Title of Invention

AN INK-JET RECORDING METHOD AND AN INK-JET RECORDING APPARATUS

Abstract An ink-jet recording ink including a colorant dispersible in water, a water-soluble organic solvent used as a wetting agent, a surfactant, a penetrant, a water-dispersible resin, and water, wherein when 2.5g of the ink is weighed, placed in a glass Petri dish having a diameter of 33mm and stored for 24hr at a temperature of 50OC+0..5OC and a humidity of 12%±5%, the evaporation rate of a solvent (water + water-soluble organic solvent) in the ink is 50% by weight or more, and an ink residue has a viscosity of 20,000mPa-S or greater, and wherein by storing the ink residue for 6hr at a temperature of 23°C±0.5°C and a high humidity of 95%±3% to allow it to absorb moisture, the amount of moisture contained in the ink residue becomes 30% by weight to 40% by weight, in which case the ink residue has a viscosity of less than 500mPas.
Full Text DESCRIPTION
RECORDING INK, INK CARTRIDGE, INK MEDIA SET, INK-JET
RECORDING METHOD AND INK-JET RECORDING
APPARATUS
Technical Field
The present invention relates to a recording ink, an ink
media set, an ink cartridge, an ink-jet recording method, an
ink-jet recording apparatus and an ink recorded matter.
Specifically, the present invention relates to an ink which is
excellent in image quality to plain paper, in adaptability to
high-speed printing, in storage stability and in ejection stability
and is harmless to a maintenance device for an ink ejection
device; an ink cartridge; and a recording method, a recording
apparatus and an ink recorded matter which use the ink.
Background Art
Ink-jet printers have been rapidly becoming commonplace
in recent years for the reasons that printing on plain paper is
enabled, colorization can be facilitated, the ink-jet printers are
compact and inexpensive, running costs are low, and so forth.
The properties generally required for an ink-jet recording ink are
exemplified by color tone, image density, bleeding, etc. for
achieving high image quality; dissolution/dispersion stability,

storage stability, ejection stability, etc. of a colorant in the ink for
achieving reliability", water resistance, light resistance, etc. for
securing storage stability of recorded images; and quick-drying
properties of the ink for achieving a high-speed process.
Accordingly, a variety of proposals have been put forward in
attempts to satisfy these requirements.
As for colorants of ink-jet recording inks, dye inks were
mainly used at an early stage in view of their favorable
color-developing ability, high reliability, etc.", in recent years,
however, note has also been taken of ink compositions using
pigments such as carbon black because recorded images can
thereby have light resistance and water resistance.
Also, for achievement of increase in printing quality and of
high-speed printing, droplets of inks tend to be miniaturized
these days, and thus the hole diameters of nozzles tend to be
reduced as well.
Therefore, it is rather difficult to secure ejection stability
in printers in which pigments are used as colorants and the hole
diameters of nozzles are reduced; and despite many attempts to
balance ejection stability and other properties of inks, sufficient
measures have not been taken, as things stand.
Hitherto, for improvement in the reliability of printers,
inks have been designed such that increase in viscosity can be
restrained as much as possible. For instance, Patent Literature

1 discloses that by not allowing the viscosity and particle
diameter of an ink to increase more than ten-fold and more than
three-fold respectively when the ink is twice as concentrated, the
ink is not restrained by flocculation of pigment from spreading
and thus it is possible to prevent pinholes from arising; however,
it is difficult for this ink to form high-quality images on plain
paper. Patent Literature 2 discloses an ink wherein after
volatile components in the ink have evaporated, the remainder is
a liquid, and the viscosity of the remainder is equal to or less
than ten times the initial viscosity; however, although this ink is
a dye ink and is therefore highly reliable, it is inferior in image
quality on plain paper. Patent Literature 3 discloses an ink
characterized by gelating or solidifying when left to stand at a
temperature of 25°C and a relative humidity of 50% until it does
not substantially change in weight, and becoming a liquid when
left to stand for 24hr at a temperature of 30°C and a relative
humidity of 50%; however, although this ink is a dye ink and is
therefore highly reliable, it is inferior in drying property and
image quality on plain paper. Patent Literature 4 discloses a
method of securing ejection stability by means of an ink using a
sugar alcohol such as maltitol or lactitol; however, the sugar
alcohol instanced is a solid, and it is hardly possible for the sugar
alcohol-based ink to secure ejection stability sufficiently. Patent
Literature 5 discloses an ink wherein the rate of increase in

viscosity (mPa.s/%) caused by evaporation of moisture of an ink is
5.0 or less when, the amount of evaporation of moisture is 30wt%
or less to the total weight of the ink, and the rate of increase in
viscosity attains a value of greater than 50 when the amount of
evaporation of moisture is between 30% by weight and 45% by
weight, and wherein when the rate of increase in viscosity stands
at a value of greater than 50, the average particle diameter of a
colorant in the ink is equal to or less than five times the initial
average particle diameter and is 0.8 µm or less. The ink of
Patent Literature 5 has favorable drying properties and exhibits
adaptability to high-speed printing and high printing quality on
plain paper to be sure, but the ink dries so quickly as to be
inferior in ejection stability, and further, causes troubles such as
breakage of a maintenance device (a wiper cleaner, an ink
sweeping portion, etc.) for an ink ejection device, which stems
from adhesion of waste ink therein. As described above, in order
to secure high-speed printing and high printing quality, it is
necessary to use an ink having a high viscosity; however, it is
difficult for the ink having a high viscosity to secure reliability
and handle ability, as things stand.
[Patent Literature l] Japanese Patent Application
Laid-Open (JP-A) No. 2002-337449
[Patent Literature 2] JP-A No. 2000-95983
[Patent Literature 3] Jp-ANo. 2007-39680

[Patent Literature 4] JP-A No. 2006-348125
[Patent Literature 5] JP-A No. 2006-16412
Disclosure of Invention
The present invention is aimed at solving the problems in
related art and achieving the following object. Specifically, an
object of the present invention is to provide an ink which is
excellent in image quality to plain paper, in adaptability to
high-speed printing, in storage stability and in ejection stability
and is harmless to a maintenance device for an ink ejection
device; an ink cartridge; and a recording method, a recording
apparatus and an ink recorded matter which use the ink.
The ink of the present invention is characterized in that
when 2.5g of the ink is weighed, placed in a glass Petri dish
having a diameter of 33mm and stored for 24hr at a temperature
of 50°C±0.5°C and a humidity of 12%±5%, the evaporation rate of
a solvent with respect to the total weight of the ink is 50% by
weight or more, and an ink residue has a viscosity of 20,000mPa.s
or greater, and also characterized in that by storing the ink
residue for 6hr at a temperature of 23°C±0.5°C and a high
humidity of 95%±3% to allow it to absorb moisture, the amount of
moisture contained in the ink residue becomes 30% by weight to
40% by weight, in which case the ink residue has a viscosity of
less than 500mPa.s. Thus, the ink is thickened by evaporation

of the solvent that occurs before the ink comes into contact with
paper after ejected from a nozzle and at the time when it comes
into contact with the paper, thereby enabling high-quality images
to be formed at high speed on plain paper as well. Also, since
the amount of moisture contained in the ink residue that has
absorbed moisture is 30% by weight to 40% by weight, in which
case the ink residue has a viscosity of less than 500mPa.s, it is
possible to achieve securement of ejection stability, and
prevention of breakage of a maintenance device for an ink
ejection device caused by adhesion of waste ink in the
maintenance device, which are included in the object of the
present invention, and thus long-term reliability can be secured.
An ink used for obtaining an ink having the features of the
present invention is mainly composed of a colorant, a wetting
agent, a surfactant, a penetrant and a water-dispersible resin,
and how these components are combined and the compounding
ratios thereof are important. Further, addition of a particular
pH adjuster as a pigment agglomeration preventing agent makes
it possible to obtain a highly-reliable ink whereby higher-quality
images can be produced.
The following explains one example of a method for
producing "an ink wherein the evaporation rate of a solvent of the
ink with respect to the total weight of the ink is 50% by weight or
more, and an ink residue has a viscosity of 20,000mPa.s or

greater (a state in which, there is almost no fluidity), and wherein
by leaving the ink residue to stand at high humidity to allow it to
absorb moisture, the amount of moisture contained in the ink
residue becomes 30% by weight to 40% by weight, in which case
the ink residue has a viscosity of less than 500mPa.s" mentioned
above. It is useful to prepare an appropriate amount of a
wetting agent A (a polyhydric alcohol that has an equilibrium
moisture content of 30% by weight or more at a temperature of
23°C and a relative humidity of 80%) which has a very high
boiling point and viscosity in comparison with water and an
appropriate amount of a wetting agent B which has a somewhat
high boiling point and viscosity, and to mix water with these
wetting agents (it goes without saying that this method merely
represents one example for facilitating understanding of the
present invention and that the present invention is not limited
thereto). Besides, use of a compound which is high in
coordinating ability, hydrogen-bonding ability and equilibrium
moisture content in the liquid phase is effective, and it is
desirable to consider the amount of the colorant added, the
affinity between the colorant and dispersion medium components,
effects caused by the addition of the surfactant and the penetrant,
and the like.
Meanwhile, as to an ink wherein the evaporation rate of a
solvent of the ink with respect to the total weight of the ink is

50% by weight or more, and an ink residue has a viscosity of
20,000mPas or greater (a state in which there is no fluidity), and
wherein by leaving the ink residue to stand at high humidity to
allow it to absorb moisture, the amount of moisture contained in
the ink residue becomes 30% by weight to 40% by weight, in
which case the ink residue has a viscosity of over 500mPas, the
ink is inferior in ejection stability and may possibly cause, for
example, breakage of a maintenance device for an ink ejection
device, caused by adhesion of waste ink in the maintenance
device.
Furthermore, the ink of the present invention causes less
beading (nonuniformity of density), has superior drying
properties and makes it possible to form high-quality images
suitable for printing image quality, when general-purpose
printing paper (a recording medium with low ink-absorbing
ability, including a support, and a coating layer applied onto at
least one surface of the support, in which the amount of purified
water transferred to the recording medium at a contact period of
100ms measured by a dynamic scanning absorptometer is 2ml/m2
to 35ml/m2 and the amount of purified water transferred to the
recording medium at a contact period of 400ms measured by the
dynamic scanning absorptometer is 3ml/m2 to 40ml/m2) is used.
An ink-jet recording ink including a colorant dispersible in
water, a water-soluble organic solvent used as a wetting agent, a

surfactant, a penetrant, a water-dispersible resin, and water,
wherein when 2.5g of the ink is weighed, placed in a glass Petri
dish having a diameter of 33mm and stored for 24hr at a
temperature of 50°C+0.5°C and a humidity of 12%+5%, the
evaporation rate of a solvent in the ink is 50% by weight or more,
and an ink residue has a viscosity of 20,000mPa.s or greater, and
wherein by storing the ink residue for 6hr at a temperature of
23°C±0.5°C and a high humidity of 95%±3% to allow it to absorb
moisture, the amount of moisture contained in the ink residue
becomes 30% by weight to 40% by weight, in which case the ink
residue has a viscosity of less than 500mPa.s; where the
"evaporation rate of a solvent" (% by weight) is represented by
the expression (1 - amount of ink residue / total weight of
ink)xl00, the solvent includes the water and the water-soluble
organic solvent contained in the ink, and the "amount of moisture
contained in the ink residue" (% by weight) is represented by the
expression (amount of moisture absorbed / total amount of ink
residue that has absorbed moisture)xl00.
The ink-jet recording ink according to , wherein the
wetting agent is at least one of polyhydric alcohols, each of which
has an equilibrium moisture content of 30% by weight or more at
a temperature of 23°C and a relative humidity of 80%.
The ink-jet recording ink according to , wherein the
polyhydric alcohol is selected from the group consisting of

glycerin and 1,3-butanediol.
The ink-jet recording ink according to any one of to
, wherein the colorant dispersible in water is a pigment which
can be stably dispersed in water in the absence of a dispersant by
bonding at least one hydrophilic group to a surface of the colorant
directly or via other atomic group.
The ink-jet recording ink according to any one of to
, wherein the colorant dispersible in water is a polymer fine
particle containing one of a water-insoluble coloring material and
a water-sparingly soluble coloring material.
The ink-jet recording ink according to any one of to
, wherein the colorant dispersible in water contains a pigment,
a pigment dispersant and a polymeric dispersion stabilizer.
The ink-jet recording ink according to any one of to
, wherein the surfactant contains at least one of a
silicone-based surfactant and a fluorine-based surfactant.
The ink-jet recording ink according to , wherein the
silicone-based surfactant contains a polyether-modified
silicone-based surfactant.
The ink-jet recording ink according to , wherein the
fluorine-based surfactant contains at least a compound
represented by the following Structural Formula (I),
CF3CF2(CF2CF2)m-CH2CH2O(CH2CH2O)nH
Structural Formula (I)

where "m" denotes an integer of 0 to 10, and "n" denotes an
integer of 1 to 40.
The ink-jet recording ink according to any one of to
, wherein the penetrant contains at least one of a polyol
compound having 8 to 11 carbon atoms and a glycol ether
compound.
The ink-jet recording ink according to , wherein the
polyol compound having 8 to 11 carbon atoms is at least one of
2-ethyl-l,3-hexanediol and 2,2,4-trimethyl-l,3-pentanediol.
The ink-jet recording ink according to any one of to
, wherein the water-dispersible resin is at least any one of a
polyurethane resin, an acrylic-silicone resin, and a fluorine resin
having a fluoroolefin unit, and the minimum film-forming
temperature of the water-dispersible resin is 30°C or lower.
The ink-jet recording ink according to any one of to
, having a viscosity of 5mPa.s to 20mPa.s at 25°C and a
static surface tension of 35mN/m or less at 25°C.
The ink-jet recording ink according to any one of to
, being at least one selected from a cyan ink, a magenta ink,
a yellow ink and a black ink.
An ink media set including the ink-jet recording ink
according to any one of to , and a recording medium,
wherein the recording medium includes a support, and a coating
layer applied onto at least one surface of the support, the amount

of purified water transferred to the recording medium at a
contact period of 100ms measured by a dynamic scanning
absorptometer is 2ml/m2 to 35ml/m2 and the amount of purified
water transferred to the recording medium at a contact period of
400ms measured by the dynamic scanning absorptometer is
3ml/m2 to 40ml/m2.
An ink cartridge including a container to house the ink-jet
recording ink according to any one of to .
An ink-jet recording method including jetting the ink-jet
recording ink according to any one of to so as to form an
image on a recording medium, by applying a stimulus to the
ink-jet recording ink.
The ink-jet recording method according to , wherein
the stimulus is at least one selected from heat, pressure,
vibration and light.
An ink-jet recording apparatus including an ink jetting
unit configured to jet the ink-jet recording ink according to any
one of to so as to form an image on a recording medium,
by applying a stimulus to the ink-jet recording ink.
The ink-jet recording apparatus according to ,
wherein the stimulus is at least one selected from heat, pressure,
vibration and light.
The ink-jet recording apparatus according to any one of
and , further including an ink-jet head, wherein the

ink-jet head includes nozzles each having a hole diameter of
30µm or less.
An ink recorded matter including an image formed on a
recording medium, using the ink-jet recording ink according to
any one of to .
An ink recorded matter including an image formed on a
recording medium in the ink media set according to , using
the ink-jet recording ink in the ink media set.
As is evident from the following detailed and specific
explanations, the present invention makes it possible to solve the
problems in related art and provide an ink which is excellent in
image quality to plain paper, in adaptability to high-speed
printing, in storage stability and in ejection stability and is
harmless to a maintenance device for an ink ejection device; an
ink cartridge; and a recording method, a recording apparatus and
an ink recorded matter which use the ink.
Specifically, the present invention provides an ink which
makes it possible to obtain an image excellent in quality to plain
paper, particularly in image density and image durability such as
water resistance, light resistance, etc., more particularly in
image density and drying property, which is superior in drying
rate and adaptability to high-speed printing, which is excellent in
storage stability and ejection stability and which is harmless to a
maintenance device for an ink ejection device; and an ink

cartridge, a recording method, a recording apparatus and an ink
recorded matter which use the ink. The present invention
thereby produces extremely superb effects.
Brief Description of Drawings
FIG. 1 is a schematic diagram exemplarily showing an ink
cartridge of the present invention.
FIG. 2 is a schematic diagram exemplarily showing a
modified example of the ink cartridge in FIG. 1.
FIG. 3 is a perspective view exemplarily showing an ink-jet
recording apparatus when a cover provided at an ink cartridge
loading section is open.
FIG. 4 is a cross-sectional view for explaining the overall
structure of the ink-jet recording apparatus shown in FIG. 3.
FIG. 5 is a schematic enlarged view exemplarily showing
an ink-jet head of the present invention.
FIG. 6 is a plan view for explaining main parts of an
example of a subsystem including a maintenance device for an
ejection device in the present invention.
FIG. 7 is a schematic structural diagram of the subsystem
shown in FIG. 6.
FIG. 8 is a diagram for explaining the right side of the
subsystem shown in FIG. 6.
FIG. 9 is a front cross-sectional view of an example of an

idle ejection receiving section in a recording apparatus of the
present invention.
FIG. 10 is a diagram for explaining a side of the example of
the idle ejection receiving section shown in FIG. 9.
Best Mode for Carrying Out the Invention
The recording ink of the present invention includes water,
a colorant, a water-soluble organic solvent (a wetting agent), a
surfactant, a penetrant and a water-dispersible resin, and
further includes other components in accordance with the
necessity.
— Water-soluble Organic Solvent (Wetting Agent) -
The recording ink of the present invention includes at
least one polyhydric alcohol that has an equilibrium moisture
content of 30% by weight or more at a temperature of 23°C and a
relative humidity of 80%. For instance, as described above, it is
desirable for the recording ink to contain a wetting agent A which
has a very high equilibrium moisture content and a very high
boiling point (the wetting agent A has an equilibrium moisture
content of 30% by weight or more at a temperature of 23°C and a
relative humidity of 80% and has a boiling point of 250°C or
higher, with the equilibrium moisture content preferably being
40% by weight or more) and a wetting agent B which has a high
equilibrium moisture content but has a relatively low boiling

