Title of Invention

MAGENTA RECORDING INK COMPOSITION, INKJET RECORDING METHOD, AND INK RECORDED MATTER

Abstract The present invention provides a magenta recording ink composition including at least a solid solution pigment (A) containing quinacridone, a lake pigment (B) having a xanthene structure, an aqueous solvent, and water, wherein the solid solution pigment (A) has visible light absorption peaks at wavelength ranges of from 510 nm to 530 nm and from 540 nm to 560 nm, and a mass ratio (B/A) of the lake pigment (B) to the solid solution pigment (A) falls within the range of 0.1 to 5.
Full Text DESCRIPTION
MAGENTA RECORDING INK COMPOSITION, INKJET
RECORDING METHOD, AND INK RECORDED MATTER
Technical Field
The present invention relates to a magenta
recording ink composition which is suitably used for inkjet
recording, superior in ejection stability, water resistance
and light resistance and enables obtaining high-quality
images with high-color saturation and excellent color tone,
which contains at least a solid solution pigment (A)
containing quinacridone, a lake pigment (B) having a
xanthene structure, an aqueous solvent, and water,
wherein the solid solution pigment (A) has visible light
absorption peaks at wavelength ranges of from 510 nm to
530 nm and from 540 nm to 560 nm, and a mass ratio (B/A)
of the lake pigment (B) to the solid solution pigment (A)
falls within the range of 0.1 to 5. The present invention
also relates to an inkjet recording method and ink recorded
matters using the magenta recording ink composition.
Background Art
Inkjet printers have become increasingly popular
because of such advantages as low-noise pollution and
low-running cost, and inkjet color printers capable of
printing on plain paper have also been increasingly put on
the market. However, it is significantly difficult for
inkjet printers to satisfy all the requirements such as color
reproducibility of images, abrasion resistance, light
resistance, gas resistance, water resistance and drying
property of recorded images, resistance to character
feathering, resistance to bleed at boundaries between
different colors (resistance to color bleed), image density
uniformity at solid image parts (resistance to beading),
double-sided printing property and ejection stability.
Thus, in reality, an ink and a recording medium are
selected in view of preferential properties in accordance
with the intended use.
In general, inks used in inkjet recording contain
water as a main component and additionally contain a
colorant, and a wetting agent such as glycerin with a view
to preventing clogging. As for colorants, water-soluble
dyes which enable obtaining vivid colors are commonly
used. Dyes are, however, inferior in resistance to light,
gases and water, and images recorded with dyes on plain
paper are far from providing satisfactory image quality.
To solve the problem, attempts to improve these
resistances, i.e., resistance to light, gases and water, are
made by improving properties of inkjet recording paper
having an ink absorption layer. But, the improvements
have not yet reached sufficient levels.
Recently, pigments have become widely used as
colorants because of their superior light resistance, gas
resistance and water resistance. However, it is true that
pigments are inferior in color developing property to dyes.
This can be primarily explained by the fact that lights
having different wavelengths and/or phases caused by
multiple reflection inside pigment particles interfere with
each other. That is, when pigment(s) are used as inkjet
recording ink(s), a reduction in color saturation occurs on
plain paper, and a reduction in glossiness occurs on inkjet
recording paper. To solve the problems, attempts are
made to improve color saturation by making finer pigment
microparticles and to improve glossiness of pigment
particles by covering the particles with polymer. Despite
these improvements, there still exist a difference in color
developing property between pigments and dyes.
Particularly in magenta inks, quinacridone
pigments are widely used for their superior color
developing properties and light resistance. Quinacridone
pigments, however, are somewhat more reddish in color
than the standard magenta color (Japan color Ver. 2) used
in printing. This tendency has become increasingly
marked as an image is printed with higher image density.
When an attempt is made to yield a vivid color with high
image density, a resultant color inconveniently becomes
more reddish. However, at the present time, there are no
pigments that can achieve a color comparable to the
standard magenta color with high color saturation through
the use of one pigment alone. Recently, attempts to
obtain high magenta color saturation are made using a
solid solution of quinacridone pigment, but the desired
magenta color saturation has not yet been achieved.
Patent Literature 1 and other documents propose an
ink using a solid solution pigment. In most cases, use of
solid solution pigments makes it possible to obtain vivid
colors as compared with inks which contain pigments
composed of monocrystal, however, solid solution pigments
are still inferior in color developing property to dyes.
Meanwhile, attempts are made in Patent Literature
2 through Patent Literature 6 to increase color saturation,
which has been insufficient with use of one type of dye, by
mixing two or more types of water-soluble dye including
xanthene dyes, and to improve light resistance, which has
been insufficient with use of one type of dye, by mixing
dyes having higher light resistance. However, the light
resistance of dyes is still insufficient, even if a plurality of
dyes are mixed, it is incomparable with the light resistance
of pigment inks at the present time.
As an ink that satisfies both excellent light
resistance obtained from pigments and excellent brilliant
coloring effect obtained from dyes, Patent Literature 7
proposes an ink produced by mixing Rhodamine B-based
water-soluble dye and a pigment. With this method, the
light resistance can be improved as close as that provided
by using a pigment, however, when a penetration-type ink
having low-surface tension is printed on plain paper,
feathering and color bleed occur as in the case where a
dye-based ink is used, resulting in incapability of
obtaining an image with high-sharpness.
Also, an ink produced by mixing two or more types of
different organic pigments is proposed. Patent Literature
8 proposes to adjust color tone and improve color
saturation by adding from 0.01% to 1% of an organic
pigment having a hue angle of 270 degrees to 340 degrees
to a quinacridone pigment. However, even if such a small
amount as 0.01% to 1% of the pigment is added, a change in
color tone and a further improvement in color saturation
can be little expected. In contrast, when a lake pigment
(B) is added to a solid solution pigment (A) at a mass ratio
(B/A) within the range of 0.1 to 5, as in the present
invention, it is possible to adjust color tone and improve
color saturation. Patent Literature 9 proposes an inkjet
recording ink produced by mixing a quinacridone pigment
and a pigment(s) of red, violet, orange, etc. in color, but
the proposal is intended to achieve inks for use in color
filters with more transparent and more vivid color. Thus,
the object of the proposed ink differs from that of the
magenta ink of the present invention.
The present inventors proposed before in Patent
Literature 10 a technique relevant to an ink composition
containing colored polymer fine particles in which an
organic pigment (solid solution pigment), an oil-soluble
dye and an inorganic pigment are covered with a polymer,
but the ink proposed by the technique differs from an ink
according to the present invention in which an organic
pigment (specific solid solution pigment) and a lake
pigment are mixed.
