a penetrant, resin
fine particles, a pH adjustor, and other components in the
water-based medium in accordance with the necessary, and
stirring and mixing the components in accordance with the
necessity. The components can be dispersed using, for example,
a sand mill, a homogenizer, a ball mill, a paint shaker, or a
ultrasonic dispersion device, and the components can be usually
stirred and mixed by the use of a stirrer having stirring blades,
a magnetic stirrer, or a high-speed dispersion device.
In the recording ink set of the present invention, to
prevent color bleed which will be caused between a black ink
and a color ink on poorly water-absorbable coated paper, it is
effective to use at least one different water-soluble organic
solvent between a black ink and color inks other than the black
ink and to make the surface tension of the water-soluble organic
solvents used for color inks other than the black ink higher than
that of the water-soluble organic solvent used for the black ink.
Here, poorly water-absorbable coated paper represents printing
coated paper containing a coating layer on at least one surface
of a support, in which the transfer amount of pure water to the
recording medium measured by the use of a dynamic scanning
absorptometer for a contact time of 100 ms is 3 mL/m 2 to 15
mL/m 2 .
In the recording ink and the recording ink set of the present invention, the contact angle between the ink and a
recording medium right after the ink is dropped on the recording medium depends on the surface tension of the ink, and the surface tension of the ink at a temperature of 25°C is preferably adjusted to 20 mN/m to 40 mN/m, and more preferably adjusted to 23 mN/m to 36 mN/m. When the surface tension of the ink is lower than 20 mN/m, the wetting of the ink to the ink discharge nozzle surface is increased, and ink droplets easily adhere on the nozzle head, and therefore ink droplets may not be stably discharged. When the surface tension of the ink is higher than 40 mN/m, the wetting of the ink to the recording medium is insufficient, which may cause color bleeding. The contact angle between the recording ink and a recording medium right after the ink is dropped on poorly water absorbable coated paper, here, the contact angle of the each ink when measured 100 ms after 2 μL of the each ink is dropped on a recording medium is preferably 15 degrees to 35 degrees, when the recording medium is provided with a coating layer on at least one surface of a support and has a transfer amount of pure water to the recording medium measured by the use of a dynamic scanning absorptometer for a contact time of
100 ms is 3 mL/m 2 to 15 mL/m 2 . When the contact angle is
smaller than 15 degrees, color bleed easily occurs, and when the
contact angle is larger than 35 degrees, there is a tendency that
color bleed easily occurs and drying property of the ink
degrades.
Liquid absorption property can be measured by using a
dynamic scanning absorptometer (DSA) available from KYOWA
SEIKO K.K.
A dynamic scanning absorptometer ((DSA) pp. 88-92, Vol.
48 Japan Paper and Pulp Technology Journal issued in May
1994) is a device that can accurately measure an absorption
amount in a small amount of time. A dynamic scanning
absorptometer (DSA) is automated measuring device by a
method in which it directly reads the rate of liquid absorption
from movement of a meniscus in a capillary and spirally scans a
disc-shaped test sample using a liquid absorption head, and
automatically change the scanning speed according to a
previously set pattern, thereby measuring liquid absorption on
necessary points in one paper sheet sample. The liquid
supplying head which supplies a liquid to a paper sheet sample
is connected the capillary through a TEFLON tube, and the
position of the meniscus in the capillary is automatically read by
an optical sensor.
The support is not particularly limited, may be suitably
selected in accordance with the intended use, and examples
thereof include sheet-like materials like paper mainly made of wood-fiber, or nonwoven fabric mainly made of wood-fiber and synthetic fiber.
The paper is not particularly limited and may be suitably selected from among those known in the art in accordance with the intended use. For example, wood pulp, waste paper or the like is used. Examples of the wood pulp include NBKP, LBKP,
NBSP, LBSP, GP, and TMP.
As an internal filler used in the support, for example, a pigment known as a white pigment is used. Examples of the internal filler include white inorganic pigments such as light calcium carbonate, heavy calcium carbonate, kaolin, clay, talc,
calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic silica, aluminum hydroxide, alumina, lithopone, zeolite, magnesium carbonate, and magnesium hydroxide; and organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin, and melamine resin. Each of these white pigments may be used alone or in combination with two or more. Examples of the internal sizing agent to be used in papermaking the support include neutral rosin sizing agents, alkenyl succinic anhydrides (ASA), alkylketenedimer (AKD), and petroleum resin sizing agents. Of
these, neutral rosin sizing agents or alkenyl succinic anhydride
is particularly preferable. It requires less addition amount of
the alkylketenedimer because of its high-sizing effect, however,
it may be unfavorably used from the perspective of conveyance
property of recording medium during the time of inkjet
recording because the use of alkylketenedimer easily makes the
friction coefficient of the recording medium surface reduced and
slippery.
The coated layer contains a pigment and a binder and
further contains a surfactant and other components in
accordance with the necessity. For the pigment used in the
coated layer, an organic pigment or a combination of an
inorganic pigment with an organic pigment is used. Examples
of the inorganic pigment include pigments made from kaolin,
talc, heavy calcium carbonate, light calcium carbonate, calcium
sulfite, amorphous silica, white titanium, magnesium carbonate,
titanium dioxide, aluminum hydroxide, calcium hydroxide,
magnesium hydroxide, zinc hydroxide, and chloride. Kaolin is
preferably used because it is excellent in glossiness and can
make sheet paper have a texture close to offset printing sheet
paper. There are delaminated kaolin, sintered kaolin,
engineered kaolin which are respectively subjected to a surface
modification treatment or the like, however, in view of the
glossiness, it is desired that kaolin having a particle diameter
distribution of which particles having a particle diameter of 2
μm or less are contained 80% by mass or more account for 50%
by mass or more of the total kaolin content.
The blending amount of kaolin is preferably 50 parts by
mass or more. When the blending amount is less than 50 parts
by mass, a sufficient glossiness effect is hardly expected. The
upper blending amount of kaolin is not particularly limited,
however, it is preferably 90 parts by mass or less from the
perspective of coating suitability, in consideration of the
flowability of kaolin and in particular, thickening property of
kaolin under high-shearing force.
In contrast, examples of the organic pigment include
water-soluble dispersions such as styrene-acryl copolymer
particles, styrene-butadiene copolymer particles, polystyrene
particles, polyethylene particles. Two or more of these organic
pigments may be used and mixed as internal fillers in the
support. The blending amount of the organic pigment is
typically 2 parts by mass to 20 parts by mass. Since organic
pigments are excellent in glossiness and have a lower specific
gravity than those of inorganic pigments, the use of an organic
pigment makes it possible to obtain a coating layer which is
bulky, highly glossy, and excellent in surface coating property.
When the blending amount of the organic pigment is less than 2
parts by mass, the effects cannot be sufficiently exhibited, and
when the blending amount is more than 20 parts by mass, the
flowability of the coating solution is degraded, which leads to
degraded coating operation and costly production cost. Organic
pigment particles are typically formed in a densely filled shape,
a hollow shape, a doughnut shape, etc., however, the average
particle diameter is preferably ranging from 0.2 μm to 3.0 μm in
view of the balance of glossiness, surface coating property, and
flowability of the costing solution, and it is more preferably that
organic pigment particles formed in a hollow shape having a
porosity of 40% or more be employed.
For the binder, a water-based resin is preferably used.
For the water-based resin, at least any one of a
water-soluble resin or a water-dispersible resin is preferably
used. The water-soluble resin is not particularly limited, may
be suitably selected in accordance with the intended use, and
examples thereof include polyvinyl alcohol, modified polyvinyl
alcohols such as anion-modified polyvinyl alcohol,
cation-modified polyvinyl alcohol, acetal-modified polyvinyl
alcohol; polyurethane! polyvinylpyrolidone, modified
polyvinylpyrolidones such as polyvinylpyrolidone vinyl acetate
copolymers, vinylpyrolidone- dime thy laminoethyl-methacry late
copolymers, quaternized vinylpyrolidone-dimethylaminoethyl-
methacrylate copolymers, and
vinylpyrolidone-methacrylamidepropyl trimythylammonium
chloride copolymers; celluloses such as carboxymethylcellulose,
hydroxyethylcellulose, and hydroxypropylcellulose; modified
cellulose such as cationized hydroxyethyl cellulose; polyester,
polyacrylic acid (esters), melamine resins, or modified products
thereof, " synthetic resins such as polyester-polyurethane
copolymers; poly(meth)acrylic acids, poly(meth)acrylamides,
oxidized starch, phosphoesterified starch, self-modified starch,
cationized starch, oχ various modified starches; polyethylene
oxide, polyacrylate soda, and soda alginate. Each of these
water-soluble resins may be used alone or in combination with
two or more.