point (the wetting agent B has an equilibrium moisture content of
30% by weight or more at a temperature of 23°C and a relative
humidity of 80% and has a boiling point of 140°C to 250°C).
Among polyhydric alcohols, examples of the wetting agent A that
has a boiling point of over 250°C at normal pressure include
1,2,3-butanetriol (bp: 175°C / 33hPa, 38% by weight),
1,2,4-butanetriol (bp: 190°C to 191°C / 24hPa, 41% by weight),
glycerin (bp: 290°C, 49% by weight), diglycerin (bp: 270°C / 20hPa,
38% by weight), triethylene glycol (bp: 285°C, 39% by weight) and
tetraethylene glycol (bp: 324°C to 330°C, 37% by weight); and
examples of the wetting agent B that has a boiling point of 140°C
to 250°C include diethylene glycol (bp: 245°C, 43% by weight) and
1,3-butanediol (bp: 203°C to 204°C, 35% by weight). Each of
these wetting agents A and B is a hygroscopic material which has
an equilibrium moisture content of 30% by weight or more at a
temperature of 23°C and a relative humidity of 80%, with the
wetting agent B higher in evaporating ability than the wetting
agent A. It is particularly desirable that the wetting agent A be
glycerin and the wetting agent B be 1,3-butanediol. When a
combination of the wetting agent A and the wetting agent B is
used, the amount ratio B/A (mass ratio) between the wetting
agent A and the wetting agent B cannot be unequivocally
determined because it substantially depends upon the amount of
an after-mentioned extra wetting agent C and the type and

amount of other additives such, as a penetrant; however, the
amount ratio B/A is preferably in the range of 10/90 to 90/10, for
instance.
The equilibrium moisture content in the present invention
is calculated as follows: a saturated potassium chloride aqueous
solution is used, the temperature and relative humidity in a
desiccator are kept at 23°C±1°C and 80%±3% respectively, Petri
dishes each containing 1g of a water-soluble organic solvent
weighed are stored inside this desiccator, and the saturated
moisture content is calculated.
The saturated moisture content (%) is represented by the
expression-
(amount of moisture absorbed in organic solvent / amount
of organic solvent + moisture absorbed in organic solvent)xl00.
Use of the polyhydric alcohol(s) by 50% by weight or more
to the total content of wetting agents is advantageous in securing
ejection stability and preventing adhesion of waste ink in a
maintenance device for an ink ejection device.
For the recording ink of the present invention, besides the
wetting agents A and B, an extra wetting agent C (typically, the
extra wetting agent C has an equilibrium moisture content of less
than 30% by weight at a temperature of 23°C and a relative
humidity of 80%) may also be used instead of part of the wetting
agents A and B or in addition to the wetting agents A and B in

accordance with, the necessity. Examples of the wetting agent C
include polyhydric alcohols, polyhydric alcohol alkyl ethers,
polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic
compounds, amides, amines, sulfur-containing compounds,
propylene carbonate, ethylene carbonate and other wetting
agents.
Examples of the polyhydric alcohols include dipropylene
glycol (bp: 232°C), 1,5-pentanediol (bp: 242°C),
3-methyl-l,3-butanediol (bp: 203°C), propylene glycol (bp: 187°C),
2-methyl-2,4-pentanediol (bp: 197°C), ethylene glycol (bp: 196°C
to 198°C), tripropylene glycol (bp: 267°C), hexylene glycol (bp:
197°C), polyethylene glycol (viscous liquid to solid),
polypropylene glycol (bp: 187°C), 1,6-hexanediol (bp: 253°C to
260°C), 1,2,6-hexanetriol (bp: 178°C), trimethylol ethane (solid,
mp: 199°C to 201°C) and trimethylol propane (solid, mp: 61°C).
Examples of the polyhydric alcohol alkyl ethers include
ethylene glycol monoethyl ether (bp: 135°C), ethylene glycol
monobutyl ether (bp: 171°C), diethylene glycol monomethyl ether
(bp: 194°C), diethylene glycol monoethyl ether (bp: 197°C),
diethylene glycol monobutyl ether (bp: 231°C), ethylene glycol
mono-2-ethylhexyl ether (bp: 229°C) and propylene glycol
monoethyl ether (bp: 132°C).
Examples of the polyhydric alcohol aryl ethers include
ethylene glycol monophenyl ether (bp: 237°C) and ethylene glycol

monobenzyl ether.
Examples of the nitrogen-containing heterocyclic
compounds include 2-pyrrolidone (bp: 250°C, mp: 25.5°C, 47% by
weight to 48% by weight), N-methyl-2-pyrrolidone (bp: 202°C),
l,3-dimethyl-2-imidazolidinone (bp- 226°C), ε-caprolactam (bp:
270°C) and γ-butyrolactone (bp: 204°C to 205°C).
Examples of the amides include formamide (bp: 210°C),
N-methylformamide (bp: 199°C to 201°C),
N,N-dimethylformamide (bp: 153°C) and N,N-diethylformamide
(bp: 176°C to 177°C).
Examples of the amines include monoethanolamine (bp:
170°C), diethanolamine (bp: 268°C), triethanolamine (bp: 360°C),
N,N-dimethylmonoethanolamine (bp: 139°C),
N-methyldiethanolamine (bp: 243°C), N-methylethanolamine (bp:
159°C), N-phenylethanolamine (bp: 282°C to 287°C) and
3-aminopropyldiethylamine (bp: 169°C).
Examples of the sulfur-containing compounds include
dimethyl sulfoxide (bp: 139°C), sulfolane (bp: 285°C) and
thiodiglycol (bp: 282°C).
The above-mentioned other solid wetting agents are
preferably sugars and the like. Examples of the sugars include
monosaccharides, disaccharides, oligosaccharides (including
trisaccharides and tetrasaccharides) and polysaccharides.
Specific examples thereof include glucose, mannose, fructose,

ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose,
sucrose, trehalose and maltotriose. Here, the polysaccharides
denotes sugars in a broad sense, including substances that are
widespread in the nature, such as α-cyclodextrin and cellulose.
Additionally, examples of derivatives of the sugars include
reducing sugars of the sugars, exemplified by sugar alcohols
(represented by the general formula HOCH2(CHOH)nCH2OH
(where "n" denotes an integer of 2 to 5)); oxidation sugars of the
sugars, exemplified by aldonic acid and uronic acid; amino acid;
and thio acid. Among these, sugar alcohols are preferable, and
specific examples thereof include maltitol and sorbitol.
The mass ratio between a pigment and the wetting agents
greatly affects the ejection stability of ink from a head, and
further, affects prevention of adhesion of waste ink in the
maintenance device for the ink ejection device. If the
compounding amount of the wetting agents is small when there is
a high pigment solid content, evaporation of moisture in the
vicinity of an ink meniscus of a nozzle proceeds, thereby possibly
leading to ejection failure. The amount of the wetting agents
contained in the recording ink is preferably 20% by mass to 50%
by mass, more preferably 20% by mass to 40% by mass. When
the amount is less than 20% by mass, there is a decrease in
ejection stability, and adhesion of waste ink in the maintenance
device becomes serious. When it is more than 50% by mass, the

recording ink becomes inferior in drying property on paper, and
further, the quality of letters/characters on plain paper may
lower.
Also, in order to improve image quality on plain paper, a
wetting agent C1 having a boiling point of less than 240°C and an
equilibrium moisture content of less than 30% (the wetting agent
Cl is any water-soluble organic solvent having an equilibrium
moisture content of less than 30% by weight at a temperature of
23°C and a relative humidity of 80% and having a boiling point of
less than 240°C among the compounds from which the wetting
agent C is selected) is preferably added to constitute an
appropriate proportion as a wetting agent besides the polyhydric
alcohol(s) having an equilibrium moisture content of 30% by
weight or more. It is desirable that the amount of the
water-soluble organic solvent used be less than 50% by weight to
the total amount of wetting agents used, in view of securing
ejection stability and preventing adhesion of waste ink in the
maintenance device for the ink ejection device.
— Colorant —
For the colorant, a pigment is mainly used in view of
weatherability; however, a dye may also be added at the same
time for the purpose of adjusting color tone, provided that the
addition of the dye does not degrade weatherability. Also, the
pigment is not particularly limited and may be suitably selected

in accordance with, the intended use. Examples of the pigment
include pigments for black and pigments for color. Each of these
may be used alone or in combination with two or more.
Examples of inorganic pigments include titanium oxide,
iron oxide, calcium carbonate, barium sulfate, aluminum
hydroxide, barium yellow, cadmium red and chrome yellow and
also include carbon blacks produced by known methods such, as
contact method, furnace method and thermal method.
Examples of organic pigments include azo pigments (such
as azo lakes, insoluble azo pigments, condensed azo pigments and
chelate azo pigments), polycyclic pigments (such as
phthalocyanine pigments, perylene pigments, perinone pigments,
anthraquinone pigments, quinacridone pigments, dioxazine
pigments, indigo pigments, thioindigo pigments, isoindolinone
pigments and quinophthalone pigments), dye chelates (such as
basic dye chelates and acid dye chelates), nitro pigments, nitroso
pigments and aniline black. Among these pigments, particular
preference is given to those which have great affinity with water.
Among the above-mentioned pigments, specific examples of
pigments for black that are ideally used include carbon blacks (C.
I. Pigment Black 7) such as furnace black, lamp black, acetylene
black and channel black; metals such as copper, iron (C. I.
Pigment Black 11) and titanium oxide; and organic pigments such
as aniline black (C. I. Pigment Black 1).

Specific examples of pigments for color that are ideally
used include C. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35,
37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101,
104, 408, 109, 110, 117, 120, 128, 138, 150, 151, 153 and 183; C. I.
Pigment Orange 5, 13, 16, 17, 36, 43 and 51; C. I. Pigment Red 1,
2, 3, 5, 17, 22, 23, 31, 38, 48:2, 48:2 (Permanent Red 2B (Ca)),
48:3, 48:4, 49:1, 52:2, 53:1, 57:1 (Brilliant Carmine 6B), 60:1, 63:1,
63:2, 64:1, 81, 83, 88, 101 (red ochre), 104, 105, 106, 108
(cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146,
149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209 and 219;
C. I. Pigment Violet 1 (rhodamine lake), 3, 5:1, 16, 19, 23 and 38;
C. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3 (phthalocyanine blue),
16, 17:1, 56, 60 and 63; and C. I. Pigment Green 1, 4, 7, 8, 10, 17,
18 and 36.
Particularly favorable embodiments in which the colorant
is a pigment are exemplified by the following first to third
embodiments.
(1) In a first embodiment, the colorant has at least one
hydrophilic group on its surface and contains a pigment which
exhibits water dispersibility in the absence of a dispersant
(hereinafter the pigment is also referred to as "self-dispersible
pigment").
(2) In a second embodiment, the colorant dispersible in water
is a pigment dispersion containing a pigment, a pigment

dispersant and a polymeric dispersion stabilizer, wherein the
polymeric dispersion stabilizer is at least one selected from an
α-olefin-maleic anhydride copolymer represented by the following
Structural Formula (II), a styrene-(meth)acrylic copolymer, a
water-soluble polyurethane resin and a water-soluble polyester
resin.
Structural Formula (II)
In Structural Formula (II), R denotes an alkyl group, and
the alkyl group preferably has 6 to 25 carbon atoms, more
preferably 6 to 22 carbon atoms. "n" denotes a number of 30 to
100.
(3) In a third embodiment, the colorant includes a polymer
emulsion which is a polymer fine particle containing a
water-insoluble or water-sparingly-soluble coloring material (the
polymer emulsion is a water-dispersed material of a polymer fine
particle containing a coloring material).
As to colors of the colorants, examples of the colorants for
black include carbon blacks (C. I. Pigment Black 7) such as
furnace black, lamp black, acetylene black and channel black;
metals such as copper, iron (C. I. Pigment Black 11) and titanium
oxide; and organic pigments such as aniline black (C. I. Pigment
Black 1).

Examples of the colorants for color include C. I. Pigment
Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53,
55, 74, 81, 83, 95, 97, 98, 100, 101, 104, 408, 109, 110, 117, 120,
128, 138, 150, 151, 153 and 183; C. I. Pigment Orange 5, 13, 16,
17, 36, 43 and 51; C. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38,
48:2, 48:2 (Permanent Red 2B (Ca)), 48:3, 48:4, 49:1, 52:2, 53:1,
57:l (Brilliant Carmine 6B), 60:1, 63:1, 63:2, 64:1, 81, 83, 88, 101
(red ochre), 104, 105, 106, 108 (cadmium red), 112, 114, 122
(quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177,
178, 179, 185, 190, 193, 209 and 219; C. I. Pigment Violet 1
(rhodamine lake), 3, 5:1, 16, 19, 23 and 38; C. I. Pigment Blue 1, 2,
15 (phthalocyanine blue), 15:1, 15:2, 15:3 (phthalocyanine blue),
16, 17:1, 56, 60 and 63; and C. I. Pigment Green 1, 4, 7, 8, 10, 17,
18 and 36.
The self-dispersible pigment in the first embodiment has
its surface modified such that at least one hydrophilic group is
bonded to the surface directly or via other atomic group. The
surface of the pigment is modified, for example, by chemically
bonding a particular functional group (a functional group such as
sulfone group or carboxyl group) to the surface or subjecting the
surface to wet oxidation with the use of at least either a
hypohalous acid or a salt thereof. In particular, a form in which
a carboxyl group is bonded to the surface of the pigment and the
pigment is dispersed in water is favorable. Thus, since the

surface of the pigment is modified such that a carboxyl group is
bonded thereto, not only does dispersion stability improve, but
also high printing quality can be obtained and the water
resistance of a recording medium after printing improves further.
Moreover, superior in redispersibility after dried, an ink
containing the self-dispersible pigment in the first embodiment
does not cause clogging even when there is a long hiatus in
printing and an ink moisture content in the vicinity of an ink-jet
head nozzle evaporates, and thus the ink easily enables favorable
printing with a simple cleaning operation.
The volume average particle diameter (D50) of the
self-dispersible pigment in the ink is preferably 0.01µm to
0.16µm.
For instance, as self-dispersible carbon blacks, ones
having ionic properties are favorable, with anionically charged
ones and cationically charged ones being particularly suitable.
Examples of anionic hydrophilic groups include -COOM,
-SO3M, -PO3HM, -PO3M2, -SO2NH2 and -SO2NHCOR (M denotes
a hydrogen atom, an alkali metal, ammonium or an organic
ammonium. R denotes an alkyl group having 1 to 12 carbon
atoms, a phenyl group that may have a substituent, or a naphthyl
group that may have a substituent). Among these, use of
-COOM and -SO3M, each of which is bonded to the surface of a
color pigment, is preferable.

Examples of "M" in the hydrophilic groups include lithium,
sodium and potassium as alkali metals. Examples of the organic
ammonium include monomethylammonium, trimethylammonium,
monoethylammonium, triethylammonium,
monomethanolammonium and trimethanolammonium.
Examples of methods for obtaining an anionically charged color
pigment include a method of oxidizing a color pigment with
sodium hypochlorite, a method utilizing sulfonation and a method
of making the color pigment and diazonium salt react together, as
methods of introducing —COONa onto the surface of the color
pigment.
Preferable examples of cationic hydrophilic groups include
quaternary ammonium groups, more preferably the quaternary
ammonium groups shown below. In the present invention, it is
desirable that any one of these groups be bonded to a carbon
black surface to constitute a coloring material.



The method for producing a cationic self-dispersible
carbon black to which any of the hydrophilic groups is bonded is
not particularly limited and may be suitably selected in
accordance with the intended use. Examples of methods of
bonding the N-ethylpyridyl group represented by the following
structural formula to a carbon black include a method of treating
the carbon black with 3-amino-N"ethylpyridinium bromide.

The hydrophilic groups may be bonded to the surface of the
carbon black via other atomic groups. Examples of the other
atomic groups include alkyl groups having 1 to 12 carbon atoms,

phenyl groups that may have substituents, and naphthyl groups
that may have substituents. Specific examples of the
hydrophilic groups and the other atomic groups bonded to the
surface of the carbon black include —C2H4COOM (M denotes an
alkali metal or quaternary ammonium), — PhSO3M (Ph denotes a
phenyl group. M denotes an alkali metal or quaternary
ammonium) and —C5H10NH3+.
In the second embodiment, the colorant is a pigment
dispersion containing an inorganic pigment, an organic pigment,
a pigment such as a complex pigment, a pigment dispersant and a
polymeric dispersion stabilizer, wherein the polymeric dispersion
stabilizer is at least one selected from an α-olefin-maleic
anhydride copolymer represented by the following Structural
Formula (II), a styrene-(meth)acrylic copolymer, a water-soluble
polyurethane resin and a water-soluble polyester resin.
Structural Formula (II)
In Structural Formula (II), R denotes an alkyl group, and
the alkyl group preferably has 6 to 25 carbon atoms, more
preferably 6 to 22 carbon atoms. "n" denotes a number of 30 to
100.
The polymeric dispersion stabilizer is a material which is
effective in stabilizing the dispersed state of the pigment

dispersion finely dispersed in water in a uniform manner by the
pigment dispersant. The a-olefin-maleic anhydride copolymer
represented by Structural Formula (II), the styrene-(meth)acrylic
copolymer, the water-soluble polyurethane resin and the
water-soluble polyester resin are solids at normal temperature
and are hardly soluble in cold water. However, when dissolved
in an alkaline solution or an alkaline aqueous solution having an
alkalinity value that is equivalent to or greater than the acid
value of the copolymers and the resins (preferably 1.0 to 1.5 times
the acid value), the copolymers and the resins become effective as
a polymeric dispersion stabilizer.
The copolymers and the resins can be easily dissolved in
the alkaline solution or the alkaline aqueous solution by heating
and stirring. When the olefin chain of the a-olefin-maleic
anhydride copolymer is long, it is relatively difficult for them to
dissolve, and so there may be insoluble matter left; nevertheless,
they can be made effective as a polymeric dispersion stabilizer by
removing the insoluble matter with a certain filter or the like.
Examples of the base in the alkaline solution or the
alkaline aqueous solution include hydroxides of alkali metals,
such as sodium hydroxide, potassium hydroxide and lithium
hydroxide; basic substances such as ammonia, triethylamine and
morpholine; and alcohol amines such as triethanolamine,
diethanolamine, N-methyldiethanolanaine,

2-amino-2-ethyl-l,3-propanediol and. choline.
For the α-olefin-maleic anhydride copolymer represented
by Structural Formula (II), a suitably synthesized compound may
be used, or a commercially available product may be used.
Examples of the commercially available product include T-YP112,
T-YP115, T-YP114 and T-YP116 (all of which are produced by
Seiko PMC Corporation).
For the styrene-(meth)acrylic copolymer, a suitably
synthesized compound may be used, or a commercially available
product may be used. Examples of the commercially available
product include JC-05 (produced by Seiko PMC Corporation); and
ARUFON UC-3900, ARUFON UC-3910 and ARUFON UC-3920
(produced by Toagosei Co., Ltd.).
For the water-soluble polyurethane resin, a suitably
synthesized compound may be used, or a commercially available
product may be used. Examples of the commercially available
product include TAKELAC W-5025, TAKELAC W-6010 and
TAKELAC W-5661 (produced by Mitsui Takeda Chemical Co.).
For the water-soluble polyester resin, a suitably
synthesized compound may be used, or a commercially available
product may be used. Examples of the commercially available
product include NICHIGO POLYESTER W-0030, NICHIGO
POLYESTER W-0005S30WO and NICHIGO POLYESTER WR-961
(produced by Nippon Synthetic Chemical Industry Co., Ltd.); and

PESRESIN A-210 and PESRESIN A-520 (produced by Takamatsu
Oil & Fat Co., Ltd.).
The acid value of the polymeric dispersion stabilizer is
preferably 40mgKOH/g to 400mgKOH/g, more preferably
60mgKOH/g to 350mgKOH/g. When the acid value is less than
40mgKOH/g, the dissolving ability of the alkaline solution may
become poor. When it is greater than 400mgKOH/g, the
viscosity of the pigments becomes high, and thus ejection of ink
may easily be degraded or the dispersion stability of the pigment
dispersant may easily decrease.
The mass average molecular weight of the polymeric
dispersion stabilizer is preferably 20,000 or less, more preferably
5,000 to 20,000. When the mass average molecular weight is
less than 5,000, the dispersion stability of the pigment dispersant
may decrease. When it is greater than 20,000, the dissolving
ability of the alkaline solution may become poor or there may be
an increase in viscosity.
The amount of the polymeric dispersion stabilizer
contained is preferably 1 part by mass to 100 parts by mass (as
the solid content equivalent), more preferably 5 parts by mass to
50 parts by mass, in relation to 100 parts by mass of the pigments.
When the amount is less than 1 part by mass, there may be no
effect of dispersion stabilization. When it is greater than 100
parts by mass, the ink viscosity increases, and thus the ability of

the ink to eject from a nozzle may easily be degraded or there may
be economic inferiority.