Patent Literature 1 Japanese Patent (JP-B)
No.3556835
Patent Literature 2 Japanese Patent (JP-B)
No.3829419
Patent Literature 3 Japanese Patent
Application Laid-Open (JP-A) No. 9-286167
Patent Literature 4 Japanese Patent
Application Laid-Open (JP-A) No. 2001-192591
Patent Literature 5 Japanese Patent
Application Laid-Open (JP-A) No. 2002-235020
Patent Literature 6 Japanese Patent
Application Laid-Open (JP-A) No. 2003-238875
Patent Literature 7 Japanese Patent
Application Publication (JP-B) No. 60-045669
Patent Literature 8 Japanese Patent (JP-B)
No. 3670148
Patent Literature 9 Japanese Patent
Application Laid-Open (JP-A) No. 2003-292812
Patent Literature 10 Japanese Patent
Application Laid-Open (JP-A) No. 2008-255241:
Disclosure of Invention
An object of the present invention is to eliminate
shortcomings arose from the conventional techniques and
to provide a magenta recording ink composition which is
superior in ejection stability, water resistance and light
resistance and enables obtaining high-quality images with
high-color saturation and excellent color tone, which
contains at least a solid solution pigment (A) containing
quinacridone, a lake pigment (B) having a xanthene
structure, an aqueous solvent, and water, wherein the solid
solution pigment (A) has visible light absorption peaks at
wavelength ranges of from 510 nm to 530 nm and from 540
nm to 560 nm, and a mass ratio (B/A) of the lake pigment
(B) to the solid solution pigment (A) falls within the range
of 0.1 to 5; and to provide an inkjet recording method as
well as ink recorded matters using the ink composition.
The present inventors carried out extensive studies
and examinations in order to solve the problems pertinent
to the art of the present invention and have found that
when an ink composition contains at least a solid solution
pigment (A) having visible light absorption peaks at
wavelength ranges of from 510 nm to 530 nm and from 540
nm to 560 nm and containing quinacridone, a lake pigment
(B) having a xanthene structure, an aqueous solvent, and
water, and a mass ratio (B/A) of the lake pigment (B) to the
solid solution pigment (A) falls within the range of 0.1 to 5,
the ink composition becomes superior in ejection stability,
water resistance and light resistance and enables
obtaining high-quality images with high-color saturation
and excellent color tone, which leads to the
accomplishment of the present invention.
The present invention is based on this finding.
Means for solving the aforesaid problems are as follows.
A magenta recording ink composition
including: at least a solid solution pigment (A) containing
quinacridone, a lake pigment (B) having a xanthene
structure, an aqueous solvent, and water, wherein the solid
solution pigment (A) has visible light absorption peaks at
wavelength ranges of from 510 nm to 530 nm and from 540
nm to 560 nm, and a mass ratio (B/A) of the lake pigment
(B) to the solid solution pigment (A) falls within the range
of 0.1 to 5.
The magenta recording ink composition
according to the item. , wherein the solid solution
pigment (A) is a solid solution (a) formed between an
unsubstituted quinacridone and a dimethylquinacridone, a
solid solution (b) formed between an unsubstituted
quinacridone and a dichloroquinacridone or a mixture of
(a) and (b), and the lake pigment (B) is C.I. Pigment Violet
1 and/or C.I. Pigment Violet 2.
The magenta recording ink composition
according to any one of the items and , wherein
the aqueous solvent contains one or two or more of glycerin,
1,3-butandiol, 3-methyl-1,3-butandiol, hexylene glycol,
polyethylene glycol, polypropylene glycol, 1,5-pentanediol,
1,6-hexanediol, propylene glycol, dipropylene glycol, and
trimethylolpropane.
The magenta recording ink composition
according to any one of the items to , wherein
each of the solid solution pigment (A) and the lake pigment
(B) is dispersed by using a dispersant represented by any
one of the following General Formulas (1) and (2),

where A1 is any one of an alkyl group that has 8 to
12 carbon atoms and may be branched, a benzyl group, a
styrenated phenol group, a distyrenated phenol group and
a p-naphthyl group; k is an integer of 5 to 30; and Ml
represents any one of an alkali metal, ammonium,
phosphonium, and alkanol amine;

where Al is any one of an alkyl group that has 8 to
12 carbon atoms and may be branched, a benzyl group, a
styrenated phenol group, a distyrenated phenol group and
a p-naphthyl group; and i is an integer of 20 to 60.
The magenta recording ink composition
according to the item , further including a
water-soluble polymer having a weight average molecular
mass of 2,000 to 50,000.
The magenta recording ink composition
according to any one of the items to , further
including polymer microparticles having a volume average
particle diameter of 20 nm to 150 nm and/or a polymer
emulsion containing the polymer microparticles.
The magenta recording ink composition
according to any one of the items to , further
including any one of a polyol having 8 or more carbon
atoms, and glycol ether having 8 or more carbon atoms.
The magenta recording ink composition
according to any one of the items to , having a
viscosity of 5 mPa-s to 30 mPa-s at 25°C and a surface
tension of 20 mN/m to 35 mN/m and a pH of 7 to 11.
An inkjet recording method including-
printing an ink on a recording medium by making
the magenta recording ink composition according to any
one of the items to adhere on the recording
medium.
The inkjet recording method according to the
item , wherein the printing is performed in such a
manner that the ink is ejected by the action of thermal
energy applied to the ink.
The inkjet recording method according to the
item , wherein the printing is performed in such a
manner that the ink is ejected by the action of mechanical
energy transmitted to the ink.
A recorded matter including: an image
formed by the inkjet recording method according to any one
of the items and .
With the use of a magenta recording ink composition
which contains at least a solid solution pigment (A)
containing quinacridone, a lake pigment (B) having a
xanthene structure, an aqueous solvent, and water,
wherein the solid solution pigment (A) has visible light
absorption peaks at wavelength ranges of from 510 nm to
530 nm. and from 540 nm to 560 nm, and a mass ratio (B/A)
of the lake pigment (B) to the solid solution pigment (A)
falls within the range of 0.1 to 5, it is possible to provide
an image with high color saturation and with color
comparable to the hue of the standard color.
With the use of a magenta recording ink composition
in which the solid solution pigment (A) is a solid solution
formed between an unsubstituted quinacridone and a
dimethyl quinacridone and/or a solid solution formed
between an unsubstituted quinacridone and a
dichloroquinacridone, and the lake pigment (B) is a C.I.
Pigment Violet 1 and/or C.I. Pigment Violet 2, it is possible
to provide an image with further higher color saturation
and with color comparable to the hue of the standard color.