Of these water-based resins, from the perspective of
absorption property of ink, polyvinyl alcohol, cation-modified
polyvinyl alcohol, acetal-modified polyvinyl alcohol, polyester,
polyurethane, and polyester-polyurethane copolymers are
particularly preferable. The method for forming the coating
layer is not particularly limited, may be suitably selected in
accordance with the intended use, and the coating layer can be
formed by a method in which a support is impregnated with a
coating layer solution or a coating layer solution is applied to a
support surface. The method of the impregnating the support
surface with a coating layer solution or the method of applying a
coating solution to the support surface is not particularly
limited, may be suitably selected in accordance with the
intended use. For example, the support surface can be coated with the coating layer solution using one of various coaters such as conventional size presses, gate roll size presses, film transfer size presses, blade coaters, rod coaters, air-knife coaters, and curtain coaters, however, from the viewpoint of cost performance, the support may be impregnated in the coating layer solution or may be applied with the coating layer solution using a conventional size press, gate roll size press, or a film transfer size press set in a paper machine and then surfaced on the machine.
Examples of commercially available coating solution to be used for the coating layer solution include OK Topcoat, OK Astro-Gloss, OK Non-wrinkle, SA Kinfuji+, OK Kinfujií, OK Non-wrinkle, (F) MCOP, OK Astro-dull, OK Astro-matt, OK Ultra-aquasatin, OK Emboss-matt, OK Emboss-pearskin finish, OK Emboss grain, OK Emboss homespun, OK Opt-gloss, OK Kasao, OK Casablanca, OK Casablanca V, OK Casablanca-X, OK Kinfuji single-side, OK Coat L, OK Coat L Green 100, OK Coat N Green 100, OK Coat V, OK medium-quality coat (for offset), OK Topcoat S, OK Topcoat dull, OK Topcoat matt N, OK Trinity, OK Trinity NaVi, OK Trinity NaVi-V, OK Neo Topcoat, OK Neo Topcoat-matt, OK Non-wrinkle AL, OK Non-wrinkle DL, OK Non wrinkle BL, OK White L, OK Matt Coat L Green 100, OK Matt Coat Green 100, OK Royal Coat, OK White L, Z Coat, Z
Coat Green 100, Ultra-satin Kifuji N, Golden Matt, Satin Kinfuji
N, New Age, New Age Green 100, Mirror Coat-Gold, Mirror
Coat-Platinum, Royal Coat L, LOSTON color, POD Super Gloss,
POD Gloss Coat, and POD Matt Coat (available from OJI Paper
Co.); Brode Matt A, Brode Gloss A, White Pearl Coat N, New V
Matt, Pearl Coat, Dignity, Vista Gloss, N Pearl Coat L, Utrillo,
EP D Gloss, EP-L Gloss, EP-L Matt, EP D Premium White, and
EP-Super High-quality (available from Mitsubishi Paper Mills
Ltd.), ' and Hi-α, crMatt, Kinmari Hi-L, Mew Coat, Mew Matt,
and Mew White (available from Hokuetsu Paper Mills Ltd.).
The recording ink and the recording ink set of the present
invention can be preferably used in various areas and can be
preferably used in an image recording apparatus (printers, etc.)
based on an inkjet recording method. For example, before or
after printing, recording subject paper and the recording ink can
be heated at 50 0 C to 200 0 C for use in a printer having a function
to accelerate fixing of the printing ink. The recording ink of
the present invention can be particularly preferably used in the
ink cartridge, ink record, inkjet recording apparatus, and inkjet
recording method, which will be described below.
- Ink Cartridge -
The ink cartridge suitably used in the present invention
contains a container containing the recording ink of the present
invention and other suitably selected members in accordance
with the necessity.
The container is not particularly limited and its shape,
structure, size, and material can be suitably selected in
accordance with the intended use. Preferred examples thereof
include those having at least an ink pouch formed by aluminum
laminated film or resin film.
Hereinafter, the ink cartridge will be described with
reference to FIGS. 1 .and 2. FIG. l is an illustration showing an
example of the ink cartridge suitably used in the present
invention. FIG.2 is an illustration of the ink cartridge of FIG. l
including a case (exterior).
In an ink cartridge 200, as shown in FIG. l, an ink pouch
241 is filled with an ink through an ink inlet 242. The ink inlet
242 is closed by fusion bonding after the air is exhausted. An
ink outlet 243 made of a rubber material is pierced by a needle
on the apparatus body for use, thereby the ink is supplied to the
apparatus.
The ink pouch 241 is formed by a packaging member such
as a non-permeable aluminum laminated film. The ink pouch
241 is housed in a cartridge case 244 generally made of plastics
as shown in FIG.2 and detachably mounted on various types of
inkjet recording apparatus.
The ink cartridge of the present invention contains the
recording ink (ink set) of the present invention. The ink
cartridge can be detachably mounted on variety types of inkjet
recording apparatus, and it is particularly preferable that the
ink cartridge of the present invention be detachably mounted on
the inkjet recording apparatus described later. '
- InkJet Recording Apparatus and InkJet Recording Method -
The inkjet recording apparatus suitably used in the
present invention is provided with at least an ink drop
discharging unit .and is further provided with other
appropriately selected units as required such as an impulse
generation unit and a control unit.
The inkjet recording method of the present invention
includes at least an ink drop discharging step and further
includes other appropriately selected steps as required such as
an impulse generation step, and a control step.
The inkjet recording method of the present invention can
be preferably performed by means of the inkjet recording
apparatus, and the ink drop discharging step can be preferably
performed by means of the ink drop discharging unit. The
other steps can be preferably performed by means of the other
units.
■ Ink Drop Discharging Step and Ink Drop Discharging Unit -
The ink drop discharging step is a step in which an
impulse is applied on the recording ink of the present invention
to discharge recording ink drops to thereby record an image.
The ink drop discharging unit is a unit configured to
discharge ink drops to record an image by applying an impulse
to the recording ink of the present invention. The ink drop
discharging unit is not particularly limited, and examples
thereof include various types of nozzle for discharging an ink.
In the present invention, it is preferable that at least
part of a liquid chamber, a fluid dragging part, a diaphragm,
and nozzle member be made of a material containing at least
any one of silicon and nickel.
The nozzle diameter of the inkjet nozzle is preferably
30μm or less, and more preferably 1 μm to 20 μm.
It is preferable that subtanks for supplying ink be
provided on the inkjet head and the ink be supplied to the
subtanks from the ink cartridge via supply tubes.
The impulse may be generated by using, for example, the
impulse generating unit, and the impulse is not particularly
limited, may be suitably selected in accordance with the
intended use, and examples thereof include heat (temperature),
pressure, vibration, and light. Each of these may be used alone
or in combination with two or more. Of these, heat, and
pressure are preferable.
The impulse generation unit may be, for example, a
heating apparatus, a pressurizing apparatus, a piezoelectric
element, a vibration generation apparatus, an ultrasonic
oscillator, or a light. Specifically, examples of the impulse
generation unit include a piezoelectric actuator such as a
piezoelectric element, a thermal actuator using an
electrothermal conversion element such as an exothermic
resistor to cause film boiling and, accordingly, phase change of a
liquid, a shape-memory alloy actuator using metal phase
changes due to temperature changes, an electrostatic actuator
using electrostatic fojce.
The aspect of the ink drop discharging is not particularly
limited and varies depending on the type of the impulse. For
example, when the impulse is "heat," thermal energy
corresponding to recording signals is applied to the recording
ink in the recording head, for example, using a thermal head,
the thermal energy causes the ink to bubble, and the bubble
pressure urges the ink to be discharged as ink droplets from the
nozzle hole of the recording head. When the impulse is
"pressure," for example, an electric voltage is applied to a
piezoelectric element bonded at a position called a pressure
chamber within the ink passage of the recording head, the
piezoelectric element is bent and the pressure chamber is
reduced in volume, thereby the ink is discharged as droplets
from the nozzle hole of the recording head.
The discharged ink droplets preferably have a particle
size of 3pl to 4 pi. The discharge jet speed is preferably 5m/sec
to 20m/sec; the driving frequency is preferably IkHz or more;
and. the resolution is preferably 300dpi or more.