In the" second embodiment, it is desirable that the colorant
contain a pigment dispersant. For the pigment dispersant,
either an anionic surfactant or a nonionic surfactant having an
HLB value of 10 to 20 is suitable.
Examples of the anionic surfactant include
polyoxyethylene alkyl ether acetates, alkylbenzene sulfonates
(e.g. NH4, Na and Ca), alkyl diphenyl ether disulfonates (e.g. NH4,
Na and Ca), dialkylsuccinate sodium sulfonates,
naphthalenesulfonic acid formalin condensate sodium salts,
polyoxyethylene polycyclic phenylether sulfate salts (e.g. NH4
and Na), laurates, polyoxyethylene alkyl ether sulfate salts and
oleates. Among these, dioctylsulfosuccinate sodium salts and
polyoxyethylene styrenephenylether sulfonate NH4 salts are
particularly preferable.
Examples of the nonionic surfactant having an HLB value
of 10 to 20 include polyoxyethylene alkyl ethers, polyoxyalkylene
alkyl ethers, polyoxyethylene polycyclic phenylethers, sorbitan
fatty esters, polyoxyethylene sorbitan fatty esters,
polyoxyethylene alkylphenyl ethers, polyoxyethylene
alkylamines, polyoxyethylene alkylamides and acetylene glycol.
Among these, polyoxyethylene lauryl ether, polyoxyethylene

β-naphthyl ether, polyoxyethylene sorbitan monooleate and
polyoxyethylene styrenephenylether are particularly preferable.
The amount of the pigment dispersant contained is
preferably 1 part by mass to 100 parts by mass, more preferably
10 parts by mass to 50 parts by mass, in relation to 100 parts by
mass of the pigments. When the amount of the pigment
dispersant contained is small, the pigments cannot be sufficiently
micronized. When it is too large, excessive dispersant
components not adsorbed onto the pigments have an adverse
effect on ink properties, thereby leading to image bleeding and
degradation of water resistance and friction resistance.
The pigment dispersion finely dispersed in water in a
uniform manner by the pigment dispersant can be produced as
follows: the pigment dispersant is dissolved in an aqueous
medium; subsequently, the pigments are added for sufficient
wetness, then the pigment dispersion is stirred at high speed by a
homogenizer and dispersed by a dispersing machine using a ball
such as a bead mill or ball mill, a kneading and dispersing
machine utilizing shearing force such as a roll mill, an ultrasonic
dispersing machine, etc. It should be noted that after such a
kneading and dispersing step, the pigment dispersion often
includes coarse particles, which cause clogging of an ink-jet
nozzle and a supply path. Therefore, it is necessary to remove
particles which are 1µm or greater in diameter, using a filter or a

centrifugal separator.
The average particle diameter (D50) of the pigment
dispersant in the ink is preferably 150nm or less, more preferably
100nm or less. When the average particle diameter (D50) is
greater than 150nm, there is a dramatic decrease in ejection
stability, and thus nozzle clogging and deviation of ink ejection
are liable to arise. When it is 100nm or less, ejection stability
improves, and image color saturation improves as well.
For the water-dispersible colorant of the third embodiment,
use of a polymer emulsion in which polymer fine particles contain
a pigment is favorable as well as use of any of the
above-mentioned pigments. The polymer emulsion in which
polymer fine particles contain a pigment means either a polymer
emulsion in which a pigment is encapsulated in polymer fine
particles or a polymer emulsion in which a pigment is adsorbed
onto surfaces of polymer fine particles. In this case, it is not
that all of the pigment needs to be encapsulated or adsorbed but
that the pigment may be dispersed in the emulsion to such an
extent that the effects of the present invention are not impaired.
Examples of the polymer constituting the polymer emulsion (the
polymer of the polymer fine particles) include vinyl polymers,
polyester polymers and polyurethane polymers. Among these,
particular preference is given to vinyl polymers and polyester
polymers, or more specifically, the polymers disclosed in

Japanese Patent Application Laid-Open (JP-A) Nos. 2000-53897
and 2001-139849.
The amount of the colorant contained in the recording ink
is preferably 2% by mass to 15% by mass, more preferably 3% by
mass to 12% by mass, as a solid content. When the amount is
less than 2% by mass, the color-developing ability of the ink and
image density may decrease. When it is greater than 15% by
mass, the ink thickens, and thus the ability of the ink to eject
may degrade, which is unfavorable from an economical viewpoint
as well.
— Surfactant -
For the surfactant, what is preferable is a surfactant
which is low in surface tension and high in penetrability and
leveling ability and does not impair dispersion stability
regardless of the type of the colorant or the combination of the
wetting agents. And for the surfactant, at least one selected
from an anionic surfactant, a nonionic surfactant, a
silicone-based surfactant and a fluorine-based surfactant is
suitable. Among these, a silicone-based surfactant and a
fluorine-based surfactant are particularly preferable.
Each of these surfactants may be used alone or in
combination with two or more.
The fluorine-based surfactant is preferably a
fluorine-substituted compound having 2 to 16 carbon atoms, more

preferably a fluorine-substituted compound having 4 to 16 carbon
atoms. When the fluorine-substituted compound has less than
two carbon atoms, effects of the fluorine may not be obtained.
When it has more than 16 carbon atoms, there may be problems
with ink storage stability, etc.
Examples of the fluorine-based surfactant include
perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic
compounds, perfluoroalkyl phosphoric acid ester compounds,
perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether
polymer compounds having perfluoroalkylether groups in side
chains. Among these, polyoxyalkylene ether polymer compounds
having perfluoroalkylether groups in side chains are particularly
preferable because they have low foaming properties.
Fluorine-based surfactants represented by the following
Structural Formula (III) are ideal.
CF3CF2(CF2CF2)m-CH2CH2O(CH2CH2O)nH
Structural Formula (III)
In Structural Formula (III), "m" denotes an integer of 0 to
10, and "n" denotes an integer of 1 to 40.
Examples of the perfluoroalkyl sulfonic acid compounds
include perfluoroalkyl sulfonic acids and perfluoroalkyl
sulfonates.
Examples of the perfluoroalkyl carboxylic compounds
include perfluoroalkyl carboxylic acids and perfluoroalkyl

carboxylates.
Examples of the perfluoroalkyl phosphoric acid ester
compounds include perfluoroalkyl phosphoric acid esters and
salts of perfluoroalkyl phosphoric acid esters.
Examples of the polyoxyalkylene ether polymer compounds
having perfluoroalkylether groups in side chains include
polyoxyalkylene ether polymers having perfluoroalkylether
groups in side chains, sulfuric acid ester salts of polyoxyalkylene
ether polymers having perfluoroalkylether groups in side chains,
and salts of polyoxyalkylene ether polymers having
perfluoroalkylether groups in side chains.
Examples of counterions for salts in these fluorine-based
surfactants include Li, Na, K, NH4) NH3CH2CH2OH,
NH2(CH2CH2OH)2 and NH(CH2CH2OH)3.
For the fluorine-based surfactants, suitably synthesized
compounds may be used, or commercially available products may
be used.
Examples of the commercially available products include
SURFLON S-111, S-112, S-113, S-121, S-131, S-132, S-141 and
S-145 (all of which are produced by Asahi Glass Co., Ltd.),
FLUORAD FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C,
FC-430 and FC-431 (all of which are produced by Sumitomo 3M
Limited), MEGAFAC F-470, F-1405 and F-474 (all of which are
produced by Dainippon Ink And Chemicals, Incorporated),

ZONYL TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300
and UR (all of which are produced by E. I. du Pont de Nemours
and Company), FT-110, FT-250, FT-251, FT-400S, FT-150 and
FT-400SW (all of which are produced by Neos Company Limited),
and POLYFOX PF-151N (produced by OMNOVA Solutions Inc.).
Among these, FS-300 produced by E. I. du Pont de Nemours and
Company, FT-110, FT-250, FT-251, FT-400S, FT-150 and
FT-400SW produced by Neos Company Limited, and POLYFOX
PF-151N produced by OMNOVA Solutions Inc. are particularly
preferable in that printing quality, particularly color-developing
ability and uniform dying ability to paper, improves remarkably.
Specific examples of the fluorine-based surfactant include
compounds represented by the following structural formulae,
(l) Anionic Fluorine-based Surfactant

In the structural formula, Rf denotes a mixture of
fluorine-containing hydrophobic groups represented by the
following structural formulae. "A" denotes -SO3X, -COOX or
—PO3X (where X is a counter anion, specifically a hydrogen atom,
Li, Na, K, NH4, NH3CH2CH2OH, NH2(CH2CH2OH)2 or
NH(CH2CH2OH)3).


In the structural formula, Rf' denotes a
fluorine-containing group represented by the following structural
formula. X denotes the same as defined above, "n" denotes an
integer of 1 or 2, and "m" denotes 2-n.

In the structural formula, "n" denotes an integer of 3 to 10.

In the structural formula, Rf' and X denote the same as
defined above.
Rf'—SO3x
In the structural formula, Rf and X denote the same as
defined above.
(2) Nonionic Fluorine "based Surfactant

In the structural formula, Rf denotes the same as defined

above, "n" denotes an integer of 5 to 20.

In the structural formula, Rf denotes the same as defined
above, "n" denotes an integer of 1 lo 40.
(3) Ampholytic Fluorine-based Surfactant

In the structural formula, Rf denotes the same as defined
above.
(4) Oligomer-Type Fluorine-based Surfactant

In the structural formula, Rf denotes a
In the structural formula, "n" denotes an integer of 1 to 4.
fluorine-containing group represented by the following structural
formula, "n" denotes an integer of 0 to 10. X denotes the same
as defined above.



In the structural formula, Rf" denotes the same as defined
above. "1" denotes an integer of 0 to 10, "m" denotes an integer
of 0 to 10, and "n" denotes an integer of 0 to 10.
The silicone-based surfactant is not particularly limited
and may be suitably selected in accordance with the intended use,
with preference given to a compound which does not decompose
even at high pH values. Examples thereof include
side-chain-modified polydimethylsiloxane, both-end-modified
polydimethylsiloxane, one-end-modified polydimethylsiloxane
and side-chain-both-end-modified polydimethylsiloxane. Among
these, polyether-modified silicone-based surfactants having
polyoxyethylene groups or polyoxyethylenepolyoxypropylene
groups as modifying groups are particularly preferable because
they exhibit favorable properties as aqueous surfactants.
For such surfactants, suitably synthesized compounds may
be used, or commercially available products may be used.
The commercially available products can be easily
obtained from BYK-Chemie, Shin-Etsu Chemical Co., Ltd. and
Dow Corning Toray Co., Ltd., for instance.
The polyether-modified silicone-based surfactants are not

particularly limited and may be suitably selected in accordance
with, the intended use. Examples thereof include a compound
represented by the following structural formula, that is prepared
by introducing polyalkyleneoxide units into side chains of Si
portions of a dimethylpolysiloxane.

In the structural formula, "m", "n", "a" and "b" each denote
an integer. R and R' each denote an alkyl group or an alkylene
group.
For the polyether-modified silicone-based surfactants,
commercially available products can be used. Examples thereof
include KF-618, KF-642 and KF-643 (all of which are produced by
Shin-Etsu Chemical Co., Ltd.).
Examples of the anionic surfactant include
polyoxyethylene alkyl ether acetates, dodecylbenzene sulfonates,
laurates, and salts of polyoxyethylene alkyl ether sulfates.
Examples of the nonionic surfactant include polyoxyethylene
alkyl ethers, polyoxypropylene polyoxyethylene alkyl ethers,
polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty
esters, polyoxyethylene alkylphenyl ethers, polyoxyethylene

alkylamines and polyoxyethylene alkylamides.
The amount of any of the surfactants contained in the
recording ink is preferably 0.01% by mass to 3.0% by mass, more
preferably 0.5% by mass to 2% by mass.
When the amount is less than 0.01% by mass, the addition
of the surfactant may be ineffective. When it is greater than
3.0% by mass, the ink has more penetrability to a recording
medium than necessary, and thus image density may decrease or
ink strike-through may arise.
— Penetrant —
It is desirable for the recording ink of the present
invention to contain as a penetrant at least a polyol compound
having 8 to 11 carbon atoms, or a glycol ether compound. The
penetrant is different from the wetting agents, and it is not that
the penetrant has no wetting properties. However, having lower
wetting properties than the wetting agents have, the penetrant
can be referred to as a material having nonwetting properties.
Here, the term "nonwetting properties" is defined as follows.
The penetrant preferably has a solubility of 0.2% by mass to 5.0%
by mass in water at 25°C. For the penetrant,
2-ethyM,3-hexanediol (solubility- 4.2% at 25°C) and
2,2,4-trimethyl-l,3-pentanediol (solubility: 2.0% at 25°C) are
particularly suitable.
Other polyol compounds suitable for the penetrant, as

aliphatic diols, are exemplified by
2-ethyl-2-methyl-l,3-propanediol, 3,3-dimethyl-l,2-butanediol,
2,2-diethyl-l,3-propanediol, 2-methyl-2-propyl-l,3-propanediol,
2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol and
5-hexene-l,2-diol.
As for other penetrants able to be additionally used, they
are not particularly limited and may be suitably selected in
accordance with the intended use as long as they dissolve in the
ink and can be adjusted to have desired properties. Examples
thereof include alkyl and allyl ethers of polyhydric alcohols, such
as diethylene glycol monophenyl ether, ethylene glycol
monophenyl ether, ethylene glycol mono allylether, diethylene
glycol monobutyl ether, propylene glycol monobutyl ether and
tetraethylene glycol chlorophenyl ether; and lower alcohols such
as ethanol.
The amount of the penetrant contained in the recording
ink is preferably 0.1% by mass to 4.0% by mass. When the
amount is less than 0.1% by mass, the ink does not have
quick-drying properties and thus image bleeding may arise.
When it is greater than 4.0% by mass, the dispersion stability of
the colorant is impaired, and thus a nozzle becomes easily
clogged; also, the ink has more penetrability to a recording
medium than necessary, and thus image density may decrease or
offset may arise.

- Water-dispersible Resin -
The water-dispersible resin is superior in film-forming
property (image-forming property), has high water repellency,
high water resistance and high weatherability and is useful for
recording images with high water resistance and high density
(high color-developing ability). Examples thereof include
condensed synthetic resins, additional synthetic resins and
natural polymer compounds.
Examples of the condensed synthetic resins include
polyester resins, polyurethane resins, polyepoxy resins,
polyamide resins, polyether resins, poly(meth)acrylic resins,
acrylic-silicone resins and fluorine resins. Examples of the
additional synthetic resins include polyolefin resins, polystyrene
resins, polyvinyl alcohol resins, polyvinyl ester resins,
polyacrylic resins and unsaturated carboxylic resins. Examples
of the natural polymer compounds include celluloses, rosins and
natural rubbers.
Among these, polyurethane resin fine particles,
acrylic-silicone resin fine particles and fluorine resin fine
particles are particularly preferable. Also, each of these
water-dispersible resins can be used in combination with two or
more without any problems.
For the fluorine resins, fluorine resin fine particles having
fluoroolefin units are suitable. Among these,

fluorine-containing vinyl ether resin fine particles composed of
fluoroolefin units and vinyl ether units are particularly
preferable.
The fluoroolefin units are not particularly limited and may
be suitably selected in accordance with the intended use.
Examples thereof include -CF2CF2-, -CF2CF(CF3)- and
-CF2CFCl-.
The vinyl ether units are not particularly limited and may
be suitably selected in accordance with the intended use.
Examples thereof include the compounds represented by the
following structural formulae.