A magenta recording ink composition superior in
ejection stability can be provided by incorporating as the
aqueous solvent to the magenta recording ink composition
one or two or more of glycerin, 1,3-butandiol,
3-methyl-l,3-butandiol, hexylene glycol, polyethylene
glycol, polypropylene glycol, 1,5-pentanediol,
1,6-hexanediol, propylene glycol, dipropylene glycol, and
trimethylolpropane.
Also, a magenta recording ink composition still more
superior in ejection stability can be provided by further
incorporating into the magenta recording ink composition
a water-soluble polymer having a weight average molecular
mass of 2,000 to 50,000.
An image superior in fixing property and abrasion
resistance can be provided by further incorporating into
the magenta recording ink composition polymer
microparticles having a volume average particle diameter
of 20 nm to 150 nm and/or a polymer emulsion containing
the polymer microparticles.
A magenta recording ink composition superior in
ejection stability can be provided by further incorporating
into the magenta recording ink composition a polyol having
8 or more carbon atoms or glycol ether.
A magenta recording ink composition further
superior in ejection stability can be supplied by adjusting
so as to have a viscosity of 5 mPa.s to 30 mPa.s at a
temperature of 25°C, a surface tension of 20 mN/m to 35
mN/m, and a pH of 7 to 11.
An image with high color saturation and with color
comparable to the hue of the standard color and superior in
fixing property and abrasion resistance can be stably
supplied by an inkjet recording method which includes
printing an ink on a recording medium by making the
magenta recording ink composition according to any one of
the items to adhere on the recording medium.
Thermal energy is applied to the ink so as to eject
the ink, thereby making it possible to stably supply an
image with high, color saturation and with color
comparable to the hue of the standard color and superior in
fixing property and abrasion resistance.
Further, mechanical energy is transmitted to the
ink so as to eject the ink, thereby making it possible to
stably supply an image with high color saturation and with
color comparable to the hue of the standard color and
superior in fixing property and abrasion resistance.
An ink recorded matter high color saturation and
with color comparable to the hue of the standard color and
superior in fixing property and abrasion resistance, which
is formed by the inkjet recording method according to any
one of the items and , can be stably supplied.
Brief Description of Drawings
FIG- 1 is a schematic front view exemplarily showing
a configuration of a serial type inkjet recording apparatus
mounted with an ink cartridge accommodating therein a
recording liquid of the present invention.
FIG. 2 is a perspective external view of an ink
cartridge before being mounted to a recording apparatus.
FIG. 3 is a front cross-sectional view of an ink
cartridge.
FIG. 4 is a perspective external view of a recording
unit which is integrally supported with a recording head.
FIG. 5 is a view showing visible light spectrum.
Best Mode for Carrying Out the Invention
The following explains a magenta recording ink
composition of the present invention in detail. The
magenta recording ink composition of the present
invention contains at least a solid solution pigment (A)
containing quinacridone and having visible light
absorption peaks at wavelength ranges of from 510 nm to
530 nm and from 540 nm to 560 nm, a lake pigment (B)
having a xanthene structure, an aqueous solvent, and
water, and may further contain other components.
Hereinbelow, these components will be described more
specifically.
[Solid Solution Pigment (A)]
The solid solution pigment (A) may be a solid
solution pigment capable of forming a solid solution having
visible light absorption peaks at wavelengths of 510 nm to
530 nm and 540 nm to 560 nm. For example, solid
solutions each consisting of a combination of a
dimethyl-substituted quinacridone and an unsubstituted
quinacridone, a combination of an unsubstituted
quinacridone and a dichloro-substituted quinacridone, and
a combination of a dimethylquinacridone and a
diketopyrrolopyrrole; solid solutions each consisting of two
components." and mixtures of these solid solutions are
preferably exemplified. Depending on the combination
selected and the mixing ratio, a more brilliant color can be
obtained, as compared to the case where an organic
pigment is used alone.
The unsubstituted quinacridone may be any one of
a-type, ß-type and ?-type, and ß-type or ?-type
unsubstituted quinacridone is preferable from the
viewpoint of storage stability. A mixing ratio of the two
types of pigment constituting the solid solution pigment
(A) is preferably 10/90 to 90/10, and more preferably 15/85
to 85/15. It should be noted that the solid solution
pigment (A) is not merely a mixture of the two components
and is preferably composed of solid solutions derived from
the two components.
[Lake Pigment (B)]
As the lake pigment (B), pigments having a xanthene
structure such as Rhodamine B, and Rhodamine 6G are
exemplified, for example. Specific examples thereof
include G.I. Pigment Violet 1, C.I. Pigment Violet 2, C.I.
Pigment Violet 3, C.I. Pigment Violet 81:2. Those
pigments have high transparency and develop a vivid
violet color.
The total amount of coloring material particles of the
solid solution pigment (A) and the lake pigment (B)
contained in the recording ink is preferably 1% by mass to
15% by mass, on solid content basis, and more preferably
3% by mass to 10% by mass.
[Additional pigment]
- Organic pigment -
In the present invention, additional pigments can be
used. These additional pigments encompass pigments
capable of forming the solid solution pigment (A) and
pigments other than the solid solution pigment (A) and the
lake pigment (B) and are used within such a range that
achievement of the object of the present invention should
not be inhibited. For the organic pigments, aniline blacks
as black pigments are exemplified. As color pigments,
anthraquinone, phthalocyanine blue, phthalocyanine green,
diazo pigments, monoazo pigments, perylene, heterocyclic
yellow, other quinacridones and (thio)indigoide are
exemplified. Among these, phthalocyanine pigments,
quinacridone pigments, other diketopyrrolopyrrole
pigments, monoazo yellow pigments, disazo yellow
pigments, heterocyclic yellow pigments are superior in
color developing property.
Typical examples of phthalocyanine blue pigments
include metal-free copper phthalocyanine blue C.I.
Pigment Blue 16, phthalocyanine blue and derivatives
thereof (C.I. Pigment Blue 15:1, 15:3 and 15:4), and
aluminum phthalocyanine.
Typical examples of other quinacridones include C.I.
Pigment Orange 48 and 49, C.I. Pigment Red 122, 192, 202,
206, 207 and 209, C.I. Pigment Violet 19 and 42.
Typical examples of diketopyrrolopyrrole pigments
include C.I. Pigment Red 254, 255, 264 and 272.
Typical examples of monoazo yellow pigments
include C.I. Pigment Yellow 74, 109, 128 and 151.
Typical examples of disazo yellow pigments include
C.I. Pigment Yellow 14, 16, 17 and 155.
Typical examples of heterocyclic yellow pigments
include C.I. Pigment Yellow 117 and 138.
Other suitable coloring pigments are described in
"The Colour Index 3rd edition (The Society of Dyers and
Colourists, 1982).