An embodiment of the inkjet recording method of the
present invention using the inkjet recording apparatus will be
described hereinafter, with reference to the drawings. An
inkjet recording apparatus shown in FIG. 3 contains an
apparatus body 101, a feeder tray 102 attached to the apparatus
body 101 for feeding, papers, paper output tray 103 attached to
the apparatus body 101 for receiving papers on which images are
recorded (formed), and an ink cartridge mounting part 104. An
operation part 105 having operation keys and indicators is
provided on the top surface of the ink cartridge mounting part
104. The ink cartridge mounting part 104 has a front cover 115
that can be opened and/or closed to remove and/or place ink
cartridges 201.
As shown in FIGS. 4 and 5, a carriage 133 is supported
slidably in the scan direction by a guide rod 131 that is a guide
member laid across right and left side plates which are omitted
in the figures and a stay 132 and moved by a main scan-motor
(not shown) in the arrowed directions in FIG.5 for scanning
within the apparatus body 101.
Recording heads 134 consisting of four inkjet recording
heads that discharge yellow (Y), cyan (C), magenta (M), and
black (B) recording ink droplets, respectively, have ink discharge
ports arranged in the intersecting direction with the main
scanning direction and they are placed with their ink discharge
direction downward.
InkJet recording heads constituting the recording heads
134 are provided with an energy generation unit for discharging
recording ink such as a piezoelectric actuator such as an
piezoelectric element, a thermal actuator using an
electrothermal conversion element such as an exothermic
resistor to cause film boiling and, accordingly, phase change of a
liquid, a shape-memory alloy actuator using metal phase
changes due to temperature changes, and an electrostatic
actuator using electrostatic force.
The carriage 133 is provided with subtanks 135 for
supplying each ink to the recording heads 134. The subtanks
135 are filled with the recording ink of the present invention
from the ink cartridge 200 mounted in the ink cartridge
mounting part 104 via a not-shown recording ink supply tube.
In the meanwhile, a paper feed part for feeding paper 142
stuck on a paper load part (platen) 141 of the feed tray 102 is
provided with a half-moon roller (a feed roller 143) that
separates and supplies the paper 142 from the paper load part
141 one by one and a separation pad 144 that faces the feed
roller 143 and is made of a large friction coefficient material.
The separation pad 144 is biased toward the feed roller 143.
A conveying part for conveying the paper 142 supplied
from the feed part underneath the recording heads 134 is
provided with a conveying belt 151 for electrostatically
adsorbing and conveying the paper 142, a counter roller 152 for
conveying the paper 142 sent from the paper feed part via a
guide 145 by clamping it together with the conveying belts 151,
a conveying guide 153 for turning the paper 142 sent nearly
vertically by 90° so a.s to lay it on the conveying belt 151, and a
leading end pressure roller 155 that is biased toward the
conveying belt 151 by a presser member 154. A charging roller
156 that is a charging unit for charging the surface of the
conveying belt 151 is also provided.
The conveying belt 151 is an endless belt, being spanned
over conveying roller 157 and a tension roller 158 and running
around in the belt conveying direction. For example, the
conveying belt 151 has a front layer that is a paper adsorbing
surface made of a dragging-uncontrolled resin, for example a
copolymer of tertafluoroethylene and ethylene (ETFE), having a
thickness of around 40 μm and a back layer (an intermediate
dragging layer or an earth layer) made of the same material as
the front layer, but dragging-controlled with carbon. A guide
member 161 is provided behind the conveying belt 151 at the
corresponding position to the printing area by the recording
heads 134. An output part for discharging the paper 142 on
which recording was done by the recording heads 134 is provided
with a separation click 171 for separating the paper 142 from
the conveying belt 151, a paper output roller 172, and an paper
output roller 173. Paper output tray 103 is disposed below
paper output roller 172.
A double-side feed unit 181 is detachably mounted in the
back of the apparatus body 101. The double-side feed unit 181
takes in the paper 142 that is moved backward as the conveying
belt 151 is rotated in the reverse direction, turns it over, and
feeds it again between the counter roller 152 and the conveying
belt 151. A manual feeder 182 is provided on the top surface of
the double-side feed unit 181.
By receiving a recording end signal or a signal indicating
that the rear end of the paper 142 has reached the recording
area, the recording operation is terminated and the paper 142 is
discharged to the paper output tray 103.
When it is detected that the remaining amount of the
recording ink in the subtank 135 is nearly to the end, a certain
amount of recording ink is supplied to the subtank 135 from the
ink cartridge 200.
In this inkjet recording apparatus, when the recording
ink in the ink cartridge 200 is used up, the case of the ink
cartridge 200 is disassembled and only the ink pouch contained
therein can be exchanged. The ink cartridge 200 allows for
stable recording ink supply even in a vertical and front
mounting structure. Therefore, when the apparatus body 101 is
installed with the top being blocked by something, for example,
even when the inkjet recording apparatus body 101 is housed in
a rack, or even when something is placed on the top surface of
the apparatus body 101, the ink cartridge 200 can be easily
replaced.
Here, the explanation is made with reference to an
application in a serial type (shuttle type) inkjet recording
apparatus in which the carriage scans is described. The inkjet
recording apparatus is also applicable to a line type inkjet
recording apparatus having a line head.
The inkjet recording apparatus and inkjet recording
method of the present invention are applicable to various
recording using inkjet recording system. For example, the
inkjet recording apparatus and inkjet recording method can be
particularly preferably applied to inkjet recording printers,
inkjet recording facsimiles, inkjet recording copiers, and inkjet
recording printer/fax/copy complex machines.
An inkjet head to which the present invention is applied
will be described hereinafter.
FIG.6 is an enlarged view exemplarily showing the core
part of an inkjet head according to an embodiment of the present
invention. FIG. 7 is an enlarged cross-sectional view of the
core part of the same head in the inter-channel direction.
This inkjet head is provided with a frame 10 having
cutouts serving as an ink supply port (not shown) which supplies
an ink from the front side of the figure toward the inner side
direction thereof and a common liquid chamber 12 formed
thereon? a passage plate 20 having cutouts serving as a fluid
dragging part 21 and a pressurized liquid chamber 22 and a
communication port 23 that communicates to a nozzle 31 formed
thereon? a nozzle plate constituting the nozzle3l; a diaphragm
60 having a raised part 61, a diaphragm part 62 and an ink
inflow port 63; a laminated piezoelectric element 50 connected to
the diaphragm 60 via an adhesive layer 70, " and a base 40 on
which the laminated piezoelectric element 50 is fixed. The base
40 is made of barium titanate ceramics, on which two rows of
laminated piezoelectric element 50 are arranged and connected.
The piezoelectric element 50 consists of alternately
laminated piezoelectric layers 51 of lead zirconate titanate
(PZT) having a thickness of 10 μm to 50 μm per layer and
internal electrode layers 52 of silver palladium (AgPd) having a
thickness of several μm per layer. The internal electrode layers
52 are connected to external electrodes 53 at both ends.
The alternately laminated piezoelectric element 50 is
divided into a comb-like shape by half-cut dicing, having driving
parts 56 and supporting parts (non-driving part) 57 every other
division (FIG. 7). The outer end of one of the two external
electrodes 53 is processed, for example, is notched, for limiting
on length, thereby being divided by half-cut dicing. The outer
end is connected to one end of the internal electrodes 52 at a
position in the front side direction of the figure or the inner side
direction. Then, the division of the external electrode 53 makes
multiple separate electrodes 54. The other is not divided by
dicing, and is conductive and serves as a common electrode 55.
A FPC (reference numeral 80) is soldered to the
individual electrodes 54 of the driving part. The common
electrode 55 is turned in an electrode layer provided at the end
of the laminated piezoelectric element and connected to the Gnd
electrode of the FPC 80. An not-shown driver IC is mounted on
the FPC 80 to control the application of driving voltage to the
driving part 56.
As for the diaphragm 60, a thin film diaphragm part 62,
an island-shaped raised part (island part) 61 formed at the
center of the diaphragm part 62 and connected to the laminated
piezoelectric element 50 serving as the driving parts 56, a thick
part including beams to be connected to the supporting part, and
an opening serving as in ink inflow port 63 are formed by
electroforming two nickel plated films in piles. The diaphragm
part has a thickness of 3 μm and a width (one side) of 35 μm.
The connections between the island-shaped raised part 61
of the diaphragm 60 and the movable parts 56 of the laminated
piezoelectric element 50 and between the diaphragm 60 and the
frame 10 are made by patterning the adhesive layer 70 including
a gap material.