For the fluorine-containing vinyl ether resin fine particles
composed of fluoroolefin units and vinyl ether units, alternate
copolymers are suitable in which the fluoroolefin units and the
vinyl ether units are alternately copolymerized.
For such fluorine resin fine particles, suitably synthesized

compounds may be used, or commercially available products may
be used. Examples of the commercially available products
include FLUONATE FEM-500, FEM-600, DICGUARD F-52S, F-90,
F-90M, F-90N and AQUAFURAN TE-5A produced by Dainippon
Ink And Chemicals, Incorporated; and LUMIFLON FE4300,
FE4500, FE4400, ASAHIGUARD AG-7105, AG-950, AG-7600,
AG-7000 and AG-1100 produced by Asahi Glass Co., Ltd.
The water-dispersible resin may be used as a homopolymer
or may be subjected to copolymerization and used as a composite
resin; and any one of a single-phase emulsion, a core-shell
emulsion and a power feed emulsion can be used therefor.
For the water-dispersible resin, what can be used is a resin
in which the resin itself has a hydrophilic group and
self-dispersibility, or a resin in which the resin itself does not
have dispersibility, but a surfactant or a resin having a
hydrophilic group gives dispersibility. Among such resins,
ionomers of polyester resins and polyurethane resins, and
emulsions of resin particles obtained by emulsion polymerization
and suspension polymerization of unsaturated monomers are
ideal. In the case of emulsion polymerization of an unsaturated
monomer, since a resin emulsion is obtained by a reaction using
water to which the unsaturated monomer, a polymerization
initiator, a surfactant, a chain transfer agent, a chelator, a pH
adjuster and the like have been added, it is easily possible to

obtain a water-dispersible resin and change the resinous
structure, and thus desired properties can be easily created.
Examples of the unsaturated monomers include
unsaturated carboxylic acids, monofunctional or multifunctional
(meth)acrylic acid ester monomers, (meth)acrylic acid amide
monomers, aromatic vinyl monomers, vinyl cyano compound
monomers, vinyl monomers, allyl compound monomers, olefin
monomers, diene monomers and oligomers having unsaturated
carbon. Each of these may be used alone or in combination. It
is possible to improve properties flexibly by combining these
monomers together, and it is also possible to improve the
characteristics of the resin by producing polymerization reaction
or graft reaction with the use of an oligomer-type polymerization
initiator.
Examples of the unsaturated carboxylic acids include
acrylic acid, methacrylic acid, itaconic acid, fumaric acid and
maleic acid.
Examples of the monofunctional (meth)acrylic acid ester
monomers include methyl methacrylate, ethyl methacrylate,
isopropyl methacrylate, n-butyl methacrylate, isobutyl
methacrylate, n-amyl methacrylate, isoamyl methacrylate,
n-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl
methacrylate, decyl methacrylate, dodecyl methacrylate,
octadecyl methacrylate, cyclohexyl methacrylate, phenyl

methacrylate, benzyl methacrylate, glycidyl methacrylate,
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,
dimethylaminoethyl methacrylate, methacryloxyethyltrimethyl
ammonium salts, 3-methacryloxypropyltrimethoxysilane, methyl
acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate,
isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl
acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate,
dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, phenyl
acrylate, benzyl acrylate, glycidyl acrylate, 2-hydroxyethyl
acrylate, 2-hydroxypropyl acrylate, dimethylaminoethyl acrylate
and acryloxyethyltrimethyl ammonium salts.
Examples of the multifunctional (meth)acrylic acid ester
monomers include ethylene glycol dimethacrylate, diethylene
glycol dimethacrylate, triethylene glycol dimethacrylate,
polyethylene glycol dimethacrylate, 1,3-butylene glycol
dimethacrylate, 1,4-butylene glycol dimethacrylate,
1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate,
dipropylene glycol dimethacrylate, polypropylene glycol
dimethacrylate, polybutylene glycol dimethacrylate,
2,2'-bis(4-methacryloxydiethoxyphenyl)propane,
trimethylolpropane trimethacrylate, trimethylolethane
trimethacrylate, polyethylene glycol diacrylate, triethylene
glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene
glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol

diacrylate, 1,9-nonanediol diacrylate, polypropylene glycol
diacrylate, 2,2'-bis(4-acryloxypropyloxyphenyl)propane,
2,2'-bis(4-aeryloxydiethoxyphenyl)propane trimethylolpropane
triacrylate, trimethylolethane triacrylate, tetramethylolmethane
triacrylate, ditrimethylol tetraacrylate, tetramethylolmethane
tetraacrylate, pentaerythritol tetraacrylate and
dipentaerythritol hexaacrylate.
Examples of the (meth)acrylic acid amide monomers
include acrylamide, methacrylamide, N,N-dimethyl acrylamide,
methylenebisacrylamide and
2-acrylamide-2-methylpropanesulfonic acid.
Examples of the aromatic vinyl monomers include styrene,
α-methylstyrene, vinyltoluene, 4-t-butylstyrene, ehlorostyrene,
vinylanisole, vinylnaphthalene and divinylbenzene.
Examples of the vinyl cyano compound monomers include
acrylonitrile and methacrylonitrile.
Examples of the vinyl monomers include vinyl acetate,
vinylidene chloride, vinyl chloride, vinyl ether, vinyl ketone,
vinylpyrrolidone, vinyl sulfonic acid or salts thereof,
vinyltrimethoxysilane and vinyltriethoxysilane.
Examples of the allyl compound monomers include allyl
sulfonic acid or salts thereof, allylamine, allyl chloride,
diallylamine and diallyldimethylammonium salts.
Examples of the olefin monomers include ethylene and

propylene.
Examples of the diene monomers include butadiene and
chloroprene.
Examples of the oligomers having unsaturated carbon
include styrene oligomers having methacryloyl groups,
styrene-acrylonitrile oligomers having methacryloyl groups,
methyl methacrylate oligomers having methacryloyl groups,
dimethylsiloxane oligomers having methacryloyl groups and
polyester oligomers having acryloyl groups.
Since the water-dispersible resin has its molecular chains
broken by dispersion destruction, hydrolysis or the like under
strongly alkaline or acidic conditions, the pH thereof is
preferably 4 to 12, more preferably 6 to 11 and even more
preferably 7 to 9 especially in view of its miscibility with the
water-dispersible colorant.
The average particle diameter (D50) of the
water-dispersible resin is related to the viscosity of dispersion
solution. As to water-dispersible resins having the same
composition, the smaller the average particle diameter is, the
greater the viscosity is per the same solid content. In order to
avoid excessively high ink viscosity when ink has been formed, it
is desirable for the average particle diameter (D50) of the
water-dispersible resin to be 50nm or greater. Also, when the
water-dispersible resin has a particle diameter that reaches up to

several tens of micrometers, particles become larger in size than
a nozzle orifice of the ink-jet head, and thus the water-dispersible
resin is impossible to use. When particles which are smaller in
size than the nozzle orifice but still large in diameter are present
in the ink, the ability of the ink to eject is degraded. Accordingly,
in order to prevent the ink ejection ability from being impaired, it
is desirable for the average particle diameter (D50) to be 200nm or
less, more desirably 150nm or less.
The water-dispersible resin has a function of fixing the
water-dispersible colorant onto paper and preferably forms into a
coating at normal temperature so as to enhance coloring material
fixing properties. For that reason, the minimum film-forming
temperature (MFT) of the water-dispersible resin is preferably
30°C or lower. Also, when the water-dispersible resin has a
glass transition temperature of-40°C or lower, the resin coating
becomes highly viscous, and so printed matter becomes tacky;
therefore, the water-dispersible resin preferably has a glass
transition temperature of —30°C or higher.
The amount of the water-dispersible resin contained in the
recording ink is preferably 1% by mass to 15% by mass, more
preferably 2% by mass to 7% by mass, as a solid content.
Here, the amounts of the colorant, pigment in the colorant,
and the water-dispersible resin contained in the ink as solid
contents can be measured, for example, by separating only the

colorant and the water-dispersible resin from the ink. When a
pigment is used as the colorant, it is possible to measure the ratio
between the colorant and the water-dispersible resin by
evaluating the weight decrease rate according to
thermogravimetric analysis. Also, when the molecular structure
of the colorant is obvious, it is possible in the case of pigment and
dye to determine the amount of the colorant as a solid content by
means of NMR, and it is possible in the case of inorganic pigment,
gold-containing organic pigment and gold-containing dye
contained in heavy-metal atoms and molecular frameworks to
determine the amount of the colorant as a solid content by means
of fluorescent X-ray analysis.
As to the ink of the present invention, the moisture
content is normally 50% by weight or more, and the total amount
of resin and pigment is normally 3% by weight or more. Thus,
the evaporation rate of a solvent is normally 50% by weight to
97% by weight.
— Other Components —
The above-mentioned other components are not
particularly limited and may be suitably selected in accordance
with the necessity. Examples thereof include a pH adjuster, an
antiseptic/antifungal agent, a chelating reagent, an antirust
agent, an antioxidant, a UV absorber, an oxygen absorber and a
light stabilizer.

The pH adjuster is not particularly limited and may be
suitably selected in accordance with the intended use, as long as
it can adjust the pH to the range of 7 to 11 without having an
adverse effect on a recording ink to be prepared. Examples
thereof include alcohol amines, hydroxides of alkali metals,
ammonium hydroxides, phosphonium hydroxides, and carbonates
of alkali metals. When the pH is less than 7 or greater than 11,
the ink-jet head and/or an ink supply unit are/is dissolved by
large amounts, and thus troubles such as degradation or leakage
of the ink and ejection failure may arise.
Examples of the alcohol amines include diethanolamine,
triethanolamine and 2-amino-2-ethyl-l,3-propanediol.
Examples of the hydroxides of alkali metals include
lithium hydroxide, sodium hydroxide and potassium hydroxide.
Examples of the ammonium hydroxides include ammonium
hydroxide, quaternary ammonium hydroxides and quaternary
phosphonium hydroxides.
Examples of the carbonates of alkali metals include
lithium carbonate, sodium carbonate and potassium carbonate.
Examples of the antiseptic/antifungal agent include
sodium dehydroacetate, sodium sorbate, sodium
2-pyridinethiol"l-oxide, sodium benzoate and sodium
pentachlorophenol.
Examples of the chelating reagent include sodium

ethylenediamine tetraacetate, sodium nitrilotriacetate, sodium
hydroxyethylethylenediamine triacetate, sodium
diethylenetriamine pentaacetate and sodium uramil diacetate.
Examples of the antirust agent include acid sulfites,
sodium thiosulfate, ammonium thiodiglycolate,
diisopropylammonium nitrate, pentaerythritol tetranitrate and
dicyclohexylammonium nitrate.
Examples of the antioxidant include phenolic antioxidants
(including hindered phenol antioxidants), amine antioxidants,
sulfur antioxidants and phosphorus antioxidants.
Examples of the phenolic antioxidants (including hindered
phenol antioxidants) include butylated hydroxyanisole,
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-methyphenyl)
propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane,
l,l,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)benz
ene and
tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propio
nate]methane.

Examples of the amine antioxidants 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, butyl
hydroxyanisole, 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)propi
onate] methane and
l,l,3-tris(2-methyl-4-hydroxy-5-tert-butylpbhenyl)butane.
Examples of the sulfur antioxidants include dilauryl
3,3'-thiodipropionate, distearyl thiodipropionate, lauryl stearyl
thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl
β,β'-thiodipropionate, 2-mercaptobenzimidazole and dilauryl
sulfide.
Examples of the phosphorus antioxidants include
triphenyl phosphite, octadecyl phosphite, triisodecyl phosphite,
trilauryl trithiophosphite and trinonylphenyl phosphite.
Examples of the UV absorber include benzophenone UV
absorbers, benzotriazole UV absorbers, salicylate UV absorbers,
cyanoacrylate UV absorbers and nickel complex salt UV
absorbers.
Examples of the benzophenone UV absorbers include

2-hydroxy-4-n-octoxybenzophenone,
2-hydroxy-4-n-dodecyloxybenzophenone,
2,4-dihydroxybenzophenone, 2-hydroxy4-methoxybenzophenone
and 2,2',4,4'-tetrahydroxybenzophenone.
Examples of the benzotriazole UV absorbers include
2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole,
2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole and
2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazol
e.
Examples of the salicylate UV absorbers include phenyl
salicylate, p-tert-butylphenyl salicylate and p-octylphenyl
salicylate.
Examples of the cyanoacrylate UV absorbers include
ethyl-2-cyano-3,3'-diphenyl acrylate,
methyl-2-cyano-3-methyl-3-(p-methoxyphenyl) acrylate and
butyl-2-cyano-3-methyl-3-(p-methoxyphenyl) acrylate.
Examples of the nickel complex salt UV absorbers include
nickel bis(octylphenyl) sulfide,
2,2'-thiobis(4-tert-octylphelate)-n-butylamine nickel (II),
2,2'-thiobis(4-tert-octylphelate)-2-ethylhexylamine nickel (II)
and 2,2'-thiobis(4-tert-octylphelate) triethanolamine nickel (II).
The recording ink of the present invention is produced by
dispersing or dissolving in an aqueous medium a colorant, a

water-soluble organic solvent (a wetting agent), a surfactant, a
penetrant, a water-dispersible resin and water, with the addition
of other components in accordance with the necessity, and
stirring and mixing the ingredients if need be. The dispersion
can be carried out, for example, by a sand mill, a homogenizer, a
ball mill, a paint shaker, an ultrasonic dispersing machine, etc.,
and the stirring and mixing can be carried out, for example, by an
ordinary stirrer using stirring blades, a magnetic stirrer, a
high-speed dispersing machine, etc.
The properties of the recording ink of the present
invention are not particularly limited and may be suitably
selected in accordance with the intended use. For instance, it is
desirable that the viscosity, surface tension and the like of the
recording ink be in the following ranges.
The viscosity of the recording ink at 25°C is preferably
5mPas to 20mPa.s. By making the ink viscosity equal to or
greater than 5mPa.s, it is possible to obtain the effects with
which to increase printing density and the quality of
letters/characters. By making it equal to or less than 20mPa.s,
it is possible to secure ejection stability.
Here, the viscosity can be measured at 25°C, using a
viscometer (RL-500, manufactured by Toki Sangyo Co., Ltd.), for
instance.
The surface tension of the recording ink is preferably

35mN/m or less, more preferably 32mN/m or less, at 25°C. When
the surface tension is greater than 35mN/m, leveling of the ink on
a recording medium hardly takes place, and thus it may take a
longer time for the ink to dry.
The coloring of the recording ink of the present invention
is not particularly limited and may be suitably selected in
accordance with the intended use. For instance, the recording
ink is colored yellow, magenta, cyan or black. When recording is
carried out using an ink set in which two or more of the colors are
used together, it is possible to form a multicolor image, and when
recording is carried out using an ink set in which all the colors
are used together, it is possible to form a full-color image.
The recording ink of the present invention can be suitably
used for printers equipped with ink-jet heads of any type,
including the piezo type in which ink droplets are ejected by
deforming a diaphragm that forms a wall surface of an ink flow
path, with the use of a piezoelectric element as a pressure
generating unit that pressurizes ink in the ink flow path, and
thusly changing the volume of the ink flow path (refer to JP-A No.
02-51734); the thermal type in which bubbles are generated by
heating ink in an ink flow path with the use of an exothermic
resistive element (refer to JP-ANo. 61-59911); and the
electrostatic type in which ink droplets are ejected by placing a
diaphragm and an electrode, which form a wall surface of an ink

flow path, to face each other, then deforming the diaphragm by
electrostatic force generated between the diaphragm and the
electrode, and thusly changing the volume of the ink flow path
(refer to JP-A No. 06-71882).
The recording ink of the present invention can be suitably
used in a variety of fields such as ink-jet recording inks, fountain
pens, ballpoint pens, markers and felt-tip pens, notably in
image-forming apparatuses (printers, etc.) each employing an
ink-jet recording method. For instance, the recording ink can be
used in a printer which has a function of encouraging printing
fixation by heating recording paper and the recording ink to a
temperature of 50°C to 200°C during, before or after printing.
The recording ink can be particularly suitably used in the ink
media set, the ink cartridge, the ink-jet recording method, the
ink-jet recording apparatus and the ink recorded matter of
present invention described below.
(Ink Media Set)
The ink media set of the present invention is a
combination of the recording ink of the present invention and a
recording medium.