- Other lake pigment -
There are other water-insoluble lake pigments to
which extender pigment(s), metal salt, tannin,
phosphomolybdic acid, phosphotungstic acid, etc, are
added so as to be insoluble in water. These other
water-insoluble lake pigments are broadly classified into
acidic dye lakes and basic dye lakes.
Acidic dye lakes are each made by laking a dye having
an acidic group such as sulfonic acid group and carboxyl
group in its molecules with the use of a metal salt such as
aluminum, calcium and barium so as to be a pigment
insoluble in water. Examples thereof include C.I.
Pigment Yellow 100, C.I. Pigment Yellow 104, C.I. Pigment
Red 172, C.I. Pigment Red 193, C.I. Pigment Blue 24 = 1 and
C.I. Pigment Blue 63.
Basic dye lakes are each made by laking a dye having
an amino group or derivatives thereof in its molecules with
the use of a tannic acid, phosphotungstic acid,
phosphomolybdic acid and complex acids thereof.
Examples thereof include C.I. Pigment Violet 3, C.I.
Pigment Violet 27, C.I. Pigment Violet 81:2, C.I. Pigment
Blue 1, C.I. Pigment Blue 56, C.I. Pigment Blue 61, and C.I.
Pigment Blue 62, besides C.I. Pigment Violet 1 and C.I.
Pigment Violet 2.
- Dispersant -
After microparticulating the above-mentioned
pigment(s), a dispersant is used for dispersing the
microparticulated pigments in an aqueous solution so as to
prepare a dispersoid. The dispersant may be suitably
selected from among primarily nonionic surfactants and
anionic surfactants, or polymer dispersants in accordance
with the intended use.
(Nonionic dispersant)
Examples of the nonionic dispersants (surfactants)
include polyoxyethylene alkyl ethers, polyoxyethylene
alkylallylethers, polyoxyethylene polyoxypropylene glycols,
glycerin esters, sorbitan esters, sucrose esters,
polyoxyethylene ethers of glycerin esters, polyoxyethylene
ethers of sorbitan esters, polyoxyethylene ethers of
sorbitol esters, fatty acid alkanolamides, polyoxyethylene
fatty acid amides, amine oxides, polyoxyethylene
alkylamines, polyoxyethylene-p-nap hthylet hers,
polyoxyethylene styryl phenyl ethers, and polyoxyethylene
distyryl phenyl ethers. In the present invention,
dispersants each having a structure, in particular, as
shown in the following Formulas (lA), (IB) and (1C) may be
effectively used.

(Anionic dispersant)
Examples of the anionic dispersants (surfactants)
include alkyl sulfates, alkyl ether sulfates, alkylester
sulfates, alkylallyl ether sulfates, alkyl sulfonates,
sulfosuccinates, alkylallyl and alkylnaphthalene
sulfonates, alkyl phosphates, polyoxyethylene alkyl ether
phosphates, alkylallyl ether phosphates, polyoxyethylene
alkyl ether sulfates, polyoxyethylene styrylphenyl ether
sulfates, and polyoxyethylene distyrylphenyl ether
sulfates. In the present invention, dispersants each
having a structure, in particular, as shown in the following
Formulas (2A) and (2B) may be effectively used.

(Polymer dispersant)
Examples of the polymer dispersants include
polyacrylic acids, polymethacrylic acids, acrylic
acid-acrylonitrile copolymers, vinyl acetate-acrylic acid
ester copolymers, acrylic acid-acrylic acid alkylester
copolymers, styrene-acrylic acid copolymers,
styrene-methacrylic acid copolymers, styrene-acrylic
acid-acrylic acid alkylester copolymers,
styrene-methacrylic acid-acrylic acid alkylester
copolymers, styrene-ormethylstyrene-acrylic acid
copolymers, styrene-a-methylstyrene-acrylic acid
copolymers, acrylic acid alkylester copolymers,
styrene-maleic acid copolymers, vinylnaphthalene-maleic
acid copolymers, vinylacetate-ethylene copolymers,
vinylacetate-fatty acid vinylethylene copolymers,
vinylacetate-maleic acid ester copolymers,
vinylacetate-crotonic acid copolymers, and vinyl
acetate-acrylic acid copolymers. These dispersants may
be used alone or in combination.
The dispersoid is produced by the following method.
Specifically, the dispersant mentioned above is dissolved
in an aqueous medium, then the pigment particles are
added thereto, the mixture solution thus prepared is
sufficiently wetted and then agitated at high speed by
means of a homogenized or kneaded and dispersed by a
dispersing kneader using a ball, such as a bead mill or ball
mill; a high-shear dispersing kneader like a roll mill; a
ultrasonic dispersing device or the like. However, after
such a kneading dispersion step, coarse particles are often
contained in the resultant dispersoid, which may cause
inkjet nozzle clogging of an inkjet nozzle and clogging at
an ink supply path. Thus, there is a need to remove
particles of 1 µm or larger in diameter using a filter or
centrifuge.
The amount of the dispersant added to the coloring
material particles is preferably 1% by mass to 100% by
mass, and more preferably 10% by mass to 50% by mass.
When the amount is small, the pigment contained may not
be sufficiently microparticulated. When the amount is
excessively large, an excessive amount of dispersant
component that is not adsorbed to the pigment adversely
affects the ink properties, thereby possibly leading to
image feathering and degradation in water resistance and
image abrasion resistance.
The mixing ratio of the dispersant to the coloring
material particles in the recording ink is preferably 10% to
100%, and more preferably 25% to 50%.
- Polymer -
As the water-soluble polymer, and the polymer
constituting the polymer microparticles or polymer
emulsion used in the present invention, polyester resin,
polyurethane resin, vinyl resin, and acrylic resin may be
suitably used.
(Polyester resin)
The polyester resin is constituted by polyvalent
carboxylic acid and polyhydric alcohol.
Examples of the polyvalent carboxylic acid include
aromatic dicarboxylic acids such as terephthalic acid,
isophthalic acid, orthophthalic acid,
1,5-naphthalenedicarboxylic acid,
2,6-naphthalendicarboxylic acid, diphenic acid,
sulfoterephthalic acid, 5-sulfoisophthalic acid,
hexahydrophthalic anhydride, 4-sulfophthalic acid,
4-sulfonapthalene_2,7 dicarboxylic acid, and
5[4-sulfophenoxy]isophthalic acid; aliphatic dicarboxylic
acids such as succinic acid, adipic acid, azelaic acid,
sebacic acid, and dodecanedicarboxylic acid; and other
trivalent or higher polyvalent carboxylic acids.