The passage plate 20 is made of a silicon mono-crystalline
substrate, in which cutouts serving as a liquid dragging part 21
and a pressurized liquid chamber 22 and a through-hole 23
provided at the corresponding position to the nozzle 31 and
serving as a communication port 23 are patterned by etching.
The remaining part after the etching serves as a partition
wall 24 of the pressurized liquid chamber 22. In this head, a
part etched in a smaller width is provided, which serves as the
liquid dragging part 21.
The nozzle plate 30 is made of a metal material such as a
nickel plated film formed by electroforming and has a number of
nozzles 31 serving as fine discharge openings for discharging ink
droplets. The nozzle 31 has a horn-like (nearly cylindrical or
nearly truncated cone) internal shape (inner shape). The
nozzle 31 has a diameter of approximately 20 μm to 35 μm at the
ink droplets discharge side. The nozzle pitch in each row is
150dpi.
The ink discharging surface (nozzle front side) of the
nozzle plate 30 is provided with an ink-repellent layer 90
serving as a water-repellent finish film. A water-repellent
finish film selected according to ink's physical properties, such
as from PTFE-Ni eutectoid plating, ' and electrodeposition of
fluororesin; deposition of volatile fluororesin such as fluoro
pitch; and silicone resin and fluororesin solvent application and
baking can be provided to stabilize ink droplet shapes and
discharging property to ensure a high image quality. Among
them, for example many fluororesins are known, and excellent
water-repellency can be obtained by depositing modified
perfluoropolyoxethane (trade name: Optool DSX available from
Daikin Industries, Ltd.) to a thickness of 300 nm to 1,00 * 0 nm
(30 angstroms to 100 angstroms).
The frame 10 in which cutouts serving as an ink supply
inlet and a common liquid chamber 12 are formed is made by
molding a resin.
In an inkjet head having the above structure, a driving
waveform (lOV to 50V pulse voltage) is applied to the driving
part 56 according to recording signals. The driving part 56 is
shifted in the lamination direction. The pressurized liquid
chamber 22 is pressurized via the nozzle plate 30 and the
pressure is increased, thereby ink droplets are discharged
through the nozzle 31.
After the ink droplets discharge is completed, the ink
pressure in the pressurized liquid chamber 22 is reduced. The
inertia ink flow and driving pulse discharge process causes
negative pressure within the pressurized liquid chamber 22, leading to the ink supply process. Meanwhile, the ink supplied
from the ink tank enters the common liquid chamber 12 and further fills the pressurized liquid chamber 22 from the common liquid chamber 12 via the ink inflow port 63 and fluid dragging
part 21.
The fluid dragging part 21 effectively attenuates residual pressure fluctuation while it stands against recharging
(refilling) due to surface tension. Appropriately selected dragging part balances residual pressure attenuation with refilling time and shortens the transition time to the next ink
droplets discharge operation (driving cycle). (Ink Record)
An ink record on which an image is recorded by means of the inkjet recording apparatus and the recording method of the present invention are the ink records of the present invention.
The ink record of the present invention has images recorded on recording media using the recording ink of the present
invention. The ink record has high quality images, causes less exudation of ink, excels in temporal stability and can be suitably applied to various purposes as documents with various prints
and/or images recorded thereon, and the like.
Example
Hereafter, the present invention will be further described
in detail referring to specific Examples and Comparative
Examples, however, the present invention is not limited to the
disclosed Examples.
Preparation Example 1 (Surface-finished carbon black pigment
dispersion)
Ninety grams . (9Og) of a carbon black having a CTAB
specific surface area of 150 m 2 /g and a DBP oil absorption of 100
mL/100g was added to 3,000 mL of a sodium sulfate solution
2.5N, and the mixture was stirred at 60 0 C and a stirring rate of
300 rpm to be reacted for 10 hours for oxidation treatment.
The reactant was filtrated, and the filtrated carbon black was
neutralized with a sodium hydroxide solution, and the
neutralized carbon black was ultrafiltrated. The obtained
carbon black was washed, dried, and then dispersed in pure
water in such a way that the carbon black content was 20% by
mass.
Preparation Example 2 (Preparation of surface-finished cyan
pigment)
C.I. Pigment Cyan 15^3 was used as a cyan pigment, and
the pigment was plasma-treated at a low temperature to prepare
a pigment into which a carboxylic acid group was introduced.
The prepared pigment was dispersed in an ion exchange water,
and the pigment dispersion was desalinated and condensed to
thereby yield a cyan pigment dispersion 1 having a pigment
concentration of 15%.
Preparation Example 3 (Preparation of surface -finished magenta
pigment)
A surface-modified magenta pigment was prepared in the
same manner as in Preparation Example 2 except that C.I.
Pigment Red 122 wa.s used instead of C.I. Pigment Cyan 15:3.
Similarly to the above-noted examples, the obtained
surface-modified color pigment was easily dispersed in the
water-based medium during the stirring process.
Preparation Example 4 (Preparation of surface-finished yellow
pigment dispersion)
A surface-modified yellow pigment was prepared in the
same manner as in Preparation Example 2 except that C.I.
Pigment Yellow 128 was used instead of C.I. Pigment Cyan 15 ^3.
Similarly to the above-noted examples, the obtained
surface -modified color pigment was easily dispersed in the
water-based medium during the stirring process.
Synthesis Example 1 (Preparation of polymer dispersion)
The inside of a IL flask equipped with a mechanical
stirrer, a thermometer, a nitrogen gas inlet tube, a reflux tube,
and a dropping funnel was sufficiently nitrogen-substituted.
Then, 11.2g of styrene, 2.8g of acrylic acid, 12.Og of lauryl
methacrylate, 4.0g of polyethylene glycol methacrylate, 4.Og of
styrene macromer (trade name: AS-6, available from TOA KASEI
Co., Ltd.), and 0.4g of mercapto-ethanol were poured in the flask,
and the temperature was raised to 65°C. Next, a mixture
solution containing 100.8g of styrene, 25.2g of acrylic acid,
108.Og of lauryl methacrylate, 36.Og of polyethylene glycol
methacrylate, 60.Og of hydroxyethyl methacrylate, 36.Og of
styrene macromer (trade name^ AS-6, available from TOA KASEI
Co., Ltd.), 3.6g of mercapto-ethanol, 2.4g of azobisdimethyl
valeronitrile, and 18g of methylethylketone was delivered by
drops into the flask through the dropping funnel over a period of
2.5 hours. After the dropping was completed, a mixture
solution containing 0.8g of azobisdimethyl valeronitril and 18g
of methylethylketone was delivered by drops into the flask
through the dropping funnel over a period of 0.5 hours. The
mixture was aged at 65°C for 1 hour, 0.8g of azobisdimethyl
valeronitrile was added to the mixture, and the mixture was
further aged for 1 hour. After the completion of reaction, 364g
of methylethylketone was added into the flask to yield 80Og of a
polymer solution having a polymer concentration of 50%.
Preparation Example 5 (Preparation of polymer fine particle
dispersion containing carbon black)
Twenty-eight grams (28g) of the polymer solution
prepared in Synthesis Example 1 and 26g of carbon black, 13.6g
of 1 mole/L potassium hydroxide solution, 2Og of
methylethylketone, and 3Og of ion exchange water were
sufficiently stirred and then kneaded using a three-roller mill.
The obtained paste was put in 20Og of ion exchange water and
sufficiently stirred, and then methylethylketone and water were
distilled away using an evaporator to thereby yield a black-color
polymer fine particle dispersion.
Preparation Examplβ 6 (Preparation of polymer fine particle
dispersion containing a phthalocyanine pigment)
A black-color polymer fine particle dispersion was
obtained in the same manner as in Preparation Example 5
except that the carbon black pigment was changed to a
phthalocyanine pigment.
Preparation Example 7 (Preparation of polymer fine particle
dispersion containing a dimethylquinacridone pigment)
A magenta-color polymer fine particle dispersion was
obtained in the same manner as in Preparation Example 5
except that the carbon black pigment was changed to C.I.
Pigment Red 122.
Preparation Example 8 (Preparation of polymer fine particle
dispersion containing a monoazo yellow pigment)
A yellowcolor polymer fine particle dispersion was
obtained in the same manner as in Preparation Example 5
except that the carbon black pigment was changed to C.I.
Pigment Yellow 74.