The recording medium is not particularly limited and may
be suitably selected in accordance with the intended use.
Suitable examples thereof include plain paper, gloss paper,

special paper, cloth, films, OHP sheets and general-purpose
printing paper.
In order to obtain an exquisite ink recorded matter such as
a printed image, what is used among these is a recording medium
including a support, and a coating layer applied onto at least one
surface of the support, in which the amount of purified water
transferred to the recording medium at a contact period of 100ms
measured by a dynamic scanning absorptometer is 2ml/m2 to
35ml/m2 and the amount of purified water transferred to the
recording medium at a contact period of 400ms measured by the
dynamic scanning absorptometer is 3ml/m2 to 40ml/m2.
The amount of purified water transferred to the recording
medium at a contact period of 100ms measured by the dynamic
scanning absorptometer is preferably 2ml/m2 to 5ml/m2 and the
amount of purified water transferred to the recording medium at
a contact period of 400ms measured by the dynamic scanning
absorptometer is preferably 3ml/m2 to 10ml/m2.
When the amount of the ink and purified water transferred
at the contact period of 100ms is too small, beading
(nonuniformity of density) may easily arise. When it is too large,
the ink dot diameter after recording may become far smaller than
desired.
When the amount of the ink and purified water transferred
at the contact period of 400ms is too small, sufficient drying

properties cannot be obtained, and thus spur marks may easily
appear. When it is too large, the glossiness of an image portion
after dried may easily lower.
Here, the dynamic scanning absorptometer (DSA, Japan
TAPPI Journal, vol. 48, May 1994, pp. 88-92, Shigenori Kuga) is
an apparatus which can precisely measure the amount of liquid
absorbed in a very short period of time. The dynamic scanning
absorptometer automatically conducts the measurement by a
method in which the rate of liquid absorption is directly read on
the basis of the transfer of a meniscus in a capillary, a sample is
shaped like a disc, a liquid absorption head is spirally moved for
scanning on the sample, the scanning rate is automatically
changed in accordance with a preset pattern, and measurement is
repeated according to the required number of points per sample.
A head for supplying liquid to a paper sample is connected to the
capillary via a Teflon (trademark) tube, and the position of the
meniscus in the capillary is automatically read by an optical
sensor. Specifically, the amount of purified water transferred
was measured using a dynamic scanning absorptometer (K350
series, Model D, manufactured by Kyowaseiko Corporation).
The transfer amount at a contact period of 100ms and the
transfer amount at a contact period of 400ms can be calculated by
means of interpolation based upon the measurement values of the
transfer amounts at contact periods close to the above-mentioned

contact periods.
- Support -
The support is not particularly limited and may be
suitably selected in accordance with the intended use.
Examples thereof include paper made mainly from wood fiber,
and sheet-like materials such as unwoven fabrics made mainly
from wood fiber and synthetic fiber.
The paper is not particularly limited and may be suitably
selected from known materials in accordance with the intended
use. For instance, wood pulp or recycled pulp is used therefor.
Examples of the wood pulp include leaf bleached kraft pulp
(LBKP), needle bleached kraft pulp (NBKP), NBSP, LBSP, GP and
TMP.
Examples of the raw material for the recycled pulp include
articles shown in the "Used Paper Standard Quality Specification
List" released by Paper Recycling Promotion Center, such as
high-quality white paper, white paper with lines and marks,
cream-colored paper, card, medium-quality white paper,
low-quality white paper, simili paper, white-colored paper, Kent
paper, white art paper, medium-quality colored paper, low-quality
colored paper, newspaper and magazine. Specific examples
thereof include used paperboards and used papers of the
following papers: printer papers such as uncoated computer paper,
thermosensitive paper and pressure-sensitive paper that are

related to information; OA (office automation) related papers
such as paper for PPC (plain paper copier); coated papers such as
art paper, coated paper, finely coated paper and matte paper; and
uncoated papers such as high-quality paper, high color quality
paper, notebook, letter paper, packing paper, fancy paper,
medium-quality paper, newspaper, woody paper, super wrapping
paper, simili paper, pure white roll paper and milk carton. More
specific examples thereof include chemical pulp paper and
high-yield pulp-containing paper. Each of these may be used
alone or in combination with two or more.
The recycled pulp is generally produced by a combination
of the following four steps.
(1) Defibration: used paper is treated with mechanical force
and chemicals using a pulper and thusly fiberized, and printing
ink is separated from the fiber.
(2) Dust removal: foreign matter (plastic, etc.) and dust
contained in the used paper is removed by a screen, a cleaner or
the like.
(3) Ink removal: the printing ink that has been separated from
the fiber using a surfactant is removed from the system by a
flotation method or washing method.
(4) Bleaching: the whiteness of the fiber is enhanced utilizing
oxidation or reduction.
When the recycled pulp is mixed with other pulp, it is

desirable that the mixture ratio of the recycled pulp in the whole
pulp be 40% or less so as to prevent curl after recording.
For an internally added filler used in the support, a
conventionally known pigment as a white pigment is used, for
instance. Examples of the white pigment 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-based plastic pigments, acrylic plastic pigments,
polyethylene, microcapsules, urea resins and melamine resins.
Each of these may be used alone or in combination with two or
more.
Examples of an internally added sizing agent used in
producing the support include neutral rosin sizing agents used in
neutral papermaking, alkenyl succinic anhydrides (ASA), alkyl
ketene dimers (AKD) and petroleum resin sizing agents. Among
these, neutral rosin sizing agents and alkenyl succinic
anhydrides are particularly suitable. Although any of the alkyl
ketene dimers only needs to be added in small amounts due to its
strong sizing effect, it may be unfavorable in terms of conveyance

at the time of ink-jet recording because the friction coefficient of
a recording paper (medium) surface decreases and the surface
easily becomes slippery.
The thickness of the support is not particularly limited
and may be suitably selected in accordance with the intended use,
with the range of 50µm to 300µm being preferable. The basis
weight of the support is preferably 45g/m2 to 290g/m2.
— Coating Layer —
The coating layer includes a pigment and a binder, and
further includes a surfactant and other components in accordance
with the necessity.
For the pigment, an inorganic pigment or a combination of
an inorganic pigment and an organic pigment can be used.
Examples of the inorganic pigment include kaolin, talc,
heavy calcium carbonate, light calcium carbonate, calcium sulfite,
amorphous silica, titanium white, magnesium carbonate,
titanium dioxide, aluminum hydroxide, calcium hydroxide,
magnesium hydroxide, zinc hydroxide and chlorites. Among
these, kaolin is particularly preferable in that it is superior in
gloss developing property and makes it possible to yield a texture
which approximates that of paper for offset printing.
Examples of the kaolin include delaminated kaolin,
calcined kaolin, and engineered kaolin produced by surface
modification or the like. In view of gloss developing property, it

is desirable that 50% by mass or more of the whole kaolin be
occupied by kaolin having a particle size distribution in which
80% by mass or more of the particles are 2µm or less in diameter.
The amount of the kaolin added is preferably 50 parts by
mass or more in relation to 100 parts by mass of the binder.
When the amount is less than 50 parts by mass, sufficient
effectiveness may not be obtained with respect to glossiness.
Although the maximum value of the amount is not particularly
limited, it is desirable in terms of coating suitability that the
amount be 90 parts by mass or less, in view of the kaolin's fluidity,
especially thickening properties in the presence of high shearing
force.
Examples of the organic pigment include water-soluble
dispersions containing styrene-acrylic copolymer particles,
styrene-butadiene copolymer particles, polystyrene particles,
polyethylene particles, etc. Each of these organic pigments may
be used in combination with two or more.
The amount of the organic pigment added is preferably 2
parts by mass to 20 parts by mass in relation to 100 parts by mass
of the whole pigment of the coating layer. The organic pigment
is superior in gloss developing property and smaller in specific
gravity than an inorganic pigment, thereby making it possible to
obtain a coating layer which is bulky, highly glossy and excellent
in surface coating property. When the amount is less than 2

parts by mass, such effects cannot be obtained. When it is
greater than 20 parts by mass, the fluidity of a coating solution
degrades, which leads to decrease in coating operationality and
which is economically unfavorable as well.
Examples of the form of the organic pigment include dense
type, hollow type and doughnut type. However, in light of a
balance among the gloss developing property, the surface coating
property, and the fluidity of the coating solution, it is desirable
that the average particle diameter (D50) be 0.2µm to 3.0µm, and it
is further desirable to employ a hollow type with a void ratio of
40% or more.
For the binder, an aqueous resin is preferably used.
For the aqueous resin, at least either a water-soluble resin
or a water-dispersible resin can be suitably used. The
water-soluble resin is not particularly limited and may be
suitably selected in accordance with the intended use.
Examples thereof include polyvinyl alcohol and modified products
of polyvinyl alcohol such as anion-modified polyvinyl alcohol,
cation-modified polyvinyl alcohol and acetal-modified polyvinyl
alcohol; polyurethane; polyvinylpyrrolidone and modified
products of polyvinylpyrrolidone such as copolymers of
polyvinylpyrrolidone and vinyl acetate, copolymers of
vinylpyrrolidone and dimethylaminoethyl methacrylate,
copolymers of quaternized vinylpyrrolidone and

dimethylaminoethyl methacrylate and copolymers of
vinylpyrrolidone and methacrylamide propyl trimethyl
ammonium chloride; celluloses such, as carboxymethyl cellulose,
hydroxyethyl cellulose and hydroxypropyl cellulose; modified
products of cellulose such as cationated hydroxyethyl cellulose;
synthetic resins such as polyester, polyacrylic acid (ester),
melamine resins, modified products thereof, and copolymers of
polyester and polyurethane; and poly(meth)acrylic acid,
poly(meth)acrylamide, oxidized starch, phosphoric acid-esterified
starch, self-modifying starch, cationated starch, various types of
modified starch, polyethylene oxide, sodium polyacrylate and
sodium alginate. Each of these may be used alone or in
combination with two or more.
Among these, polyvinyl alcohol, cation-modified polyvinyl
alcohol, acetal-modified polyvinyl alcohol, polyester,
polyurethane, copolymers of polyester and polyurethane, and the
like are particularly preferable in terms of ink absorption.
The water-dispersible resin is not particularly limited and
may he suitably selected in accordance with the intended use.
Examples thereof include polyvinyl acetate, ethylene-vinyl
acetate copolymers, polystyrene, styrene-(meth)acrylic acid ester
copolymers, (meth)acrylic acid ester polymers, vinyl
acetate-(meth) acrylic acid (ester) copolymers, styrene-butadiene
copolymers, ethylene-propylene copolymers, polyvinyl ethers and

silicone-acrylic copolymers. Also, the water-dispersible resin
may contain a crosslinking agent such as methylolated melamine,
methylolated urea, methylolated hydroxypropylene urea or
isocyanate or may be a copolymer with self-crosslinking ability
that includes N-methylolacrylamide or other unit. A plurality of
these aqueous resins can be used at the same time.
The amount of the aqueous resin added is preferably 2
parts by mass to 100 parts by mass, more preferably 3 parts by
mass to 50 parts by mass, in relation to 100 parts by mass of the
pigment. The amount of the aqueous resin added is determined
such that the liquid absorption properties of the recording
medium are within a desired range.
When a water-dispersible colorant is used as the colorant,
a cationic organic compound is not necessarily required for the
coating layer, and a cationic organic compound mixed into the
coating layer is not particularly limited and may be suitably
selected in accordance with the intended use. Examples of the
cationic organic compound mixed into the coating layer include
monomers, oligomers and polymers of primary to tertiary amines
and quaternary ammonium salts, that form insoluble salts by
reacting with functional groups such as sulfonic acid group,
carboxyl group and amino group in direct dye or acid dye present
in water-soluble ink. Among these, oligomers and polymers are
preferable.

Examples of the cationic organic compound include
dimethylamine-epichlorhydrin polycondensates,
dimethylamine-ammonia-epichlorhydrin condensates,
poly(trimethylaminoethyl methacrylate - methylsulfate),
diallylamine hydrochloride-acrylamide copolymers,
poly(diallylamine hydrochloride-sulfur dioxide), polyallylamine
hydrochloride, poly(allylamine hydrochloride-diallylamine
hydrochloride), acrylamide-diallylamine copolymers,
polyvinylamine copolymers, dicyandiamide,
dicyandiamide-ammonium chloride-urea-formaldehyde
condensates, polyalkylene polyamine-dicyandiamide ammonium
salt condensates, dimethyldiallylammonium chloride,
polydiallylmethylamine hydro chloride,
poly(diallyldimethylammonium chloride),
poly(diallyldimethylammonium chloride-sulfur dioxide),
poly(diallyldimethylammonium chloride-diallylamine
hydrochloride derivatives),
acrylamide-diallyldimethylammonium chloride copolymers,
acrylate-acrylamide-diallylamine hydrochloride copolymers,
polyethylenimine, ethylenimine derivatives such as acrylamine
polymers, and modified products of polyethylenimine alkylene
oxides. Each of these may he used alone or in combination with
two or more.
Among these, any one of low-molecular cationic organic

compounds such as dimethylamine-epichlorhydrin
polycondensates and polyallylamine hydrochloride and any one of
relatively high-molecular cationic organic compounds such as
poly(diallyldimethylammonium chloride) are preferably combined
together. The combination makes it possible to increase image
density more than in the case of independent use and further
reduce feathering.
The cation equivalent of the cationic organic compound
measured in accordance with a colloid titration method (using
potassium polyvinyl sulfate and toluidine blue) is preferably
3meq/g to 8meq/g. When the cation equivalent is in this range, a
favorable result can be obtained with respect to the range of the
amount of the cationic organic compound dried and attached.
Here, in the measurement of the cation equivalent in
accordance with the colloid titration method, the cationic organic
compound is diluted with distilled water such that the solid
content stands at 0.1% by mass, and pH adjustment is not made.
The amount of the cationic organic compound dried and
attached is preferably 0.3g/m2 to 2.0g/m2. When the amount of
the cationic organic compound dried and attached is less than
0.3g/m2, such effects as sufficient increase in image density and
reduction in feathering may not be obtained.
The surfactant included in the coating layer in accordance
with the necessity is not particularly limited and may be suitably


selected in accordance with the intended use, and any one of an
anionic surfactant, a cationic surfactant, an amphoteric
surfactant and a nonionic surfactant can be used therefor.
Among these, a nonionic surfactant is particularly preferable.
By addition of the surfactant, the water resistance of images
improves, image density increases, and bleeding can be reduced.
Examples of the nonionic surfactant include higher alcohol
ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty
acid ethylene oxide adducts, polyhydric alcohol fatty acid ester
ethylene oxide adducts, higher aliphatic amine ethylene oxide
adducts, fatty acid amide ethylene oxide adducts, ethylene oxide
adducts of fats, polypropylene glycol ethylene oxide adducts, fatty
acid esters of glycerol, fatty acid esters of pentaerythritol, fatty
acid esters of sorbitol and sorbitan, fatty acid esters of sucrose,
alkyl ethers of polyhydric alcohols, and fatty acid amides of
alkanolamines. Each of these may be used alone or in
combination with two or more.
The polyhydric alcohols are not particularly limited and
may be suitably selected in accordance with the intended use.
Examples thereof include glycerol, trimethylolpropane,
pentaerythrite, sorbitol and sucrose. As to the ethylene oxide
adducts, ones in which an alkylene oxide, for example propylene
oxide or butylene oxide, is substituted for part of ethylene oxide
to such an extent that their water solubility can be maintained

are also effective. The substitution ratio is preferably 50% or
less. The HLB (hydrophile-lipophile balance) of the nonionic
surfactant is preferably 4 to 15, more preferably 7 to 13.
The amount of the surfactant added is preferably 0 parts
by mass to 10 parts by mass, more preferably 0.1 parts by mass to
1.0 part by mass, in relation to 100 parts by mass of the cationic
organic compound.
Further, other components may be added to the coating
layer in accordance with the necessity, to such an extent that the
object and effects of the present invention are not impaired.
Examples of the other components include additives such as
alumina powder, a pH adjuster, an antiseptic agent and an
antioxidant.
The method for forming the coating layer is not
particularly limited and may be suitably selected in accordance
with the intended use. For instance, a method in which the
support is impregnated or coated with a coating layer solution
can be employed. The method of impregnating or coating the
support with the coating layer solution is not particularly limited
and may be suitably selected in accordance with the intended use.
For instance, the impregnation or the coating can be carried out
using a coating machine such as a conventional size press, gate
roll size press, film transfer size press, blade coater, rod coater,
air knife coater, curtain coater or the like. Also, in view of cost,

the support may be impregnated or coated with the coating layer
solution using a conventional size press, gate roll size press, film
transfer size press, etc. installed in a papermaking machine and
may be finished using an on-machine coater.
The amount of the coating layer solution applied is not
particularly limited and may be suitably selected in accordance
with the intended use. It is preferably 0.5g/m2 to 20g/m2, more
preferably 1g/m2 to 15g/m2, as a solid content.
If necessary, the coating layer solution may be dried after
the impregnation or the coating, in which case the drying
temperature is not particularly limited and may be suitably
selected in accordance with the intended use, with the range of
approximately 100°C to 250°C being preferable.
The recording medium may further include a back layer
formed on the back surface of the support, and other layers
formed between the support and the coating layer and between
the support and the back layer. It is also possible to provide a
protective layer on the coating layer. Each of these layers may
be composed of a single layer or a plurality of layers.
For the recording medium, it is possible to use
commercially available general-purpose printing paper, coated
paper for offset printing, coated paper for gravure printing, etc.
besides an ink-jet recording medium.
The commercially available coated paper for printing

denotes coated paper such as cast-coated paper, so-called art
paper (A0 size and A1 size), A2 size coated paper, A3 size coated
paper, B2 size coated paper, lightweight coated paper or finely
coated paper, used for commercial printing or publication
printing, e.g. offset printing or gravure printing.
Specific examples thereof include AURORA COAT
(produced by Nippon Paper Industries Co., Ltd.) and POD GLOSS
COAT (produced by Oji Paper Company, Limited).
(Ink Cartridge)
The ink cartridge of the present invention includes a
container to house the recording ink of the present invention, and
further includes other members, etc. suitably selected in
accordance with the necessity.
The container is not particularly limited, and the shape,
structure, size, material and the like thereof may be suitably
selected in accordance with the intended use. Suitable examples
thereof include a container having an ink bag or the like formed
of an aluminum laminated film, resin film, etc.
Next, the ink cartridge will be explained with reference to
FIGS. 1 and 2. Here, FIG. 1 is a schematic diagram exemplarily
showing the ink cartridge of the present invention, and FIG. 2 is
a schematic diagram exemplarily showing a modified example of
the ink cartridge in FIG. 1.
As shown in FIG. 1, the recording ink of the present

invention is supplied, from an ink inlet (242) into an ink bag (241),
and the ink inlet (242) is closed by means of fusion bonding after
air is discharged. When the ink cartridge is used, an ink
ejection outlet (243) made of a rubber member is pricked with a
needle of an ink-jet recording apparatus main body (101) later
described with reference to FIG. 3, and the ink is thus supplied to
the apparatus main body (101).
The ink bag (241) is formed of an air-impermeable packing
member such as an aluminum laminated film. As shown in FIG.
2, this ink bag (241) is normally housed in a plastic cartridge case
(244) and detachably mounted on a variety of ink-jet recording
apparatuses.
The ink cartridge (201) of the present invention houses the
recording ink (ink set) of the present invention and can be
detachably mounted on a variety of ink-jet recording apparatuses.
It is particularly desirable that the ink cartridge (201) be
detachably mounted on the after-mentioned ink-jet recording
apparatus of the present invention.
(Ink-jet Recording Method and Ink-jet Recording Apparatus)
The ink-jet recording method of the present invention
includes at least an ink jetting step, and further includes other
steps suitably selected in accordance with the necessity, such as a
stimulus generating step and a controlling step.
The ink-jet recording apparatus of the present invention

includes at least an ink jetting unit, and further includes other
units suitably selected in accordance with the necessity, such as a
stimulus generating unit and a controlling unit.
The ink-jet recording method of the present invention can
be suitably performed by the ink-jet recording apparatus of the
present invention, and the ink jetting step can be suitably
performed by the ink jetting unit. Also, the other steps can be
suitably performed by the other units.
- Ink Jetting Step and Ink Jetting Unit -
The ink jetting step is a step of jetting the recording ink of
the present invention so as to form an image on a recording
medium, by applying a stimulus (energy) to the recording ink.
The ink jetting unit is a unit configured to jet the
recording ink of the present invention so as to form an image on a
recording medium, by applying a stimulus (energy) to the
recording ink. The ink jetting unit is not particularly limited,
and examples thereof include nozzles for ejecting ink.
In the present invention, at least part of a liquid chamber,
a fluid resistance unit, a diaphragm and a nozzle member of the
ink-jet head is preferably formed of a material containing at least
either silicone or nickel.
Also, the diameter of the ink-jet nozzle is preferably 30µm
or less, more preferably 1µm. to 20µm.
The stimulus (energy) can, for example, be generated by