Examples of the polyhydric alcohol include aliphatic
polyhydric alcohols such as ethylene glycol, propylene
glycol, 1,3-propahediol, 2,3-butanediol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol,
dipropylene glycol, dipropylene glycol,
2,2,4-trimethyl-l,3pentanediol, polyethylene glycol,
polypropylene glycol, polytetramethylene glycol,
trimethylolethane, trimethylolpropane, glycerin,
pentaerythritol, 1,4-cyclohexanediol,
1,4-cyclohexanedimethanol, spiro glycol, tricyelodecane
diol, tricyclodecanedimethanol, metaxylene glycol,
orthoxylene glycol, 1,4-phenylene glycol, bisphenol A, and
lactone-based polyester polyols; other aliphatic polyhydric
alcohols and aromatic polyhydric alcohols.
(Polyurethane resin)
The polyurethane resins are constituted by
isocyanates and compounds having a functional group
capable of reacting with isocyanates. Examples of the
polyurethane resins include resins polymerized by using
each of these components alone or a combination of two or
more.
Examples of the isocyanates include aliphatic
polyisocyanates such as ethylene diisocyanate,
trimethylene diisocyanate, tetramethylene diisocyanate,
hexamethylene diisocyanate, octamethylene diisocyanate,
and nonamethylene diisocyanate; aliphatic
polyisocyanates such as isophorone diisocyanate,
bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane
diisocyanate, cyclohexane diisocyanate,
methylcyclohexane diisocyanate, and
dicyclohexyldimethylmethane diisocyanate,' aromatic
polyisocyanates such as phenylene diisocyanate, tolylene
diisocyanate, ethylphenylene diisocyanate,
isopropylenephenylene diisocyanate, dimetliylphenylene
diisocyanate, diisopropylphenylene diisocyanate,
trimethylbenzene triisocyanate, benzene triisocyanate,
naphthalene diisocyanate, methyl naphthalene
diisocyanate, biphenyl diisocyanate, and
tolidinediisocyanate; and other isocyanates such as
sulfur-containing aliphatic isocyanates, aliphatic
disulfide-based isocyanates, aromatic sulfone-based
isocyanates, sulfonate-based isocyanates, aromatic sulfone
amides, and sulfur-containing heterocyclic compounds.
Examples of the compound having a functional group
capable of reacting with isocyanates include aliphatic
polyols such as ethylene glycol, diethylene glycol,
triethylene glycol, tetraethylene glycol, propylene glycol,
dipropylene glycol, butylene glycol, neopentyl glycol,
glycerin, trimethylolethane, trimethylolpropane,
butanetriol, 1,2-methylglycoside, pentaerythritol,
dipentaerythritol, sorbitol, erythritol, threitol, ribitol,
arabinitol, xylitol, allitol, mannitol, dorsitol, iditol, glycol,
inositol, hexanetriol, triglycerose, diglyperol,
polyethylene glycol, polypropylene glycol,
polytetramethylene ether glycol, tris(2-hydroxyethyl)
isocyanurate, cyclobutanediol, cyclopentanediol,
cyclohexanediol, cycloheptanediol, cyclooctanediol,
polylactonediol, cyclohexane dimethanol,
hydroxyp ropylcyclonexanol, dicyclohexanediol,
cyclohexanetriol, multitol, and lactitol; aromatic polyols
such as dihydroxynaphthalene, trihydroxynaphthalene,
tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol,
biphenyltetraol, pyrogallol, (hydroxynapthtyl)pyrogallol,
trihydroxyphenanthrene, bisphenol A, bisphenol F,
xylylene glycol, di(2-hydroxyethoxy)benzene; condensation
reaction products between organic acids, such as oxalic
acid, glutamic acid, adipic acid, acetic acid, phthalic acid,
isophthalic acid, salicylic acid, and pyromellitic acid, and
the above-mentioned polyols; halogenated polyols, addition
reaction products between the above-mentioned polyols
and alkylene oxide such as ethylene oxide and propylene
oxide, addition reaction products between alkylene
polyamine and alkylene oxide, 2,2-dimethylol lactic acid,
2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid,
2,2-dimethylol valeric acid, 3,4-diaminobutane sulfonic
acid, 3,6-diamino-2-toluene sulfonic acid, and
caprolactone-modified products thereof, polyamino
compounds, polythiol compounds, and a-amino acids.
These may be used alone or in combination in the form of
mixture.
(Vinyl resin and acrylic resin)
The vinyl resin and the acrylic resin are not
particularly limited. For example, those obtained from
the polymerizable monomers described below are
exemplified. Examples of the polymerized monomers
include o-methylstyrene, m-methylstyrene,
p-methylstyrene, a-methylstyrene, p-ethylstyrene,
2,4-dimethylstyrene, p-tert-butylstyrene, p-chlorostyrene,
p-chlorostyrene, and vinyl-based aromatic hydrocarbons
such as divinylbenzene; acrylic acid esters such as methyl
acrylate, ethyl acrylate, butyl acrylate, n-propyl acrylate,
isopropyl acrylate, n-butyl acrylate, isobutyl acrylate,
t-butyl acrylate, n-pentyl acrylate, isopentyl acrylate,
neopentyl acrylate, 3-(methyl)butyl acrylate, 2-ethylhexyl
acrylate, cyclohexyl acrylate, hexyl acrylate, octyl acrylate,
nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl
acrylate, phenyl acrylate, methyl methacrylate, n-propyl
methacrylate, isopropyl methacrylate, n-butyl
methacrylate, isobutyl methacrylate, t-butyl methacrylate,
n-pentyl methacrylate, isopentyl methacrylate, neopentyl
methacrylate, 3-(methyl)butyl methacrylate, 2-ethylhexyl
methacrylate, hexyl methacrylate, octyl methacrylate,
nonyl methacrylate, decyl methacrylate, undecyl
methacrylate, and dodecyl methacrylate; unsaturated
carboxylic acids such as acrylic acid, methacrylic acid,
itaconic acid, and maleic acid; and resins that are
polymerized by singularly using any one of
(meth)acrylamide, N-substituted maleimide, maleic
anhydride, (meth)acrylonitrile, vinyl ketone, vinyl acetate,
and vinylidene chloride or resins that are polymerized by
using a combination thereof.
- Water-soluble polymer -
The addition of a water-soluble polymer to the
recording ink of the present invention makes it possible to
improve the storage stability of the ink. The
water-soluble polymer may be added along with additives
such as aqueous solvent and surfactants when the
pigment(s) are dispersed using a dispersing device such as
bead mill, and atrighter, or when a recording ink
composition is prepared, however, it is more preferable to
add it when preparing a recording ink composition.