Production Example 1
■ Production of Black Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 1 8.0% by
mass (by solid content)
• Acrylic resin fine particles 5.5% by mass (by
solid content) (Aquabrid 4720, average particle diameter- 95 nm,
available from DAICEL CHEMICAL INDUSTRIES, LTD.)
• Glycerin (surface tension- 63.3 mN/m) 8.5% by mass
• 2-methyl-2, 4-pentanediol 17.0% by mass
(surface tension: 27 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass
CF 3 CF 2 (CF 2 CF 2 ) m - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 58.0% by mass
Production Example 2
- Production of Cyan Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to. thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 2 5.0% by
mass (by solid content)
• Acrylic resin fine particles 4.0% by mass (by solid
content) (Aquabrid 4720, available from DAICEL CHEMICAL
INDUSTRIES, LTD.)
• Glycerin (surface tension: 63.3 mN/m) 7.0% by mass
• 3-methyl- l, 3-butanediol 21.0% by mass
(surface tension^ 32.8 mN/m)
• 2 ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass
CF 3 CF 2 (CF 2 CF 2 ^ 1 - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 60.0% by mass
Production Example 3
- Production of Magenta Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition > .
• Pigment dispersion of Preparation Example 3 8.0% by
mass (by solid content)
• Acrylic resin fine particles 3.20% by mass (by solid
content) (Aquabrid 4720, available from DAICEL CHEMICAL
INDUSTRIES, LTD.)
• Glycerin (surface tension- 63.3 mN/m) 7.0% by mass
• 3-methyl- l,3-butanediol 21.0% by mass
(surface tension^ 32.8 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass CF 3 CF 2 (CF 2 CF 2 X n -CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( O
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 57.8% by mass
Production Example 4
- Production of Yellow Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 4 5.0% by
mass (by solid content)
• Acrylic resin fine particles 4.0% by mass (by solid
content) (Aquabrid 4720, available from DAICEL CHEMICAL
INDUSTRIES, LTD.)
• Glycerin (surface tension^ 63.3 mN/m) 7.0% by mass
• 3-methyl l,3-butanediol 21.0% by mass
(surface tension^ 32.8 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass CF 3 CF 2 (CF 2 CF 2 ) m - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I ) In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 60.0% by mass
Production Example 5
■ Production of Cyan Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was added thereto such that the pH value of the ink composition solution was adjusted to 9. Then, the ink composition solution was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink. < Ink Composition >
• Pigment dispersion of Preparation Example 2 5.0% by mass (by solid content)
• Acrylic resin fine particles 4.0% by mass (by solid content) (Aquabrid 4720, available from DAICEL CHEMICAL
INDUSTRIES, LTD.)
• Glycerin (surface tension: 63.3 mN/m) 7.5% by mass
• 1, 3-butanediol 22.5% by mass (surface tension^ 37.8 mN/m) • 2-ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural Formula (II) 1.0% by mass
OCH 2 -Rf OCH 2 -Rf
In the Structural Formula (II), n = 4, m = 2, p = 4, and RF= CF 2 CF 3 .
• Ion exchange water 60.0% by mass
Production Example 6
■ Production of Magenta Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink. < Ink Composition > .
• Pigment dispersion of Preparation Example 3 8.0% by mass (by solid content)
• Acrylic resin fine particles 3.2% by mass (by solid content) (Aquabrid 4720, available from DAICEL CHEMICAL
INDUSTRIES, LTD.)
• Glycerin (surface tension: 63.3 mN/m) 7.5% by mass • 1, 3-butanediol 22.5% by mass
(surface tension: 37.8 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural Formula (II) 1.0% by mass
OCH 2 - Rf OCH 2 -Rf
In the Structural Formula (II), n = 4, m = 2, p = 4, and
RF= CF 2 CF 3 .
• Ion exchange water 55.8% by mass Production Example 7
- Production of Yellow Pigment Ink -
An ink composition having the following formulation was prepared, and a 10% aqueous lithium hydroxide solution was added thereto such that the pH value of the ink composition solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore diameter of 0.8 μm to thereby prepare a recording ink. < Ink Composition >
• Pigment dispersion of Preparation Example 4 5.0% by mass (by solid content)
• Acrylic resin fine particles 4.0% by mass (by solid content) (Aquabrid 4720, available from DAICEL CHEMICAL
INDUSTRIES, LTD.)
• Glycerin (surface tension: 63.3 mN/m) 7.5% by mass
• 1, 3-butanediol 22.5% by mass (surface tension: 37.8 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass • Fluorochemical surfactant represented by Structural
Formula (II) 1.0% by mass
OCH 2 - Rf OCH 2 - Rf
In the Structural Formula (II), n = 4, m = 2, p = 4, and
RF= CF 2 CF 3 .
• Ion exchange water 58.0% by mass
Production Example 8
- Production of Black Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium ' hydroxide solution was
added thereto such .that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 1 8.0% by
mass (by solid content)
• Polyester-urethane resin fine particles 4.0% by mass (by
solid content) (Hydran HW930, average particle diameter: 102
nm, available from Dainippon Ink and Chemicals, Inc.)
• Glycerin (surface tension : 63.3 mN/m) 7.0% by mass
• 3-methyl' l, 3-butanediol 21.0% by mass
(surface tension: 32.8 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (III) 1.0% by mass
OCH 2 -Rf
In Structural Formula (III), q = 6, Ri = NH 4 , R2 = SO 3 ,
and Rf = CF 2 CF 3 .
• Ion exchange water 57.0% by mass
Production Example 9
■ Production of Cyan Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 2 5.0% by
mass (by solid content)
• Polyester-urethane resin fine particles 4.0% by mass (by
solid content) (Hydran HW930, available from Dainippon Ink
and Chemicals, Inc.)
• Glycerin (surface tension^ 63.3 mN/m) 7.5% by mass
• 1, 3-butanediol 22.5% by mass
(surface tension^ 37.8 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Nonionic surfactant 1.0% by mass (Softanol EP7025, available from NIPPON SHOKUBAI
CO., LTD.)
5 • Ion exchange water 58.0% by mass
Production Example 10
- Production of Magenta Pigment Ink -
An ink composition having the following formulation was prepared, and a 10% aqueous lithium hydroxide solution was i o added thereto such that the pH value of the ink composition solution was adjusted to 9. Then, the ink composition solution was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition > 15 • Pigment dispersion of Preparation Example 3 8.0% by
mass (by solid content)
• Polyester-urethane resin fine particles 3.2% by mass (by solid content) (Hydran HW930, available from Dainippon Ink
and Chemicals, Inc.)
20 • Glycerin (surface tension^ 63.3 mN/m) 7.5% by mass
• 1, 3-butanediol 22.5% by mass (surface tension^ 37.8 mN/m)
• 2-ethyl" l,3-hexanediol 2.0% by mass
• Nonionic surfactant 1.0% by mass
(Softanol EP7025, available from NIPPON SHOKUBAI
CO., LTD.)
• Ion exchange water 55.8% by mass
Production Example 11
- Production of Yellow Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 4 5.0% by
mass (by solid content)
• Polyester-urethane resin fine particles 4.0% by mass (by
solid content) (Hydran HW930, available from Dainippon Ink
and Chemicals, Inc.)
• Glycerin (surface tension^ 63.3 mN/m) 7.5% by mass
• 1, 3-butanediol 22.5% by mass
(surface tension: 37.8 mN/m)
• 2-ethyl" l,3-hexanediol 2.0% by mass
• Nonionic surfactant 1.0% by mass
(Softanol EP7025, available from NIPPON SHOKUBAI
CO., LTD.)
• Ion exchange water 58.0% by mass Production Example 12
- Production of Black Pigment Ink -
An ink composition having the following formulation was prepared, and a 10% aqueous lithium hydroxide solution was added thereto such that the pH value of the ink composition solution was adjusted to 9. Then, the ink composition solution was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink. < Ink Composition >
• Pigment dispersion of Preparation Example 5 8.0% by mass (by solid content)
• Glycerin (surface tension: 63.3 mN/m) 8.0% by mass
• 1, 3-butanediol 24.0% by mass (surface tension^ 37.8 mN/m)
• 2 ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural Formula (III) 1.0% by mass
OCH 2 -Rf
and Rf = CF 2 CF 3 .