the stimulus generating unit, and the stimulus is not particularly
limited and may be suitably selected in accordance with the
intended use. Examples thereof include heat (temperature),
pressure, vibration and light. Each of these may be used alone
or in combination with two or more. Among these, heat and
pressure are suitable.
Examples of the stimulus generating unit include heaters,
pressurizers, piezoelectric elements, vibration generators,
ultrasonic oscillators and lights. Specific examples thereof
include a piezoelectric actuator such as a piezoelectric element, a
thermal actuator that uses a thermoelectric conversion element
such as an exothermic resistive element and utilizes phase
change caused by film boiling of a liquid, a shape-memory-alloy
actuator that utilizes metal phase change caused by temperature
change, and an electrostatic actuator that utilizes electrostatic
force.
The aspect of the jetting of the recording ink is not
particularly limited and varies according to the type or the like of
the stimulus. In the case where the stimulus is "heat", there is,
for example, a method in which thermal energy corresponding to
a recording signal is given to the recording ink in a recording
head, using a thermal head or the like, bubbles are generated in
the recording ink by the thermal energy, and the recording ink is
ejected as droplets from nozzle holes of the recording head by the

pressure of the bubbles. Meanwhile, in the case where the
stimulus is "pressure", there is, for example, a method in which
by applying voltage to a piezoelectric element bonded to a site
called a pressure chamber that lies in an ink flow path in a
recording head, the piezoelectric element bends, the volume of
the pressure chamber decreases, and thus the recording ink is
ejected as droplets from nozzle holes of the recording head.
It is desirable that the recording ink droplets jetted be, for
example, 3x10-15m3 to 40xl0-15m3 (3pL to 40pL) in size, 5m/s to
20m/s in ejection velocity, 1kHz or greater in drive frequency and
300dpi or greater in resolution.
The controlling unit is not particularly limited and may be
suitably selected in accordance with the intended use, as long as
it can control operations of the aforementioned units. Examples
thereof include apparatuses such as a sequencer and a computer.
Here, one aspect of performing the ink-jet recording
method of the present invention by a serial-type ink-jet recording
apparatus is explained with reference to the drawings. The
ink-jet recording apparatus in FIG. 3 includes an apparatus main
body (101), a paper feed tray (102) for feeding paper into the
apparatus main body (101), a paper discharge tray (103) for
storing paper which has been fed into the apparatus main body
(101) and on which images have been formed (recorded), and an
ink cartridge loading section (104). An operation unit (105)

composed of operation keys, a display and the like is placed on
the upper surface of the ink cartridge loading section (104). The
ink cartridge loading section (104) has a front cover (245) capable
of opening and closing to attach and detach the ink cartridge
(201).
In the apparatus main body (101), as shown in FIGS. 4 and
5, a carriage (133) is freely slidably held in the main scanning
direction by a guide rod (246), which is a guide member laterally
passed between left and right side plates (not depicted), and a
stay (247); and the carriage (133) is moved for scanning in the
arrow direction in FIG. 5 by a main scanning motor (not
depicted).
A recording head (134) composed of four ink-jet recording
heads which eject recording ink droplets of yellow (Y), cyan (C),
magenta (M) and black (Bk) is installed in the carriage (133) such
that a plurality of ink ejection outlets are aligned in the direction
intersecting the main scanning direction and that the ink droplet
ejection direction faces downward.
For each of the ink-jet recording heads composing the
recording head (134), it is possible to use, for example, a head
provided with any of the following actuators as a
energy-generating unit for ejecting ink: a piezoelectric actuator
such as a piezoelectric element, a thermal actuator that uses a
thermoelectric conversion element such as an exothermic

resistive element and utilizes phase change caused by film
boiling of a liquid, a shape-memory-alloy actuator that utilizes
metal phase change caused by temperature change, and an
electrostatic actuator that utilizes electrostatic force.
Also, the carriage (133) incorporates sub-tanks (135) of
each color for supplying the inks of each color to the recording
head (134). Each sub-tank (135) is supplied and replenished
with the recording ink of the present invention from the ink
cartridge (201) of the present invention loaded into the ink
cartridge loading section (104), via a recording ink supply tube
(not depicted).
Meanwhile, as a paper feed unit for feeding sheets of paper
(142) loaded on a paper loading section (pressure plate) (250) of
the paper feed tray (102), there are provided a half-moon roller
(paper feed roller 143) which feeds the sheets of paper (142) one
by one from the paper loading section (250), and a separation pad
(144) which faces the paper feed roller (143) and is formed of a
material with a large friction coefficient. This separation pad
(144) is biased toward the paper feed roller (143) side.
As a conveyance unit for conveying the paper (142), which
has been fed from this paper feed unit, under the recording head
(134), there are provided a conveyance belt (l5l) for conveying
the paper (142) by means of electrostatic adsorption; a counter
roller (152) for conveying the paper (142), which is sent from the

paper feed unit via a guide (145), such that the paper (142) is
sandwiched between the counter roller (152) and the conveyance
belt (151); a conveyance guide (153) for making the paper (142),
which is sent upward in the substantially vertical direction,
change its direction by approximately 90° and thusly correspond
with the conveyance belt (151); and an end pressurizing roller
(155) biased toward the conveyance belt (151) side by a pressing
member (154). Also, there is provided a charging roller (156) as
a charging unit for charging the surface of the conveyance belt
(151).
The conveyance belt (151) is an endless belt and is capable
of moving in circles in the belt conveyance direction, passed
between a conveyance roller (157) and a tension roller (158).
The conveyance belt (151) has, for example, a surface layer
serving as a paper adsorbing surface, that is formed of a resinous
material such as an ethylene-tetrafluoroethylene copolymer
(ETFE) having a thickness of approximately 40µm for which
resistance control has not been conducted, and a back layer
(intermediate resistance layer, ground layer) that is formed of the
same material as this surface layer, for which resistance control
has been conducted using carbon. On the back of the conveyance
belt (151), a guide member (161) is placed correspondingly to a
region where printing is carried out by the recording head (134).
Additionally, as a paper discharge unit for discharging the paper

(142) on which images or the like have been recorded by the
recording head (134), there are provided a separation pawl (171)
for separating the paper (142) from the conveyance belt (151), a
paper discharge roller (172) and a paper discharge small roller
(173), with the paper discharge tray (103) being placed below the
paper discharge roller (172).
A double-sided paper feed unit (181) is mounted on a rear
surface portion of the apparatus main body (101) in a freely
detachable manner. The double-sided paper feed unit (181)
takes in the paper (142) returned by rotation of the conveyance
belt (151) in the opposite direction and reverses it, then refeeds it
between the counter roller (152) and the conveyance belt (151).
Additionally, a manual paper feed unit (182) is provided on an
upper surface of the double-sided paper feed unit (181).
In this ink-jet recording apparatus, the sheets of paper
(142) are fed one by one from the paper feed unit, and the paper
(142) fed upward in the substantially vertical direction is guided
by the guide (145) and conveyed between the conveyance belt
(151) and the counter roller (152). Further, the conveyance
direction of the paper (142) is changed by approximately 90°, as
an end of the paper (142) is guided by the conveyance guide (153)
and pressed onto the conveyance belt (151) by the end
pressurizing roller (155).
On this occasion, the conveyance belt (151) is charged by

the charging roller (156), and the paper (142) is electrostatically
adsorbed onto the conveyance belt (151) and thusly conveyed.
Here, by driving the recording head (134) according to an image
signal while moving the carriage (133), ink droplets are ejected
onto the paper (142) having stopped so as to carry out recording
for one line, and after the paper (142) is conveyed by a
predetermined distance, recording for the next line is carried out.
On receipt of a recording completion signal or such a signal as
indicates that the rear end of the paper (142) has reached the
recording region, recording operation is finished, and the paper
(142) is discharged onto the paper discharge tray (103).
Once the amount of recording ink remaining in the
sub-tanks (135) has been detected as too small, a required
amount of recording ink is supplied from the ink cartridge (201)
into the sub-tanks (135).
As to this ink-jet recording apparatus, when recording ink
in the ink cartridge (201) of the present invention has been used
up, it is possible to replace only the ink bag (241) inside the ink
cartridge (201) by dismantling the housing of the ink cartridge
(201). Also, even when the ink cartridge (201) is longitudinally
placed and employs a front-loading structure, it is possible to
supply recording ink stably. Therefore, even when the
apparatus main body (101) is installed with little space over it,
for example when the apparatus main body (101) is stored in a

rack or when an object is placed over the apparatus main body
(101), it is possible to replace the ink cartridge (201) with ease.
Here, a structural example of a subsystem (91) including
the maintenance device for the ejection device according to the
present invention is explained with reference to FIGS. 6 to 8.
FIG. 6 is a plan view for explaining main parts of the subsystem
(91), FIG. 7 is a schematic structural diagram of the subsystem
(91), and FIG. 8 is a diagram for explaining the right side of the
subsystem (91) in FIG. 6.
Two cap holders (112A) and (112B) serving as a cap holding
mechanism, a wiper blade (93) serving as a wiping member
including an elastic body as a cleaning unit, and a carriage lock
(115) are held in a frame (maintenance device frame) (111) of this
subsystem in such a manner as to be able to ascend and descend
(move up and down). Additionally, an idle ejection receiver (94)
is placed between the wiper blade (93) and the cap holder (112A),
and a wiper cleaner (118) serving as a cleaner unit including a
cleaner roller (96) that is a cleaning member for pressing the
wiper blade (93) from outside the frame (111) toward a wiper
cleaner (95), which is a cleaning member for the idle ejection
receiver (94), is oscillatably held to clean the wiper blade (93).
The cap holders (112A) and (112B) (referred to as "cap
holder (112)" when no distinction is made between these) hold two
caps (92a) and (92b) and two caps (92c) and (92d) respectively,

with nozzle surfaces of two recording heads being capped with the
caps (92a) and (92b), and nozzle surfaces of other two recording
heads being capped with the caps (92c) and (92d).
Here, a tubing pump (suction pump) (120) serving as a
suction unit is connected to the cap (92a) held by the cap holder
(112A) on the side closest to the printing region, via a flexible
tube (119), whereas the tubing pump (120) is not connected to the
other caps (92b), (92c) and (92d). Specifically, only the cap (92a)
is designed as a cap for suction (restoration) and moisture
retention (hereinafter simply referred to as "suction cap"),
whereas the other caps (92b), (92c) and (92d) are designed simply
as caps for moisture retention. Accordingly, when a restoration
operation is carried out on a recording head, the recording head
to be restored is selectively moved to a position where it can be
capped with the suction cap (92a).
A cam shaft (121) that is freely rotatably supported by the
frame (111) is placed below these cap holders (112A) and (112B),
and this cam shaft (121) is provided with cap cams (122A) and
(122B) for respectively allowing the cap holders (112A) and
(112B) to ascend and descend, a wiper cam (124) for allowing the
wiper blade (93) to ascend and descend, a carriage lock cam (125)
for allowing the carriage lock (115) to ascend and descend by
means of a carriage lock arm (117), a roller (126) as a rotating
body that is an idle ejection target member to which droplets idly

ejected are applied inside the idle ejection receiver (94), and a
cleaner cam (128) for allowing the wiper cleaner (118) to oscillate.
Here, the cap (92) is made to ascend and descend by the
cap cams (122A) and (122B). The wiper blade (93) is made to
ascend and descend by the wiper cam (124). When the wiper
blade (93) descends, the wiper cleaner (118) advances, and as the
wiper blade (93) descends while sandwiched between the cleaner
roller (96) of the wiper cleaner (118) and the wiper cleaner (95) of
the idle ejection receiver (94), ink that is attached to the wiper
blade (93) is swept into the idle ejection receiver (94).
The carriage lock (115) is biased upward (in the lock
direction) by a compression spring (not depicted), and made to
ascend and descend by means of the carriage lock arm (117)
driven by the carriage lock cam (125).
As for rotation of a motor (131), in order to drive the
tubing pump (120) and the cam shaft (121) rotationally, a motor
gear (132) provided on a motor shaft (131a) engages with a pump
gear (133) provided on a pump shaft (120a) of the tubing pump
(120); an intermediate gear (248) that is integrally formed with
this pump gear (133) engages with an intermediate gear (136)
having a one-way clutch (137), via an intermediate gear (249);
and an intermediate gear (138) that is coaxial with this
intermediate gear (136) engages with a cam gear (140) fixed to
the cam shaft (121), via an intermediate gear (139).

Additionally, an intermediate shaft (141) that is a rotating shaft
for the intermediate gear (138) and for the intermediate gear
(136) having the clutch (137) is rotatably supported by the frame
(111).
The cam shaft (121) is provided with a home position
sensor cam (142) for detecting home positions, a home position
lever (not depicted) is operated by means of a home position
sensor (not depicted) in the subsystem (91) when the cap (92)
reaches the bottom, and thus the sensor is brought into an open
state and detects the home position of the motor (131) (excluding
the pump (120)). When the power is on, the sensor moves up and
down (ascends and descends) regardless of the position of the cap
(92) (the cap holder (112)), does not carry out position detection
until it starts moving, and moves to the bottom by traveling a
predetermined distance after having detected the home position
of the cap (92) (in the midst of ascending). Thereafter, the
carriage moves from side to side and then returns to a capping
position after having carried out position detection, and the
recording head (134) is subjected to capping.
Next, an idle ejection receiving section will be explained
with reference to FIGS. 9 and 10. Note that FIG. 9 is a front
cross-sectional view for explaining an idle ejection receiving
section, and FIG. 10 is a diagram for explaining a side of the idle
ejection receiving section.

An idle ejection receiving section (200) includes the idle
ejection receiver (94); a roller (203), which is an idle ejection
target member, positioned on the lower side of the idle ejection
receiver (94) and provided on the cam shaft (121); sweeping
members (204A) and (204B) constituting a sweeping mechanism
(204) for gathering recording solution attached to the inner
surface of the wiper cleaner (95); and a sweeping member (205)
for sweeping off recording solution attached to the roller (203)
that is a rotating body. A waste solution tank (206) including an
absorber (207) is placed below the idle ejection receiver (94).
Here, as to the sweeping mechanism (204) for gathering
recording solution attached to the inner surface of the wiper
cleaner (95) of the idle ejection receiver (94), the bottoms of the
sweeping members (204A) and (204B) are oscillatably supported
by a pair of support shafts (210) provided at the bottom of a
holder (251), and the sweeping members (204A) and (204B) are
joined together by a joining member (211) with some play allowed
in each.
A pair of pin members (212) and (212) that can be brought
into contact with the sweeping members (204A) and (204B) by
rotation of the roller (203) are provided on a side face of the roller
(203), which serves as a rotating body and is an idle ejection
target member, provided on the cam shaft (121).
As to each of the sweeping members (204A) and (204B), an

end portion (204a) thereof is inclined so as to correspond with the
inclined surface of the wiper cleaner (95). Also, each of the
sweeping members (204A) and (204B) is provided with a convex
portion (204b), which is for reducing the contact area at the time
of oscillation, on the side facing the inner wall surface of the idle
ejection receiver (94).
Due to this configuration, when the wiper blade (93) is
cleaned, recording solution removed from the wiper blade (93) is
attached to the wiper cleaner (95).
Here, when the roller (203) is rotated in the direction of
the arrow E in FIG. 10 by rotation of the cam shaft (121), the pin
members (212) and (212) of the roller (203) come into contact with
the sweeping members (204A) and (204B), and thus the sweeping
members (204A) and (204B) move back and forth in the directions
of the arrows F and G (between the positions indicated by solid
lines and the positions indicated by broken lines) in FIG. 10.
Due to this back-and-forth movement of the sweeping members
(204A) and (204B), the recording solution attached to the wiper
cleaner (95) is gathered (collected) in one or several places on the
end portion (204a) of each of the sweeping members (204A) and
(204B), then a mass of the recording solution enlarges, and the
recording solution flows under its own weight along the inner
wall surface of the idle ejection receiver (94) and falls into the
waste solution tank (206) below.