The water-soluble polymer used in the present
invention exhibits solubility by addition of ionic groups on
the polymer surface. For such ionic groups, hydroxyl
groups, sulfonic groups, carboxyl groups, sulfate groups,
phosphate groups, phosphonate groups, and phosphine
groups or alkaline metal salt groups thereof, ammonium
salt groups thereof, or primary, secondary, or tertiary
amine groups are exemplified. Introduction of the ionic
groups is carried out in parallel with synthesis of the
polymer by adding the monomer having ionic groups.
Examples of the salt groups include ammonium-based ions,
Li, Na, K, Mg, Ca, Cu and Fe. Preferred is Li, K or Na.
In the present invention, the amount of the
water-soluble polymer relative to the total amount of a
coloring material of pigment in the ink composition is
preferably 1% by mass to 50% by mass, and more preferably
5% by mass to 30% by mass. When the amount of the
water-soluble polymer to the pigment is less than 1% by
mass, sufficient dispersion stability may not be obtained.
When it is more than 50% by mass, the ejection of the
resultant ink becomes unstable due to the high-viscosity of
the tine, thereby possibly leading to nozzle clogging.
- Polymer microparticles and polymer emulsion -
The polymer microparticles or the polymer emulsion
used in the present invention can be obtained by a
conventionally known method, e.g. by emulsification
polymerization of the polymer in water in presence of a
polymerizable catalyst and an emulsifier.
The polymer microparticles and polymer emulsion
can exhibit superior water dispersibility by incorporation
of ionic groups on the surfaces. For such ionic groups,
sulfonic groups, carboxyl groups, sulfate groups,
phosphate groups, phosphonate groups, and. phosphine
groups or alkaline metal salt groups thereof, ammonium
salt groups thereof, or primary, secondary, or tertiary
amine groups are exemplified. Preferred are carboxylic
acid-alkali metal salt groups, carboxylic acid-ammonium
salt groups, sulfonic acid-alkali metal salt groups and
sulfonic acid-ammonium salt groups, with sulfonic
acid-alkali metal salt groups and. sulfonic acid-ammonium
salt groups being particularly preferred. Introduction of
the ionic groups is carried out in parallel with synthesis of
the polymer by adding the monomer having ionic groups.
Examples of the salt groups include ammonium-based ions,
Li, Na, K, Mg, Ca, Cu and Fe. Preferred is Li, K or Na.
In the present invention, the amount of the polymer
microparticles or polymer emulsion to the ink composition
is preferably 0.5% by mass to 20% by mass, and more
preferably 1% by mass to 5% by mass. When the amount is
less than 0.5% by mass, sufficient abrasion resistance and
water resistance may not be obtained. When it is more
than 20% by mass, the ejection of the resultant ink
becomes unstable due an increase in viscosity of the ink,
resulting from air-drying, thereby possibly leading to
nozzle clogging.
- Dispersion of pigment by polymer coating -
The pigment can be dispersed in an aqueous medium
by making the pigment into microparticles and coating the
surface thereof with the polymer. For the coating, all
conventionally known methods, such as microcapsulation
or emulsification, may be employed. Examples of the
conventionally known methods include chemical
production methods, physical production methods, physical
and chemical treatments, and mechanical production
methods.
More specifically, the dispersion methods of pigment
by polymer coating are as follows:
• Acid separation method (a method in which at
least part of anionic groups of organic polymer compounds
containing the anionic groups is neutralized using a basic
compound; in accordance with this, solubility to water is
provided and the solubility-provided anionic groups are
mixed and kneaded along with a coloring material in an
aqueous medium, and then, the resultant substance is
made neutral or acidic using acidic compounds, organic
compounds are separated and bonded to the coloring
material, and then the substance is neutralized and
dispersed);
• Phase inversion emulsification method (a method
in which a mixture containing anionic organic polymers
which are dispersible in water and coloring material(s) is
prepared as an organic solvent phase, and water is
introduced to the organic solvent phase or the organic
solvent phase is introduced to water);
• Interfacial polymerization method (a method of
forming a wall film in which two types of monomers or two
types of reactants are separately dissolved in a dispersed
phase and a continuous phase and then the wall film is
formed by reacting both materials at a phase boundary
thereof);
• In-situ polymerization method (a method in which
two types of materials, namely, a liquid or gaseous
monomers and a catalyst or a reactive material are
supplied from one side of nuclear particles of continuous
phase so as to cause a reaction, thereby forming a wall
film);
• In-liquid cure coating method (a method of forming
a wall film in which droplets of a polymer solution
containing core material particles are insolubilized in the
liquid using a curing agent or the like, thereby forming a
wall film);
• Coacervation (phase separation) method (a method
of forming a wall film in which a polymer-dispersed liquid
containing core material particles dispersed therein is
separated into a coacervate with a high, concentration, of
polymers (dense phase) and a sparse phase, and a wall film
is formed);
• In-liquid drying method (a method of forming a
wall film in which a liquid containing core materials in a
solution of wall film materials is prepared and a dispersion
liquid is supplied to the liquid where a continuous phase of
the dispersion liquid is not miscihle so as to have a
complex emulsion, and then a wall film is formed by
gradually removing medium into which the wall film
materials are dissolved);
• Fusion dispersion cooling method (a method of
forming a wall film, in which wall film materials which are
fused upon heating and are solidified at normal
temperature are used, the materials are heated to be a
liquid, and core material particles are dispersed thereinto,
the core material particles are made to be microparticles
and cooled, thereby forming a wall film);
• Air suspension coating method (a method of
forming a wall film in which core material particles in a
powder form are suspended in the air using a fluidized bed,
and a coating liquid is sprayed and mixed with the core
material particles floating in an airflow, and then a wall
film is formed); and
• Spray drying method (a method of forming a wall
film in which an undiluted encapsulating solution is
sprayed and brought into contact with a heated air, and a
wall film is formed by allowing a volatile component to be
evaporated and dried).
In particular, the phase inversion emulsification
method, acid separation method, and interfacial
polymerization method are employed in inkjet process.
The mixing ratio of the coating polymer to the
coloring material of pigment in the recording ink is
preferably 30% to 200%, and more preferably 50% to 120%.
- Penetrant -
Addition of a penetrant to ink makes it possible to
decrease the surface tension of the resultant ink and to
promote penetration of the ink into a recording medium
such as paper after ink droplets adhere to the recording
medium, thereby making it possible to reduce occurrence of
feathering and color bleed. The desired surface tension
range in the present invention is 35mN/m or lower. As
the penetrant, an anionic surfactant or a nonionic
surfactant is usually used, and it should be selected
depending on the type of coloring material and the
combination of wetting agent and an aqueous organic
solvent used within such a range that the dispersion
stability is not impaired.