• Ion exchange water 57.0% by mass
Production Example 13
■ Production of Cyan Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 6 6.0% by
mass (by solid content)
• Glycerin (surface tension^ 63.3 mN/m) 8.2% by mass
• Triethylene glycol 25.6% by mass
(surface tension: 45.2 mN/m)
• 2-ethyl l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (III) 1.0% by mass
In Structural Formula (III), q = 6, Ri = NH 4 , R2 = SO 3 ,
and Rf = CF 2 CF 3 -
• Ion exchange water 57.2% by mass
Production Example 14
■ Production of Magenta Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 7 8.0% by
mass (by solid content)
• Glycerin (surface tension- 63.3 mN/m) 8.2% by mass
• Triethylene glycol 25.6% by mass
(surface tension: 45.2 mN/m)
• 2-ethyl- l,3 hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (III) 1.0% by mass
In Structural Formula (III), q = 6, Ri = NH 4 , R2 = SO 3 ,
and Rf = CF 2 CF 3 .
• Ion exchange water 55.2% by mass
Production Example 15
■ Production of Yellow Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 8 6.0% by
mass (by solid content)
• Glycerin (surface tension: 63.3 mN/m) 8.2% by mass
• Triethylene glycol 25.6% by mass
(surface tension^ 45.2 mN/m)
• 2-ethyM,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (III) 1.0% by mass
OCH 2 -Rf
In Structural Formula (III), q = 6, R 1 = NH 4 , R2 = SO 3 ,
and Rf = CF 2 CF 3 .
• Ion exchange water 57.2% by mass
Production Example 16
- Production of Black Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 1 8.0% by
mass (by solid content)
• Acrylic resin fine particles 5.5% by mass (by solid
content) (Aquabrid 4720, available from DAICEL CHEMICAL
INDUSTRIES, LTD.)
• 2-methyl-2, 4-pentanediol 20.0% by mass
(surface tension^ 27 mN/m)
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass CF 3 CF 2 (CF 2 CF 2 ) Jn - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 65.5% by mass
Production Example 17
- Production of Cyan Pigment Ink -
An ink composition having the following formulation was prepared, and a 10% aqueous lithium hydroxide solution was added thereto such that the pH value of the ink composition solution was adjusted to 9. Then, the ink composition solution was filtrated through a membrane filter having an average pore diameter of 0.8 μm to thereby prepare a recording ink. < Ink Composition >
• Pigment dispersion of Preparation Example 2 6.0% by mass (by solid content) • Acrylic resin fine particles 4.0% by mass (by solid content) (Aquabrid 4720, available from DAICEL CHEMICAL INDUSTRIES, LTD.)
• 1,5-pentanediol 18.0% by mass (surface tension : 43.2 mN/m) • Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass
CF 3 CF 2 (CF 2 CF 2 X 11 - CH 2 CH 2 O(CH 2 CH 2 O) n H • • ■ ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 71.0% by mass Production Example 18
- Production of Magenta Pigment Ink -
An ink composition having the following formulation was prepared, and a 10% aqueous lithium hydroxide solution was added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 3 8.0% by
mass (by solid content)
• Acrylic resin fine particles 5.5% by mass (by solid
content) (Aquabrid 4720, available from DAICEL CHEMICAL
INDUSTRIES, LTD.)
• 1,5-pentanediol 17.0% by mass
(surface tension^ 43.2 mN/m)
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass CF 3 CF 2 (CF 2 CF 2 X n -CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I ) In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 68.5% by mass
Production Example 19
- Production of Yellow Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 4 6.0% by
mass (by solid content)
• Acrylic resin fine particles 4.0% by mass (by 1 solid
content) (Aquabrid 4720, available from DAICEL CHEMICAL
INDUSTRIES, LTD.)
• 1,5-pentanediol 18.0% by mass
(surface tensipn: 43.2 mN/m)
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass
CF 3 CF 2 (CF 2 CF 2 )^ 1 - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 71.0% by mass
Production Example 20
■ Production of Black Pigment Ink ■
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 5 7.0% by
mass (by solid content)
• Glycerin (surface tension: 63.3 mN/m) 12.0% by mass
• 1,3-butanediol 24.0% by mass
(surface tension: 37.8 mN/m)
• 2-ethyM,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass
CF 3 CF 2 (CF 2 CF 2 ^ 1 - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 54.0% by mass
Production Example 21
- Production of Cyan Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 5 5.0% by
mass (by solid content)
• Glycerin (surface tension: 63.3 mN/m) 10.0% by mass
• 1,5-pentanediol 28.0% by mass
(surface tension: 43.2 mN/m)
• 2-ethyl" l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass CF 3 CF 2 (CF 2 CF 2 ) m — CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 54.0% by mass
Production Example 22
- Production of Magenta Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 6 7.0% by
mass (by solid content)
• Glycerin (surface tension: 63.3 mN/m) 10.0% by mass
• 1,5-pentanediol 28.0% by mass
(surface tension: 43.2 mN/m)
• 2-ethyl l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass CF 3 CF 2 (CF 2 CF 2 ) Q1 - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 52.0% by mass Production Example 23
- Production of Yellow Pigment Ink -
An ink composition having the following formulation was prepared, and a 10% aqueous lithium hydroxide solution was added thereto such that the pH value of the ink composition solution was adjusted to 9. Then, the ink composition solution was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink. < Ink Composition >
• Pigment dispersion of Preparation Example 7 5.0% by mass (by solid content)
• Glycerin (surface tension^ 63.3 mN/m) 10.0% by mass
• 1,5-pentanediol 28.0% by mass (surface tension^ 43.2 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural Formula (I) 1.0% by mass CF 3 CF 2 (CF 2 CF 2 )Q 1 - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I ) In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 54.0% by mass Production Example 24
- Production of Black Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
5 diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 1 8.0% by
mass (by solid content)
• Acrylic resin fine particles 5.0% by mass (by
i o solid content) (Aquabrid 4720, available from DAϊCEL
CHEMICAL INDUSTRIES, LTD.)
• Glycerin (surface tension- 63.3 mN/m) 9.0% by mass
• 3-methyl- l,3-pentanediol 18.0% by mass
(surface tension- 32.8 mN/m)
15 • 2-ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass CF 3 CF 2 (CF 2 CF 2 ) m - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
In the Structural Formula (I), m = 2, and n = 10.
20 • Ion exchange water 57.0% by mass
Production Example 25
- Production of Black Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 1 8.0% by
mass (by solid content)
• Acrylic resin, fine particles 5.5% by mass (by
solid content) (Aquabrid 4720, available from DAICEL
CHEMICAL INDUSTRIES, LTD.)
• 2-methyl-2,4-pentanediol 14.0% by mass
(surface tension: 27 mN/m)
• 2-ethyl l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass
CF 3 CF 2 (CF 2 CF 2 X n - CH 2 CH 2 O(CH 2 CH 2 O) n H • • ■ ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 69.5% by mass
Production Example 26
- Production of Cyan Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 2 6.0% by
mass (by solid content)
• Acrylic resin fine particles 4.0% by mass (by
solid content) (Aquabrid 4720, available from DAICEL
CHEMICAL INDUSTRIES, LTD.)
• 1,5-pentanediol (surface tension: 43.2 mN/m) 7.5% by
mass
• 1,3-butanediol 14.0% by mass
(surface tension^ 43.2 mN/m)
• 2 ethyl l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass
CF 3 CF 2 (CF 2 CF 2 ) H1 - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 73.0% by mass
Production Example 27
- Production of Magenta Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 3 8.0% by
mass (by solid content)
• Acrylic resin fine particles 5.5% by mass (by
solid content) (Aquabrid 4720, available from DAICEL
CHEMICAL INDUSTRIES, LTD.)
• 1,5-pentanediol 14.0% by mass (surface tension- 43.2 mN/m)
• 2 ethyl- l,3 hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass CF 3 CF 2 (CF 2 CF 2 ) m — CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I ) In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 69.5% by mass
Production Example 28
- Production of Yellow Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 4 6.0% by
mass (by solid content)
• Acrylic resin fine particles 4.0% by mass (by
solid content) (Aquabrid 4720, available from DAICEL
CHEMICAL INDUSTRIES, LTD.)