In other words, in the case where a wiper cleaning
mechanism is employed in which recording solution attached to
the wiper blade (93) is pressed against the wiper cleaner (95) and
thusly removed, simply pressing and moving the wiper blade (93)
results in the recording solution remaining on an end of the wiper
cleaner (95). Especially when the viscosity of the recording
solution used is high, the recording solution remains on an end
portion of the wiper cleaner (95), thereby possibly making it
impossible to remove the recording solution attached to the wiper
blade (93) the next time cleaning is carried out.
Accordingly, even in the case where a high-viscosity
recording solution is used, since the volume of droplets of the
recording solution with respect to the surface in contact with the
wiper cleaner (95) can be increased by collecting (gathering) in
one or several places the recording solution attached to the wiper
cleaner (95), the droplets easily fall (flow) from the surface in
contact with the wiper cleaner (95), which enables the wiper
blade (93) to be subsequently cleaned in a purified state, and thus
the ability to clean the wiper blade (93) improves.
According to an experiment, it was confirmed that when
the viscosity of a recording solution was 5mPas or greater at
25°C, the recording solution was liable to remain on a cleaner end,
and the ability to remove the recording solution from a blade
decreased the next time cleaning was carried out. When the

sweeping members (204A) and (204B) were provided in light of
the foregoing, it was confirmed that the recording solution
effectively flowed downward.
Moreover, the structure of the sweeping mechanism (204)
can be simplified because the sweeping members (204A) and
(204B) are operated by rotation of the roller (203), which is an
idle ejection target member, provided on the cam shaft (121).
Also, since the idle ejection receiver (94) houses the roller
(203), which is an idle ejection target member, rotated by the cam
shaft (121), a mist of idly ejected droplets can be reduced in speed
or attached to the roller (203) and thusly collected. This makes
it possible to prevent the mist of the recording solution from
dispersing.
Since the sweeping member (205) configured to sweep off
recording solution attached to the roller (203) is provided, the
recording solution attached to the roller (203) is swept off by the
sweeping member (205) and falls under its own weight into the
waste solution tank (206) below. As just described, a member
configured to sweep off recording solution attached to the roller
(203) is placed under the roller (203) and over a waste solution
receiver (waste solution tank); by doing so, it becomes possible to
remove the recording solution attached to the roller and dispose
of it as a waste solution by a simple structure and at a low cost.
It should be noted that although the ink-jet recording

method of the present invention has been explained referring to
an example in which it is applied to a serial-type (shuttle-type)
ink-jet recording apparatus where a carriage performs scanning,
the ink-jet recording method of the present invention can also be
applied to line-type ink-jet recording apparatuses provided with
line-type heads.
Also, the ink-jet recording apparatus and the ink-jet
recording method of the present invention can be applied to a
variety of types of recording based upon ink-jet recording systems.
For example, they can be particularly suitably applied to ink-jet
recording printers, facsimile apparatuses, copiers,
printer/fax/copier complex machines, and so forth.
(Ink Recorded Matter)
The ink recorded matter of the present invention is a
recorded matter recorded by the ink-jet recording apparatus and
the ink-jet recording method of the present invention.
The ink recorded matter of the present invention includes
an image formed on a recording medium, using the recording ink
of the present invention.
Alto, the ink recorded matter of the present invention
includes an image formed on a recording medium in the ink media
set of the present invention, using a recording ink in the ink
media set of the present invention.
The recording medium is not particularly limited and may

be suitably selected in. accordance with, the intended use.
Examples thereof include plain paper, gloss paper, special paper,
cloth, films, OHP sheets and general-purpose printing paper.
Each of these may be used alone or in. combination with two or
more.
The ink recorded matter is high in image quality, free of
bleeding and superior in temporal stability and can be suitably
used for a variety of purposes as a material on which,
letters/characters or images of any type are recorded, or the like.
Examples
The following explains Examples of the present invention;
however, it should be noted that the present invention is not
confined to these Examples in any way.
(Preparation Example 1)
- Preparation of Water-soluble Polymeric Compound Aqueous
Solution A —
• α-olefin-maleic anhydride copolymer (T-YP112, olefin chain
(R): 20 to 24 carbon atoms, 190mgKOH/g in acid value, weight
average molecular weight =10,000, produced by Seiko PMC
Corporation) represented by the following Structural Formula
(II)
10.0 parts by mass


In Structural Formula (II), R denotes an alkyl group "n"
denotes an integer of 30 to 100.
• normal LiOH aqueous solution (1.2 times the amount of the
acid value of the α-olefin-maleic anhydride copolymer
represented by Structural Formula (II)) 17.34 parts by mass
• ion-exchange water 72.66 parts by mass
Next, the mixture was heated and stirred with a stirrer to
dissolve the a-olefin-maleic anhydride copolymer represented by
Structural Formula (II), and a tiny amount of insoluble matter
was filtered out using a filter of 5p.m. in average pore diameter to
prepare a water-soluble polymeric compound aqueous solution A.
(Preparation Example 2)
— Preparation of Surface-treated Black Pigment Dispersion
Solution —
Into 3,000ml of 2.5 normal sodium sulfate solution, 90g of
carbon black having a CTAB specific surface area of 150m2/g and
a DBP oil absorption of 100ml/100g was added, then the mixture
was stirred at a temperature of 60°C and a rotational speed of
300rpm and subjected to reaction for 10hr, and the carbon black
was thus oxidized. This reaction solution was filtered, then the
carbon black which had been filtered out was neutralized with a

sodium hydroxide solution and subjected to ultrafiltration.
The carbon black obtained was washed with water, dried
and dispersed into purified water such that the solid content was
30% by mass, the mixture was sufficiently stirred, and a black
pigment dispersion solution was thus obtained. The average
particle diameter (D50) of a pigment dispersion in this black
pigment dispersion solution measured 103nm. Additionally, the
average particle diameter (D50) was measured using a particle
size distribution measuring apparatus (NANOTRAC UPA-EX150,
manufactured by Nikkiso Co., Ltd.).
(Preparation Example 3)
— Preparation of Magenta Pigment-containing Polymer Fine
Particle Dispersion Solution —

Gases inside a 1L flask equipped with a mechanical stirrer,
a thermometer, a nitrogen gas introducing tube, a reflux tube and
a dripping funnel were sufficiently substituted with nitrogen gas,
then 11.2g of styrene, 2.8g of acrylic acid, 12.0g of lauryl
methacrylate, 4.0g of polyethylene glycol methacrylate, 4.0g of
styrene macromer and 0.4g of mercaptoethanol were mixed
together therein, and the temperature was raised to 65°C.
Subsequently, a mixed solution including 100.8g of styrene,
25.2g of acrylic acid, 108.0g of lauryl methacrylate, 36.0g of
polyethylene glycol methacrylate, 60.0g of hydroxyethyl

methacrylate, 36.0g of styrene macromer, 3.6g of
mercaptoethanol, 2.4g of azobismethylvaleronitrile and 18g of
methyl ethyl ketone was kept being applied dropwise into the
flask for 2.5hr. Thereafter, a mixed solution including 0.8g of
azobismethylvaleronitrile and 18g of methyl ethyl ketone was
kept being applied dropwise into the flask for 0.5hr. The
ingredients were aged at 65°G for 1hr, then 0.8g of
azobismethylvaleronitrile was added, and further, the
ingredients were aged for lhr. After reaction had finished, 364g
of methyl ethyl ketone was added into the flask, and 800g of a
polymer solution A having a concentration of 50% by mass was
thus obtained.
Dispersion Solution>
After 28g of the polymer solution A, 42g of C. I. Pigment
Red 122, 13.6g of 1mol/I potassium hydroxide aqueous solution,
20g of methyl ethyl ketone and 13.6g of ion-exchange water had
been sufficiently stirred, they were kneaded using a roll mill.
The paste obtained was put into 200g of purified water and
sufficiently stirred, then the methyl ethyl ketone and the water
were removed by distillation using an evaporator, this dispersion
solution was filtered under pressure using a polyvinylidene
fluoride membrane filter of 5.0µm in average pore diameter to
remove coarse particles, and a magenta pigment-containing

polymer fine particle dispersion solution incorporating a pigment
by 15% by mass and having a solid content of 20% by mass was
thus obtained. The average particle diameter (D50) of polymer
fine particles in the obtained magenta pigment-containing
polymer fine particle dispersion solution measured 127nm.
Additionally, the average particle diameter (D50) was measured
using a particle size distribution measuring apparatus
(NANOTRAC UPA-EX150, manufactured by Nikkiso Co., Ltd.).
(Preparation Example 4)
- Preparation of Cyan Pigment-containing Polymer Fine Particle
Dispersion Solution -
In Preparation Example 4, a cyan pigment-containing
polymer fine particle dispersion solution was prepared similarly
to the one in Preparation Example 3, except that the C. I.
Pigment Red 122 as a pigment was changed to a phthalocyanine
pigment (C. I. Pigment Blue 15:3).
The average particle diameter (D50) of polymer fine
particles in the obtained cyan pigment-containing polymer fine
particle dispersion solution, measured using a particle size
distribution measuring apparatus (NANOTRAC UPA-EX150,
manufactured by Nikkiso Co., Ltd.), was 93nm.
(Preparation Example 5)
- Preparation of Yellow Pigment-containing Polymer Fine
Particle Dispersion Solution -

In Preparation Example 5, a yellow pigment-containing
polymer fine particle dispersion solution was prepared similarly
to the one in Preparation Example 3, except that the C. I.
Pigment Red 122 as a pigment was changed to a monoazo yellow
pigment (C. I. Pigment Yellow 74).
The average particle diameter (D50) of polymer fine
particles in the obtained yellow pigment-containing polymer fine
particle dispersion solution, measured using a particle size
distribution measuring apparatus (NANOTRAC UPA-EX150,
manufactured by Nikkiso Co., Ltd.), was 76nm.
(Preparation Example 6)
— Preparation of Carbon Black Pigment-containing Polymer Fine
Particle Dispersion Solution —
In Preparation Example 6, a carbon black
pigment-containing polymer fine particle dispersion solution was
prepared similarly to the one in Preparation Example 3, except
that the C. I. Pigment Red 122 as a pigment was changed to
carbon black (FW100, produced by Degussa GmbH).
The average particle diameter (D50) of polymer fine
particles in the obtained carbon black pigment-containing
polymer fine particle dispersion solution, measured using a
particle size distribution measuring apparatus (NANOTRAC
UPA-EX150, manufactured by Nikkiso Co., Ltd.), was 104nm.
(Preparation Example 7)

- Preparation of Yellow Pigment Surfactant Dispersion Solution —
• monoazo yellow pigment (C. I. Pigment Yellow 74, produced by
Dainichiseika Color & Chemicals Mfg. Co., Ltd.)
30.0 parts by mass
• polyoxyethylene styrenephenylether (nonionic surfactant,
NOIGEN EA-177, HLB value = 15.7, produced by Dai-ichi
Kogyo Seiyaku Co., Ltd.)
10.0 parts by mass
• ion-exchange water 60.0 parts by mass
Firstly, the surfactant was dissolved in the ion-exchange
water, and the pigment was mixed in such that it was sufficiently
wetted. Then zirconia beads having a diameter of 0.5mm were
supplied to a wet dispersing machine (DYNO-MILL KDL Model A,
manufactured by WAB (Willy A. Bachofen AG)) and dispersed at
2,000rpm for 2hr, and a primary pigment dispersion was thus
obtained.
Secondly, 4.26 parts by mass of a water-soluble
polyurethane resin (TAKELAC W-5661, active ingredient: 35.2%
by mass, acid value: 40mgKOH/g, molecular weight: 18,000,
produced by Mitsui Takeda Chemicals, Inc.) was added as a
water-soluble polymeric compound aqueous solution to the
primary pigment dispersion, the mixture was sufficiently stirred,
and a yellow pigment surfactant dispersion solution was thus
obtained. The average particle diameter (D50) of a pigment

dispersion in the obtained yellow pigment surfactant dispersion
solution measured 62nm. Additionally, the average particle
diameter (D50) was measured using a particle size distribution
measuring apparatus (NANOTRAC UPA-EX150, manufactured by
Nikkiso Co., Ltd.).
(Preparation Example 8)
- Preparation of Magenta Pigment Surfactant Dispersion
Solution —
• quinacridone pigment (C. I. Pigment Red 122, produced by
Dainichiseika Color & Chemicals Mfg. Co., Ltd.)
30.0 parts by mass
• polyoxyethylene p-naphthyl ether (nonionic surfactant,
RT-100, HLB value = 18.5, produced by Takemoto Oil & Fat
Co., Ltd.) 10.0 parts by mass
• ion-exchange water 60.0 parts by mass
Firstly, the surfactant was dissolved in the ion-exchange
water, and the pigment was mixed in such that it was sufficiently
wetted. Then zirconia beads having a diameter of 0.5mm were
supplied to a wet dispersing machine (DYNO-MILL KDL Model A,
manufactured by WAB (Willy A. Bachofen AG)) and dispersed at
2,000rpm for 2hr, and a primary pigment dispersion was thus
obtained.
Secondly, 7.14 parts by mass of a water-soluble
styrene-(meth)acrylic copolymer (JC-05, active ingredient: 21%

by mass, acid valued 170mgKOH/g, weight average molecular
weight: 16,000, produced by Seiko PMC Corporation) was added
to the primary pigment dispersion, the mixture was sufficiently
stirred, and a magenta pigment surfactant dispersion solution
was thus obtained. The average particle diameter (D50) of a
pigment dispersion in the obtained magenta pigment surfactant
dispersion solution measured 83nm. Additionally, the average
particle diameter (D50) was measured using a particle size
distribution measuring apparatus (NANOTRAC UPA-EX150,
manufactured by Nikkiso Co., Ltd.).
(Preparation Example 9)
- Preparation of Cyan Pigment Surfactant Dispersion Solution A
• phthalocyanine pigment (C. I. Pigment Blue 15:3, produced by
Dainichiseika Color & Chemicals Mfg. Co., Ltd.)
30.0 parts by mass
• polypxyethylene styrenephenylether (nonionic surfactant,
NOIGEN EA-177, HLB value = 15.7, produced by Daiichi
Kogyo Seiyaku Co., Ltd.) 10.0 parts by mass
• ion-exchange water 60.0 parts by mass
Firstly, the surfactant was dissolved in the ion-exchange
water, and the pigment was mixed in such that it was sufficiently
wetted. Then zirconia beads having a diameter of 0.5mm were
supplied to a wet dispersing machine (DYNO-MILL KDL Model A,

manufactured by WAB (Willy A. Bachofen AG)) and dispersed at
2,000rpm for 2hr, and a primary pigment dispersion was thus
obtained.
Secondly, 7.51 parts by mass of the water-soluble
polymeric compound aqueous solution A of Preparation Example
1 and 2.51 parts by mass of a water-soluble polyester resin
(NICHIGO POLYESTER W-0030, active ingredient: 29.9% by
mass, acid valued 100mgKOH/g, weight average molecular
weight: 7,000, produced by Nippon Synthetic Chemical Industry
Co., Ltd.) were added to the primary pigment dispersion, the
mixture was sufficiently stirred, and a cyan pigment surfactant
dispersion solution A was thus obtained. The average particle
diameter (D50) of a pigment dispersion in the obtained cyan
pigment surfactant dispersion solution A measured 78nm.
Additionally, the average particle diameter (D50) was measured
using a particle size distribution measuring apparatus
(NANOTRAC UPA-EX150, manufactured by Nikkiso Co., Ltd.).
(Examples 1 to 11 and Comparative Examples 1 to 5)
- Production of Recording Ink -
Each recording ink was produced according to the
following procedure. First of all, water-soluble organic solvents
(wetting agents), a penetrant (or penetrants), a surfactant, an
antifungal agent and water shown in Tables. 1-1 to 3-3 below
were mixed together and then stirred for 1hr so as to be evenly



mixed. A water-dispersible resin (or water-dispersible resins)
was/were added to this mixed solution and the mixture was
stirred for 1hr; subsequently, a pigment dispersion solution and
an antifoaming agent were added, and the mixture was stirred for
lhr. This dispersion solution was filtered under pressure using
a polyvinylidene fluoride membrane filter of 5.0µm in average
pore diameter to remove coarse particles and dust, and each one
of the recording inks of Examples 1 to 11 and Comparative
Examples 1 to 5 was thus produced.
















The word "Rest" used in the rows of "Purified water" in the
Tables above denotes the amount calculated by subtracting the
amounts of the other ingredients from 100.
The symbols, etc. in Tables 1-1 to 3-3 represent the
following compounds, etc.
Fluorine resin emulsion A-' LUMIFLON FE4300, solid
content = 50% by mass, 145nm in average particle diameter,
minimum film-forming temperature (MFT) = 30°C, produced by
Asahi Glass Co., Ltd.
Fluorine resin emulsion B: LUMIFLON FE4500, solid

content = 50% by mass, 136nm in average particle diameter,
minimum film-forming temperature (MFT) = 28°C, produced by
Asahi Glass Co., Ltd.
Acrylic-silicone resin emulsion: POLYSOL ROY6312, solid
content = 37.2% by mass, 171nm in average particle diameter,
minimum film-forming temperature (MFT) = 20°C, produced by
Showa Highpolymer Co., Ltd.
Polyurethane emulsion: HYDRAN APX-101H, solid content
= 45% by mass, 160nm in average particle diameter, minimum
film-forming temperature (MFT) = 20°C, produced by DIC
Corporation
Acrylic resin emulsion: XP8800, solid content
concentration = 45.6% by mass, 68.5nm in average particle
diameter, produced by Seiko PMC Corporation
KF-643: polyether-modified silicone-based compound
(produced by Shin-Etsu Chemical Co., Ltd., ingredient: 100% by
mass)
ZONYL FS-300: polyoxyetnylene perfluoroalkylether
(produced by E. I. du Pont de Nemours and Company, ingredient:
40% by mass)
SOFTANOL EP-7025: polyoxyalkylene alkyl ether
(produced by Nippon Shokubai Co., Ltd., ingredient- 100% by
mass)
Proxel GXL: antifungal agent including

l,2-benzisothiazolin-3"one as a main component (produced by
Avecia Biologies Limited, ingredient: 20% by mass, with
dipropylene glycol contained)
KM-72F: self-emulsifying silicone antifoaming agent
(produced by Silicone Division of Shin-Etsu Chemical Co., Ltd.,
ingredient: 100% by mass)
Next, the recording inks of Examples 1 to 11 and
Comparative Examples 1 to 5 were evaluated in accordance with
the following evaluation methods. The results are shown in
Tables 4 and 5.

The total amount of pigment and resin (emulsion +
water-soluble resin) contained in each recording ink was
calculated.

The viscosity of each ink was measured at 25°C using a
viscometer (RE-80L, produced by Toki Sangyo Co., Ltd.).

The surface tension of each ink was measured at 25°C
using an automatic surface tensiometer (CBVP-Z, produced by
Kyowa Interface Science Co., Ltd.).