Examples of the anionic surfactant include
polyoxyethylene alkyl ether acetate salts, dodecylbenzene
sulfonates, laurates, and salts of polyoxyethylene alkyl
ether sulfates.
Examples of the nonionic surfactants include
polyols, glycol ethers, polyoxyethylene alkyl ethers,
polyoxyethylene alkyl esters, polyoxyethylene sorbitan
fatty acid esters, polyoxyethylene alkyl phenyl ethers,
polyoxyethylene alkyl amines, polyoxyethylene alkyl
amides, and acetylene glycols.
For the acetylene glycol-based surfactants, acetylene
glycol-based surfactants such as
2,4,7,9-tetramethyl-5-desine-4,7-diol,
3,6-dimethyl-4-octine-3,6-diol, and
3,5-dimethyl-1-hexine-3-ol, (e.g. SURFINOL 104, 82, 465,
485 or TG available from Air Products and Chemicals Inc.
(U.S)) may be used. Particularly, SURFINOL 465, 104
and TG can provide superior printing quality.
Examples of fluorochemical surfactants include
perfluoroalkyl sulfonates, perfluoroalkyl carboxylates,
perfluoroalkyl phosphates, perfluoroalkyl ethylene oxide
adducts, perfluoroalkyl betaines, perfluoroalkyl amine
oxides, and perfluoroalkyl ether compounds. As
commercially available fluorochemical compounds,
SURFLON-111, S-112, S-113, S121, S131, S132, S-141 and
S145 (produced by Asahi Glass Co.); FRORARD FC-93,
FC-95, FC98, FC129, FC135, FC170C, FC-430 and
FC-431 (produced by Sumitomo 3M Ltd.); MEGAFAC F470,
F1405 and F-474 (produced by Dainippon Ink and
Chemicals, Inc.); ZONYL TBS, FSP, FSA, FSN-100, FSN,
FSO-100, FSO, FS-300 and UR (produced by DuPont);
FT-110, 250, 251 and 400S (produced by Neos Co.) etc. are
available with ease and may be used in the present
invention. The above-mentioned surfactants may be used
alone or in combination in the form of mixture.
In the present invention, as a penetrant, in
particular, the use of polyol having carbon atoms of 8 to 11
or a surfactant represented by any one of the following
General Formulas (3) to (9) makes it possible to obtain
further superior printing quality.

In General Formula (3), R2 is an alkyl group that
may be branched and has 6 to 14 carbon atoms; m is an
integer of 3 to 12, and M2 is an alkali metal, a quaternary
ammonium, a quaternary phosphonium or an alkanol
amine.
In General Formula (4), E3 is a branched alkyl
group having 5 to 16 carbon atoms,' and M3 is an alkali
metal, a quaternary ammonium, a quaternary
phosphonium or an alkanol amine.

In General Formula (5), R is a carbon chain that
may be branched and has 6 to 14 carbon atoms; and' k is an
integer of 5 to 20.

In General Formula (6), R5 is a carbon chain that
may be branched and has 6 to 14 carbon atoms; and 1 is an
integer of 5 to 20.
In General Formula (7), R' is a carbon chain having
6 to 14 carbon atoms; and each of m and n is an integer
equal to or smaller than 20.

In General Formula (8), each of p and q is an integer
of 0 to 40.
[Aqueous Solvent]
- Wetting agent -
In the ink of the present invention, water is used as
a liquid medium, and with a view to preventing the ink
from being dried, improving the dispersion stability and
for other purposes, the following aqueous solvents are used.
Note that these aqueous solvents may be used in
combination in the form of mixture.
Specific examples thereof include polyhydric
alcohols such as glycerin, diethylene glycol, 1,3-butanediol,
3-methyl-l,3-butanediol, triethylene glycol, propylene
glycol, dipropylene glycol, trimethylolpropane,
trimethylolethane, ethylene glycol, diethylene glycol,
dipropylene glycol, tripropylene glycol, tetraethylene
glycol, hexylene glycol, polyethylene glycol, polypropylene
glycol, 1,5-pentanediol, 1,6-hexanediol, glycerol,
1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2,3-butanetriol, and
petriol; polyhydric alcohol alkyl ethers such as ethylene
glycol monoethyl ether, ethylene glycol monobutyl ether,
diethylene glycol monomethyl ether, diethylene glycol
monoethyl ether, diethylene glycol monobutyl ether,
tetraethylene glycol monomethyl ether, and propylene
glycol monoethyl ether; polyhydric alcohol aryl ethers such
as ethylene glycol monophenyl ether, and ethylene glycol
monobenzyl ether; nitrogen-containing heterocyclic
compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone,
N-hydroxyethyl-2-pyrrolidone, 1,3- imidazolidinone,
e-caprolactam or ?-butyrolactone; amides such as
formamide, N-methyl formamide, N, N-dimethyl
formamide; amines such as monoethanolamine,
dimethanolamine, triethanolamine, monoethylamine,
diethylamine, and triethylamine; sulfur-containing
compounds such as diemthylsulfoxide, sulfolane, and
thiodiethanol; propylene carbonate, and ethylene
carbonate.
As additional wetting agents, those containing
sugar are preferred. Examples of the sugar include
monosaccharides, disaccharides, oligosaccharides
(including trisaccharide and tetrasaccharide) and
polysaccharides. Preferred examples thereof include
glucose, mannose, fructose, ribose, xylose, arabinose,
galactose, maltose, eellobiose, lactose, sucrose, trehalose,
and maltotriose. Note that the term "polysaccharides"
means general polysaccharides, including substances that
exist widely in nature, such as crcyclodextrin, and
cellulose.
Examples of derivatives of these sugars include
reducing sugars of the above-mentioned sugars (e.g. sugar
alcohols which are represented by the general formula,
HOCH2(CHOH)nCH2OH (where n is an integer of 2 to 5),
oxidized sugars (e.g. aldonic acids, and uronic acids),
amino acids, and thio acids. Of these, sugar alcohols are
preferred. Specific examples thereof include maltitol,
and sorbitol.
In the present invention, in particular, it is possible
to produce an ink superior in storage stability and ejection
stability by using, as a wetting agent, an aqueous solvent
of glycerin, 1,3-b.utanediol, 3-metyhyl-l,3-butanediol,
hexylene glycol, polyethylene glycol, polypropylene glycol,
1,5-pentanediol, 1,6-hexanediol, propylene glycol,
dipropylene glycol, or trimethylolpropane.
The mixing ratio between coloring material
microparticles and the wetting agent significantly affects
the ejection stability of the resultant ink ejected from an
inkjet head. When the amount of the wetting agent
blended is small, though the solid content of coloring
material microparticles is high, the water evaporation in
the vicinity of an ink meniscus is promoted to cause an
ejection defect.