• 1,5-pentanediol 14.0% by mass
(surface tensipn: 43.2 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass
CF 3 CF 2 (CF 2 CF 2 )^ 1 - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 73.0% by mass
Production Example 29
- Production of Black Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 5 7.0% by
mass (by solid content)
• Glycerin (surface tension: 63.3 mN/m) 13.0% by mass
• 1,3-butanediol 28.0% by mass (surface tension: 37.8 mN/m) • 2-ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural Formula (I) 1.0% by mass CF 3 CF 2 (CF 2 CF 2 ) m - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
In the Structural Formula (I), m = 2, and n = 10. • Ion exchange water 49.0% by mass
Production Example 30
- Production of Cyan Pigment Ink -
An ink composition having the following formulation was prepared, and a 10% aqueous lithium hydroxide solution was added thereto such that the pH value of the ink composition solution was adjusted to 9. Then, the ink composition solution was filtrated through a membrane filter having an average pore diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition > • Pigment dispersion of Preparation Example 5 5.0% by
mass (by solid content)
• Glycerin (surface tension: 63.3 mN/m) 10.0% by mass
• 1,5-petanediol 31.0% by mass (surface tension: 43.2 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural Formula (I) 1.0% by mass CF 3 CF 2 (CF 2 CF2) m — CH 2 CH 2 O(CH 2 CH 2 O) n H • • ■ ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 51.0% by mass
Production Example 31
- Production of Magenta Pigment Ink -
An ink composition having the following formulation was prepared, and a 10% aqueous lithium hydroxide solution was added thereto such that the pH value of the ink composition solution was adjusted to 9. Then, the ink composition solution was filtrated through a membrane filter having an average pore diameter of 0.8 μm to thereby prepare a recording ink. < Ink Composition >
• Pigment dispersion of Preparation Example 6 7.0% by mass (by solid content)
• Glycerin (surface tension- 63.3 mN/m) 10.0% by mass
• 1,5-petanediol 31.0% by mass (surface tension: 43.2 mN/m)
• 2-ethyl l,3 hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass CF 3 CF 2 (CF 2 CF 2 ) m — CH 2 CH 2 O(CH 2 CH 2 O) n H • • ■ ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 49.0% by mass
Production Example 32
- Production of Yellow Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 7 5.0% by
mass (by solid content)
• Glycerin (surface tension: 63.3 mN/m) 10.0% by mass
• 1, 5-petanediol 31.0% by mass
(surface tension: 43.2 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass CF 3 CF 2 (CF 2 CF 2 X n - CH 2 CH 2 O(CH 2 CH 2 O) n H • • ■ ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 51.0% by mass
Production Example 33
■ Production of Black Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 1 8.0% by
mass (by solid content)
• Acrylic resin fine particles 5.5% by mass (by
solid content) (Aquabrid 4720, available from DAICEL
CHEMICAL INDUSTRIES, LTD.)
• Glycerin (surface tension^ 63.3 mN/m) 8.5% by mass
• 2-methyl-2,4-pentanediol 17.0% by mass
(surface tension: 27 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Ion exchange water 59.0% by mass
Production Example 34
- Production of Cyan Pigment Ink ■
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 2 5.0% by
mass (by solid content)
• Acrylic resin fine particles 4.0% by mass (by
solid content) (Aquabrid 4720, available from DAICEL
CHEMICAL INDUSTRIES, LTD.)
• Glycerin (surface tension^ 63.3 mN/m) 7.0% by mass
• 3-methyl- l,3-butanediol 21.0% by mass (surface tension: 32.8 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Ion exchange water 61.0% by mass
Production Example 35
- Production of Magenta Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 3 8.0% by
mass (by solid content)
• Acrylic resin fine particles 3.2% by mass (by
solid content) (Aquabrid 4720, available from DAICEL
CHEMICAL INDUSTRIES, LTD.)
• Glycerin (surface tension: 63.3 mN/m) 7.0% by mass
• 3-methyl- l,3-butanediol 21.0% by msiss
(surface tension: 32.8 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Ion exchange water 58.8% by mass
Production Example 36
■ Production of Yellow Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 4 5.0% by
mass (by solid content)
• Acrylic resin fine particles 4.0% by mass (by
solid content) (Aquabrid 4720, available from DAICEL
CHEMICAL INDUSTRIES, LTD.)
• Glycerin (surface tension: 63.3 mN/m) 7.0% by mass
• 3-methyl- l,3-butanediol 21.0% by mass
(surface tension: 32.8 mN/m)
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Ion exchange water 61.0% by mass
Production Example 37
■ Production of Black Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 1 8.0% by
mass (by solid content)
• Glycerin (surface tension: 63.3 mN/m) 8.0% by mass
• 1,3-butanediol (surface tension: 37.8 mN/m) 24.0% by
mass
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (I) 1.0% by mass CF 3 CF 2 (CF 2 CF 2 ) H1 - CH 2 CH 2 O(CH 2 CH 2 O) n H • • • ( I )
In the Structural Formula (I), m = 2, and n = 10.
• Ion exchange water 57.0% by mass
Production Example 38
■ Production of Cyan Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 2 6.0% by
mass (by solid content)
• Glycerin (surface tension: 63.3 mN/m) 8.2% by mass
• Triethylene glycol (surface tension^ 45.2 mN/m) 25.6%
by mass
• 2-ethyl-l,3-hexanediol 2.0% by mass
• Nonionic surfactant 1.0% by mass
(Softanol EP7025, available from NIPPON SHOKUBAI
CO., LTD.)
• Ion exchange water 57.2% by mass
Production Example 39
■ Production of Magenta Pigment Ink ■
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 3 8.0% by
mass (by solid content)
• Glycerin (surface tension: 63.3 mN/m) 8.2% by mass
• Triethylene glycol (surface tension: 45.2 mN/m) 25.6%
by mass
• 2-ethyl- l, 3-hexanediol 2.0% by mass
• Nonionic surfactant 1.0% by mass
(Softanol EP7025, available from NIPPON SHOKUBAI
CO., LTD.)
• Ion exchange water 55.2% by mass
Production Example 40
- Production of Yellow Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 4 6.0% by
mass (by solid content)
• Glycerin (surface tension: 63.3 mN/m) 8.2% by mass
• Triethylene glycol (surface tension: 45.2 mN/m) 25.6%
by mass
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Nonionic surfactant 1.0% by mass
(Softanol EP7025, available from NIPPON SHOKUBAI
CO., LTD.)
• Ion exchange water 57.2% by mass
Production Example 41
■ Production of Black Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 1 8.0% by
mass (by solid content)
• Acrylic resin fine particles 5.5% by
mass (by solid content) (Aquabrid 4720, average particle
diameter: 95 nm, available from DAICEL CHEMICAL
INDUSTRIES, LTD.)
• Glycerin (surface tension: 63.3 mN/m) 8.5% by mass
• 2-methyl-2,4-pentandiol (surface tension: 27 mN/m)
17.0% by mass
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Nonionic surfactant 1.0% by mass (Softanol EP7025, available from NIPPON SHOKUBAI CO., LTD.)
• Ion exchange water 58.0% by mass Production Example 42
- Production of Black. Pigment Ink -
An ink composition having the following formulation was prepared, and a 10% aqueous lithium hydroxide solution was added thereto such that the pH value of the ink composition solution was adjusted to 9. Then, the ink composition solution was filtrated through a membrane filter having an average pore diameter of 0.8 μm to thereby prepare a recording ink. < Ink Composition >
• Pigment dispersion of Preparation Example 1 8.0% by mass (by solid content)
• Acrylic resin fine particles 5.5% by mass (by solid content) (Aquabrid 4720, average particle diameter: 95 nm, available from DAICEL CHEMICAL INDUSTRIES, LTD.)
• Glycerin (surface tension: 63.3 mN/m) 8.5% by mass
• 2-methyl-2,4-pentandiol (surface tension: 27 mN/m) 17.0% by mass
• 2-ethyl l,3-hexanediol 2.0% by mass
• Fluorochemical surfactant represented by Structural
Formula (II) 1.0% by mass
RF= CF 2 CF 3 .
• Ion exchange water 58.0% by mass Production Example 43
■ Production of Cyan Pigment Ink - An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was added thereto such that the pH value of the ink composition solution was adjusted to 9. Then, the ink composition solution was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink. < Ink Composition >
• Pigment dispersion of Preparation Example 2 5.0% by
mass (by solid content)
• Acrylic resin fine particles 4.0% by mass (by solid content) (Aquabrid 4720, average particle diameter : 95 nm,
available from DAICEL CHEMICAL INDUSTRIES, LTD.)
• Glycerin (surface tension^ 63.3 mN/m) 7.5% by mass
• 1,3-butanediol (surface tension: 37.8 mN/m) 22.5% by
mass
• 2-ethyl- l,3-hexanediol 2.0% by mass
• Nonionic surfactant 1.0% by mass
(Softanol EP7025, available from NIPPON SHOKUBAI
CO., LTD.)