[Dry Ink Residue]
In a glass Petri dish having a diameter of 33mm, 2.5g of

each of the recording inks of Examples and Comparative
Examples, measured using a precision electronic scale balance
capable of measuring weight down to four places of decimals, was
placed. Then it was stored for 24hr in an ETAC constant
temperature bath (manufactured by Kusumoto Chemicals, Ltd.)
having a temperature of 50°C±0.5°C and a humidity of 12%±5%.
After the storage, the ink residue was weighed using a precision
electronic scale balance before absorbing moisture, and the
evaporation rate of a solvent was calculated by means of
Equation 1. Subsequently, the viscosity of this ink residue was
measured at 25°C using an RE-550L viscometer (manufactured by
Toki Sangyo Co., Ltd.) cone rotor 3°xR14.
As to the ink of the present invention, as described above,
the moisture content is normally 50% by weight or more, and the
total amount of resin and pigment is normally 3% by weight or
more. Thus, the evaporation rate of a solvent is normally 50%
by weight to 97% by weight.
[Ink Residue after Moisture Absorption]
Subsequently, an ink residue placed in a glass Petri dish
having a diameter of 33mm, which had been produced similarly to
the aforementioned ink residue, was stored for 6hr in an ESPEC
constant temperature bath (produced by ESPEC CORP.) having a
temperature of 23°C±0.5°C and a high humidity of 95%±3%.
After the storage, the ink residue having absorbed moisture was

weighed using a precision electronic scale balance, and the
amount of moisture contained in the ink residue was calculated
by means of Equation 2. Subsequently, the viscosity of this ink
residue was measured at 25°C using an RE-550L viscometer
(manufactured by Toki Sangyo Co., Ltd.) cone rotor 3°xR14.
It goes without saying that when this ink residue has a low
viscosity at 25°C, it has high fluidity and is therefore harmless to
a maintenance device for an ink ejection device.
Equation 1- evaporation rate of solvent (% by weight) = (1 -
amount of ink residue / total weight of ink)x100
where the solvent denotes water and water-soluble organic
solvent in the ink.
Equation 2: amount of moisture contained in ink residue
(% by weight) = (amount of moisture absorbed / total amount of
ink residue that has absorbed moisture)x100
Equation 3: equilibrium moisture content (%) = (amount of
moisture absorbed in organic solvent / amount of organic solvent
+ moisture absorbed in organic solvent)x100
The reason why the testing method of [Dry Ink Residue]
and [Ink Residue after Moisture Absorption] was employed is as
follows. The test of [Dry Ink Residue] makes it possible to judge
ink drying property on plain paper: an ink in which a dry ink
residue has a viscosity of 20,000mPa.s or greater as described in
claim 1 is superior in drying property on plain paper, whereas an

ink in which a dry ink residue has a viscosity of less than
20,000mPa.s is inferior in drying property on plain paper.
Meanwhile, the test of [Ink Residue after Moisture Absorption]
makes it possible to judge ejection stability and waste ink
adhesion in the maintenance device for the ink ejection device: an
ink in which an ink residue has a viscosity of less than 500mPa.s
after moisture absorption as described in claim 1 enables waste
ink adhesion to be notably reduced in the maintenance device for
the ink ejection device, whereas an ink in which an ink residue
has a viscosity of greater than 500mPa.s after moisture
absorption causes waste ink adhesion in many places in the
maintenance device and thus breakage of the maintenance device.
The present invention has been completed by employing the
testing method of [Dry Ink Residue] and [Ink Residue after
Moisture Absorption].
- Preparation I of Printing Evaluation -
In an adjusted environment where the temperature was
28°C+0.5°C and the relative humidity was 15%±5%, the drive
voltage of a piezoelectric element was changed such that the
amount of ink ejected became uniform, using an ink-jet printer
(IPSIO G717, manufactured by Ricoh Company, Ltd.), and
settings were made such that the same amount of ink was
attached onto each recording medium.


A chart to be formed by painting 5% in area of A4 size
paper with a solid image per color, produced using MICROSOFT
WORD 2000, was printed onto sheets of TYPE 6200 (produced by
NBS Ricoh Co., Ltd.) by five sets, each of which consisted of a
succession of 200 charts; and evaluations were carried out based
upon ejection nonuniformity of each nozzle after the printing.
As for the printing mode, "Plain Paper - Standard Speed" mode
was changed to "No Color Correction" mode in user settings for
plain paper by using a driver that accompanied a printer.
[Evaluation Criteria]
A: there was no ejection nonuniformity
B: there was a little ejection nonuniformity
C: there was ejection nonuniformity or there were parts
where no ejection took place
— Preparation II of Printing Evaluation —
In an adjusted environment where the temperature was
23°C±0.5°C and the relative humidity was 50%±5%, the drive
voltage of a piezoelectric element was changed such that the
amount of ink ejected became uniform, using an ink-jet printer
(IPSIO G717, manufactured by Ricoh Company, Ltd.), and
settings were made such that the same amount of ink was
attached onto each recording medium.


A chart including a 64-point character "■", produced using
MICROSOFT WORD 2000, was printed onto sheets of TYPE 6200
(produced by NBS Ricoh Co., Ltd.), and the "■" portions on
printing surfaces were measured for color by means of the
densitometer X-Rite 938 and judged according to the following
evaluation criteria. As for the printing mode, "Plain Paper -
Standard Speed" mode was changed to "No Color Correction"
mode in user settings for plain paper by using a driver that
accompanied a printer.
[Evaluation Criteria]
A: 1.2 or greater with respect to black, 0.8 or greater with
respect to yellow, 1.0 or greater with respect to magenta, 1.0 or
greater with respect to cyan
B: 1.15 or greater and less than 1.2 with respect to black,
0.75 or greater and less than 0.8 with respect to yellow, 0.95 or
greater and less than 1.0 with respect to magenta, 0.95 or greater
and less than 1.0 with respect to cyan
C: less than 1.15 with respect to black, less than 0.75 with
respect to yellow, less than 0.95 with respect to magenta, less
than 0.95 with respect to cyan

A chart was printed onto sheets of TYPE 6200 similarly to
the case of printing density, and "■" portions printed on printing

surfaces were dried for 24hr at a temperature of 23°C and a
relative humidity of 50%. Subsequently, each chart was
immersed for 1min in water having a temperature of 30°C and
then carefully raised so as to undergo drying while standing still,
and judgments were made according to the following evaluation
criteria.
[Evaluation Criteria]
A: there was no color bleeding
B: there was color bleeding
[0201]

A chart was printed onto sheets of TYPE 6200 similarly to
the case of image density, and "■" portions printed on printing
surfaces were dried for 24hr at a temperature of 23°C and a
relative humidity of 50%. These image portions were irradiated
with xenon light approximating to outdoor sunlight at an
irradiance of 0.35W/m2 (340nm) for 24hr in an environment
where the temperature was 70°C, the relative humidity was 50%
and the black panel temperature was 89°C, using
WEATHER-OMETER Ci35AW manufactured by Atlas Material
Testing Technology LLC, and color fading and color change
caused by the irradiation were judged according to the following
evaluation criteria.

[Evaluation Criteria]
A: there was almost no change
B: there was change that could be accepted
C: there were great color fading and color change

A chart was printed onto sheets of TYPE 6200 similarly to
the case of printing density, and filter paper was pressed against
"■" portions printed on printing surfaces immediately after the
printing so as to judge the presence/absence of transfer.
[Evaluation Criteria]
A: there was no transfer smear
B: there was a little transfer smear
C: there was transfer smear

In an adjusted environment where the temperature was
28°C±0.5°C and the relative humidity was 15%±5%, the drive
voltage of a piezoelectric element was changed such that the
amount of ink ejected became uniform, using an ink-jet printer
(IPSIO G717, manufactured by Ricoh Company, Ltd.).
Thereafter, head cleaning operation was continuously conducted
ten times every one hour, and this head cleaning operation was
conducted a total of 100 times in 10hr, then ink adhesion in a
wiper section and a wiper cleaner section of the maintenance
device was judged by visual observation after left to stand for

12hr.
[Evaluation Criteria]
A: there was no ink adhesion
B: there was a little ink adhesion
C: there was ink adhesion



Next, the recording inks of Examples 1 to 4 were used on
the following recording papers (1) to (4) respectively, and image
quality evaluations were carried out in the following manner.

- Recording Paper (1) -
Commercially available paper (product name: AURORA
COAT, basis weight = 104.7g/m2, produced by Nippon Paper
Industries Co., Ltd.)
- Recording Paper (2) -
POD GLOSS COAT 100g/m2 paper, produced by Oji Paper
Company, Limited
- Recording Paper (3) -
Commercially available ink-jet matte coated paper
(product name: SUPER FINE PAPER, produced by Seiko Epson
Corporation)
- Recording Paper (4) -
Transparent polyester film (product name: LUMIRROR
U10, 100µm in thickness, produced by Toray Industries, Inc.)
The amount of purified water transferred was measured in
the following manner, with respect to each of the recording
papers (1) to (4). The results are shown in Table 6.
Scanning Absorptometer>
The absorption curve of purified water was measured
using a dynamic scanning absorptometer (Model: KS350D,
manufactured by Kyowaseiko Corporation), with respect to each
of the recording papers (1) to (4). The absorption curve was
made as a straight line with a fixed inclination by plotting

transfer amount (mL/m2) against the square root of contact
period (ms), and the values of the transfer amount after two
different predetermined periods of time were measured by means
of interpolation.

The recording inks of Examples 1 to 4 were used on the
recording papers (1) to (4) respectively, and image quality
evaluations were carried out in the following manner, using an
ink-jet recording apparatus (IPSIO G7570, manufactured by
Ricoh Company, Ltd.).
(1) Beading (Nonuniformity of density)
The extent of nonuniformity of density at each solid edge
portion obtained was evaluated by visual observation.
Evaluations with ranks were carried out using a classification
sample (rank- 1.0 (poor) to 5.0 (excellent)).
(2) Spur mark
The extent of offset smear that spread from each red solid

portion to each background portion obtained, which was caused
by a spur, was evaluated by visual observation. Evaluations
with ranks were carried out according to the following criteria.
Rank 1- clearly visible
Rank 2- barely visible
Rank 3- none whatsoever
(3) Glossiness
The 60-degree glossiness of each cyan solid portion
obtained was measured using a glossmeter (4501, manufactured
by BYK-Gardner GmbH).

[1] The glossiness of the recording paper (4) could not be
measured because it did not dry.
Industrial Applicability
An object of the present invention is to provide a recording
ink which makes it possible to obtain an image excellent in
quality to plain paper, particularly in image density and image
durability such as water resistance, light resistance, etc., which

is superior in drying rate and adaptability to high-speea printing,
which is excellent in storage stability and ejection stability and
which is harmless to a maintenance device for an ink ejection
device; and an ink cartridge, a recording method, a recording
apparatus and an ink recorded matter which use the recording
ink.
The recording ink is excellent in ejection stability from a
nozzle, makes it possible to form high-quality images and can be
suitably used for an ink cartridge, an ink recorded matter, an
ink-jet recording apparatus and an ink-jet recording method.
Furthermore, the recording ink causes less beading
(nonuniformity of density), has superior drying properties and
makes it possible to form images of high quality such as printing
image quality, when general-purpose printing paper (a recording
medium with low ink-absorbing ability, including a support, and
a coating layer applied onto at least one surface of the support, in
which the amount of purified water transferred to the recording
medium at a contact period of 100ms measured by a dynamic
scanning absorptometer is 2ml/m2 to 35ml/m2 and the amount of
purified water transferred to the recording medium at a contact
period of 400ms measured by the dynamic scanning
absorptometer is 3ml/m2 to 40ml/m2) is used.
The ink-jet recording apparatus and the ink-jet recording
method of the present invention can be applied to a variety of

types of recording based upon ink-jet recording systems. For
example, they can be particularly suitably applied to ink-jet
recording printers, facsimile apparatuses, copiers,
printer/fax/copier complex machines, and so forth.

CLAIMS
1. An ink-jet recording ink comprising:
a colorant dispersible in water,
a water-soluble organic solvent, which, is used as a wetting
agent,
a surfactant,
a penetrant,
a water-dispersible resin, and
water,
wherein when 2.5g of the ink is weighed, placed in a glass
Petri dish having a diameter of 33mm and stored for 24hr at a
temperature of 50oC±0.5°C and a humidity of 12%±5%, the
evaporation rate of a solvent in the ink is 50% by weight or more,
and an ink residue has a viscosity of 20,000mPa.s or greater, and
wherein by storing the ink residue for 6hr at a
temperature of 23°C+0.5°C and a high humidity of 95%±3% to
allow it to absorb moisture, the amount of moisture contained in
the ink residue becomes 30% by weight to 40% by weight, in
which case the ink residue has a viscosity of less than 500mPa.s;
where the "evaporation rate of a solvent" is represented by
the expression (1 - amount of ink residue / total weight of
ink)xl00, the solvent includes the water and the water-soluble
organic solvent contained in the ink, and the "amount of moisture

contained in the ink residue" is represented by the expression
(amount of moisture absorbed / total amount of ink residue that
has absorbed moisture)x100.
2. The ink-jet recording ink according to claim 1, wherein the
wetting agent is at least one of polyhydric alcohols, each of which
has an equilibrium moisture content of 30% by weight or more at
a temperature of 23°C and a relative humidity of 80%.
3. The ink-jet recording ink according to any one of claims 1
to 2, wherein the colorant dispersible in water is a pigment which
can be stably dispersed in water in the absence of a dispersant by
bonding at least one hydrophilic group to a surface of the colorant
directly or via other atomic group.
4. The ink-jet recording ink according to any one of claims 1
to 3, wherein the surfactant comprises at least one of a
silicone-based surfactant and a fluorine-based surfactant.
5. The ink-jet recording ink according to any one of claims 1
to 4, wherein the penetrant contains at least one of a polyol
compound having 8 to 11 carbon atoms and a glycol ether
compound.

6. The ink-jet recording ink according to any one of claims ±
to 5, wherein the water-dispersible resin is at least any one of a
polyurethane resin, an acrylic-silicone resin, and a fluorine resin
having a fluoroolefin unit, and the minimum film-forming
temperature of the water-dispersible resin is 30°C or lower.
7. The ink-jet recording ink according to any one of claims 1
to 6, having a viscosity of 5mPa.s to 20mPa.s at 25°C and a static
surface tension of 35mN/m or less at 25°C.
8. An ink-jet recording method comprising:
jetting the ink-jet recording ink according to any one of
claims 1 to 7 so as to form an image on a recording medium, by
applying a stimulus to the ink-jet recording ink,
wherein the recording medium comprises a support, and a
coating layer applied onto at least one surface of the support, the
amount of purified water transferred to the recording medium at
a contact period of 100ms measured by a dynamic scanning
absorptometer is 2ml/m2 to 35ml/m2 and the amount of purified
water transferred to the recording medium at a contact period of
400ms measured by the dynamic scanning absorptometer is
3ml/m2 to 40ml/m2.
9. An ink-jet recording apparatus with an ink cartridge to

house the ink-jet recording ink according to any one 01 claims 1 to
7, comprising:
an ink jetting unit configured to jet the ink-jet recording
ink so as to form an image on a recording medium, by applying a
stimulus to the ink-jet recording ink.

An ink-jet
recording ink including a
colorant dispersible in water, a
water-soluble organic solvent used
as a wetting agent, a surfactant,
a penetrant, a water-dispersible
resin, and water, wherein when
2.5g of the ink is weighed, placed
in a glass Petri dish having a
diameter of 33mm and stored
for 24hr at a temperature of
50OC+0..5OC and a humidity of
12%±5%, the evaporation rate of
a solvent (water + water-soluble
organic solvent) in the ink is
50% by weight or more, and
an ink residue has a viscosity
of 20,000mPa-S or greater,
and wherein by storing the ink
residue for 6hr at a temperature of
23°C±0.5°C and a high humidity
of 95%±3% to allow it to absorb
moisture, the amount of moisture
contained in the ink residue
becomes 30% by weight to 40%
by weight, in which case the ink
residue has a viscosity of less than
500mPas.

Documents:

510-KOLNP-2009-(10-04-2013)-CORRESPONDENCE.pdf

510-KOLNP-2009-(10-04-2013)-FORM 3.pdf

510-KOLNP-2009-(16-08-2013)-ANNEXURE TO FORM 3.pdf

510-KOLNP-2009-(16-08-2013)-CORRESPONDENCE.pdf

510-KOLNP-2009-(16-10-2014)-ABSTRACT.pdf

510-KOLNP-2009-(16-10-2014)-ANNEXURE TO FORM 3.pdf

510-KOLNP-2009-(16-10-2014)-CLAIMS.pdf

510-KOLNP-2009-(16-10-2014)-CORRESPONDENCE.pdf

510-KOLNP-2009-(16-10-2014)-DESCRIPTION (COMPLETE).pdf

510-KOLNP-2009-(16-10-2014)-DRAWINGS.pdf

510-KOLNP-2009-(16-10-2014)-FORM-1.pdf

510-KOLNP-2009-(16-10-2014)-FORM-13.pdf

510-KOLNP-2009-(16-10-2014)-FORM-2.pdf

510-KOLNP-2009-(16-10-2014)-FORM-5.pdf

510-KOLNP-2009-(16-10-2014)-OTHERS.pdf

510-KOLNP-2009-(16-10-2014)-PETITION UNDER RULE 137-1.pdf

510-KOLNP-2009-(16-10-2014)-PETITION UNDER RULE 137.pdf

510-KOLNP-2009-(30-12-2014)-CORRESPONDENCE.pdf

510-kolnp-2009-abstract.pdf

510-KOLNP-2009-ASSIGNMENT.pdf

510-kolnp-2009-claims.pdf

510-KOLNP-2009-CORRESPONDENCE-1.1.pdf

510-kolnp-2009-correspondence.pdf

510-kolnp-2009-description (complete).pdf

510-kolnp-2009-drawings.pdf

510-kolnp-2009-form 1.pdf

510-kolnp-2009-form 18.pdf

510-KOLNP-2009-FORM 3-1.1.pdf

510-kolnp-2009-form 3.pdf

510-kolnp-2009-form 5.pdf

510-kolnp-2009-gpa.pdf

510-kolnp-2009-international publication.pdf

510-kolnp-2009-international search report.pdf

510-kolnp-2009-pct priority document notification.pdf

510-kolnp-2009-pct request form.pdf

510-kolnp-2009-specification.pdf

abstract-510-kolnp-2009.jpg


Patent Number 265627
Indian Patent Application Number 510/KOLNP/2009
PG Journal Number 10/2015
Publication Date 06-Mar-2015
Grant Date 02-Mar-2015
Date of Filing 06-Feb-2009
Name of Patentee RICOH COMPANY, LTD.
Applicant Address 3-6, NAKAMAGOME 1-CHOME, OHTA-KU, TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 NAGAI, KIYOFUMI FINE HILL VILLAGE 102, 2212-1, NARUSE, MACHIDA-SHI TOKYO 1940044
2 GOTO, HIROSHI PASTORAL GARDEN SANBANKAN 101, 265-1, TODA, ATSUGI-SHI, KANAGAWA, 2430023
3 ARUGA, TAMOTSU 1-9-13, HIGASHIDAIBA, MISHIMA-SHI, SHIZUOKA, 4110802
4 KOYANO, MASAYUKI 6-34-4-608, SAGAMIGAOKA, ZAMA-SHI, KANAGAWA 2280001
PCT International Classification Number C09D 11/00,B41M 5/50
PCT International Application Number PCT/JP2008/061178
PCT International Filing date 2008-06-12
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2007-155114 2007-06-12 Japan