• Ion exchange water 60.0% by mass
Production Example 44
- Production of Magenta Pigment Ink ■
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 3 8.0% by
mass (by solid content)
• Acrylic resin fine particles 3.2% by mass (by
solid content) (Aquabrid 4720, average particle diameter: 95 nm,
available from DAICEL CHEMICAL INDUSTRIES, LTD.)
• Glycerin (surface tension: 63.3 mN/m) 7.5% by mass
• 1,3-butanediol (surface tension: 37.8 mN/m) 22.5% by
mass
• 2-ethyl- l,3 hexanediol 2.0% by mass
• Nonionic surfactant 1.0% by mass
(Softanol EP7025, available from NIPPON SHOKUBAI
CO., LTD.)
• Ion exchange water 55.8% by mass
Production Example 45
- Production of Yellow Pigment Ink -
An ink composition having the following formulation was
prepared, and a 10% aqueous lithium hydroxide solution was
added thereto such that the pH value of the ink composition
solution was adjusted to 9. Then, the ink composition solution
was filtrated through a membrane filter having an average pore
diameter of 0.8 μm to thereby prepare a recording ink.
< Ink Composition >
• Pigment dispersion of Preparation Example 4 5.0% by
mass (by solid content)
• Acrylic resin fine particles 4.0% by mass (by
solid content) (Aquabrid 4720, average particle diameter- 95 nm,
available from DAICEL CHEMICAL INDUSTRIES, LTD.)
• Glycerin (surface tension: 63.3 mN/m) 7.5% by mass
• 1,3-butanediol (surface tension: 37.8 mN/m) 22.5% by
mass
• 2-ethyl- l,3"hexanediol 2.0% by mass
• Nonionic surfactant 1.0% by mass
(Softanol EP7025, available from NIPPON SHOKUBAI CO., LTD.)
• Ion exchange water 58.0% by mass
Examples 1 to 11 and Comparative Examples 1 to 3
Next, the obtained recording inks of Production Examples 1 to 45 were respectively evaluated as to various properties. Table 2- 1 and Table 2-5 show the evaluation results.
< Volume Average Particle Diameter of Ink > Each of the recording inks was diluted with pure water, and the volume average particle diameter (D 50%) thereof was measured using a particle size distribution measuring apparatus (Microtrack UPA, available from NIKKISO CO., LTD.).
< Ink Viscosity > The ink viscosity of each of the recording inks was measured at a temperature of 25°C using an R-type viscometer (TOKI SANGYO CO., LTD.).
< Ink Surface Tension >
The ink surface tension of each of the recording inks was measured using a static surface tension measuring device (BVP-Z, Kyowa Interface Science Co., Ltd.).
< Color Bleed >
InkJet printers shown in FIGS. 3 to 5 were respectively filled with each of the recording inks of Production Examples 1
to 36. Specifically, individual color recording inks for black, cyan, magenta, and yellow were combined to be a set of four colors as individual ink sets shown in Tables 1- 1 to 1-4, and an
image was printed on an α-matt paper (Hokuetsu Paper' Mills Ltd.) using each of the ink sets.
The obtained images were visually checked to observe the bleeding state of the boundary portion between black ink and color ink.
The transfer amount of pure water to the α-matt paper was measured using a dynamic scanning liquid-absorptoϊneter (DSA, available from KYOWA SEIKO K.K). The transfer amount of pure water to the recording medium for a contact time
of 100 ms was 3.6 mL/m 2 . [Evaluation Criteria] A: No color-bleed was found at the boundary portion between black and color, and the image was sharp and clear.
B: Color-bleed was hardly observed at the boundary portion between black and color, and the image was sharp and
clear. C : A little color-bleed was observed at the boundary
portion between black and color, and the image was slightly inferior in image sharpness.
D: Significant color bleed was observed at the boundary portion between black and color, and the image did not have the
required image sharpness.
< Secondary-Color Beading >
InkJet printers shown in FIGS. 3 to 5 were respectively
filled with each of the recording inks of Production Examples 1
to 36. Specifically, individual color recording inks for black,
cyan, magenta, and yellow were combined to be a set of four
colors as individual ink sets shown in Tables 1- 1 to 1-4, and an
image was printed an an α-matt paper (Hokuetsu Paper Mills
Ltd.) using each of the ink sets.
Secondary-color parts in red, blue, and green of the
obtained image were evaluated as to beading based on the
following criteria.
[Evaluation Criteria]
A: No color unevenness was found at secondary color
parts of the image, and the image was sharp and clear.
B: Color unevenness was hardly observed at secondary
color parts of the image, and the image was sharp and clear.
C : A little color unevenness was observed at secondary
color parts of the image, the image was slightly inferior in image
sharpness.
D: Significant color unevenness was observed at the
boundary portion between black and color, and the image did not
have the required image sharpness.
< Cockling >
InkJet printers shown in FIGS. 3 to 5 were respectively filled with each of the recording inks of Production Examples 1
to 36. Specifically, individual color recording inks for black,
cyan, magenta, and yellow were combined to be a set of four
colors as individual ink sets shown in Tables 1 1 to 1-4, and an
image was printed on an crmatt paper (Hokuetsu Paper Mills
Ltd.) using each of the ink sets.
The printed material was evaluated as to whether or not
cockling occurred, under the following criteria.
[Evaluation Criteria]
A : Neither paper curl nor wavy cockling was found in the
printed material.
B : A little wavy cockling was found in the printed
material, but paper curl was hardly observed.
C: The printed material had wavy cockles as a whole, and
paper curl was observed at the edges thereof.
D: The printed material was curled and further had wavy
cockles as a whole.
< Contact Angle >
The contact angle when each of the recording inks of
Production Examples 1 to 36 were respectively dropped in an
amount of 2 μL on ormatt paper (POD Gloss coat, available from
OJI Paper Co.) was measured from a droplet image taken
through the use of a CCD camera by using a measuring
apparatus (OCA20, Dataphysics Co.) for automatically performing curve fitting to measure a contact angle. The
contact angle was measured right after the start of dribbling of
ink, and the contact angle measured right after the start of the
dribbling was compared with the contact angle measured 100 ms
after the start of the dribbling.
< Ink Discharge Stability >
InkJet printers shown in FIGS. 3 to 5 were respectively
filled with each of the recording inks of Production Examples 1
to 36. Specifically, individual color recording inks for black,
cyan, magenta, and yellow were combined to be a set of four
colors as individual ink sets shown in Tables 1- 1 to 1-4. Then,
200 sheets of paper were consecutively printed at a resolution of
600 dpi, and the respective ink sets were evaluated as to
discharge unevenness and undischarge failure based on the
following criteria.
[Evaluation Criteria]
A: Neither discharge unevenness nor undischarge failure
was found at all.
B: Discharge unevenness and undischarge failures were
observed in not more than 5 nozzles.
C: Discharge unevenness and undischarge failures were
observed in not more than 10 nozzles.
D " Discharge unevenness and undischarge failures were
observed in 11 nozzles or more.
< Ink Storage Stability >
Individual cartridges were filled with each of the
recording inks of Production Examples 1 to 36, and the
cartridges were stored at 50°C for three weeks, and the each of
the recording inks was evaluated as to whether there was a
thickened viscosity or flocculation of ink particles, based on the
following criteria.
[Evaluation Criteria]
A: Neither thickened viscosity nor flocculation was
observed at all.
B: Two percent or less of thickened viscosity and
flocculation were observed.
C: Five percent or less of thickened viscosity and
flocculation were observed.
D: Five percent or more of thickened viscosity and
flocculation were observed.
Table 1-1
Table 1-2
Cλ
Table 1-3
Table 1-4
Table 1-5
Table 2-1
VO
Table 2-2
Table 2-3
Table 2-4
Table 2-5
The recording ink set and the recording ink of the present
invention is excellent in dry property, discharge stability, and
storage stability and allows excellent image formation not only
on regular paper but also on poorly water-absorbable printing
coated paper whose surface is applied with an inorganic pigment,
without substantially causing color bleed, and therefore, the
recording ink set and the recording ink can be suitably used for
ink records, inkjet recording apparatuses, and inkjet recording
method.
The recording method and the inkjet recording apparatus
of the present invention can be applied to various types of
recording based on inkjet recording method and can be
particularly suitably applied to, for example, inkjet recording
printers, facsimiles, copiers, and recording printer/fax/copy
complex machines.