The amount of the wetting agent blended in the ink
is preferably 10% by mass to 50% by mass, and more
preferably 15% by mass to 40% by mass. An ink
containing a wetting agent within this range achieves
exceptionally satisfactory test results of drying property,
storage stability and reliability.
- pH adjustor -
It is possible to stabilize the dispersed condition
and the ejection of the resultant ink by adding a pH
adjustor to the ink composition so as to keep it alkaline.
When the pH of the ink is 11 or higher, the amount of the
inkjet head and ink supply unit eluted is large, causing
problems such as ink degeneration, ink leakage and
ejection defects. It is more preferable to add a pH
adjustor when the pigment is kneaded and dispersed with
the dispersant in water rather than to add it with
additives such as the wetting agent and penetrant after
kneading and dispersion treatment. This is because some
pH adjustors break the dispersion by being added to
aqueous media. The pH adjustor preferably contains at
least one or more types of alcohol amines, alkali metal
hydroxides, ammonium hydroxides, phosphonium
hydroxides and alkali metal carbonates. Examples of the
alcohol amines include diethanolamine, triethanolamine,
and 2-amino-2-ethyl-1,3-propanediol. Examples of the
alkali metal hydroxides include lithium hydroxides,
sodium hydroxides, and potassium hydroxides. Examples
of the ammonium hydroxides include ammonium
hydroxides, quaternary ammonium hydroxides, and
quaternary phosphonium hydroxides. Examples of the
alkali metal carbonates include lithium carbonates,
sodium carbonates, and potassium carbonates.
Further, to the recording ink composition of the
present invention, conventionally known additives may be
suitably selected and added. Examples of the additives
include resin emulsions, antiseptic antifungal agents,
anti-corrosion agents, antioxidants, ultraviolet absorbers,
oxygen absorbers, light absorbers and anti-kogation
agents.
- Antiseptic antifungal agent -
As the antiseptic antifungal agent, dehydrosodium
acetate, sodium sorbate, sodium 2-pyridinthiol-1-oxide,
sodium benzoate, sodium pentachlorophenol or the like
may be used in the present invention.
Examples of chelate reagents include sodium
ethylene diamine tetraacetic acid, sodium nitrilotriacetic
acid, sodium hydroxyethyl-ethylene-diamine triacetic acid,
sodium diethylene triamine pentacetic acid, and sodium
uracil diacetic acid.
- Anti-corrosion agent -
Examples of the anti-corrosion agent include acidic
sulfite, sodium thiosulfate, ammonium thiodiglycolate,
diisopropyl ammonium nitrate, pentaerythritol
tetranitrate, and dicyclohexyl ammonium nitrate.
- Antioxidant -
As the antioxidant, phenol-based antioxidants
(including hindered phenol-based antioxidants),
amine-based antioxidants, sulfur-based antioxidants, and
phosphorus-based antioxidants are exemplified.
Examples of the phenol-based antioxidants
(including hindered phenol-based antioxidants) include
butylated hydroxy anisole, 2,6-di-tert-butyl-4-ethylphenol,
stearyl-p-(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-[p-(3-tert-butyl-4-hydroxy-5-
methylphenyl)propyonyloxy]ethyl]2,4,8,10-tetraixaspiro[5
,5]undecane,
1,1,3- tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butane,
l,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-
hydroxybenzyl) benzene, and
tetrakistmethylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl
) propionate] methane.
Examples of the amine-based antioxidants include
phenyl-ß-naphthylamine, a- naphthylamine,
N,N'-di-sec-butyl-p-phenylenediamine, phenothiazine,
N,N'-dip henyl-p-phenylene diamine,
2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol,
2,4-dimethyl-6-tert-butyl-phenol, butylhydroxyanisole,
2,2'-methylenebis(4-methyl-6-tert-butylphenol),
4,4'_butylidenebis(3-methyl-6-tert-butylphenol),
4,4'-thiobis(3-methyl-6-tert-butylphenol),
tetrakis[methylene-3(3,5-di-tert-butyl-4-dihydroxyphenyl)
propionate] methane, and
1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylpheny) butane.
Examples of the sulfur-based antioxidants include
dilauryl 3,3'-thiodipropyonate,distearylthiodipropyonate,
laurylstearylthiodipropyonate,
dimyristyl-3,3'-thiodipropyonate,
distearylß,ß'-thiodipropyonate, 2-mercaptobenzoimidazole,
and dilauryl sulfide.
Examples of the phosphoric antioxidants include
triphenyl phosphite, octadecyl phosphite, triisodecyl
phosphite, trilauryltrithio phosphite, and trinonylphenyl
phosphite.
- Ultraviolet absorber -
Examples of the ultraviolet absorber include
benzophenone-based ultraviolet absorbers,
benzotriazole-based ultraviolet absorbers,
salicylate-based ultraviolet absorbers,
cyanoacrylate-based ultraviolet absorbers, and nickel
complex salt-based ultraviolet absorbers.
Examples of the benzophenone-based ultraviolet
absorbers include 2-hydroxy-4-n-octoxybenzophenone,
2-hydroxy-4-n-dodecyloxybenzophenone,
2,4-dihydroxybenzophenone,
2-hydroxy-4-methoxyhenzophenone, and
2,2',4,4'-tetrahydroxybenzophenone.
Examples of the benzotriazole-based ultraviolet
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-chloro-
benzotriazole.
Examples of the salicylatebased ultraviolet
absorbers include phenyl salicylate, p-tert-butylphenyl
salicylate, and p-octylphenyl salicylate.
Examples of the cyanoacrylate-based ultraviolet
absorbers include ethyl-2-cyano-3,3'-diphenylacrylate,
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-based
ultraviolet absorbers include nickelbis(octylphenyl)sulfide,
2,2'-thiobis(4-tert-octylphenolate)-n-butylamine nickel
(II), 2,2'-thiobis(4-tert-octylphelate)-2-ethylhexyl amine
nickel (II), 2,2'-thiobis(4-tert-octylphelate)triethanol
amine nickel (II).
- Anti-kogation agent -
An anti-kogation agent may be added to a recording
liquid used in the present invention.
The term "kogation" is a problem that could be
caused in a thermal head which is adapted to eject a
recording liquid by utilizing a foaming effect of the
recording liquid when a current is applied to a heater so as
to instantaneously heat the recording liquid, and which
means a phenomenon that the recording liquid components
deteriorate when heated, causing adhesion of deteriorated
matters (burnt deposits of ink components) onto the heater.
When kogation occurs, heating by heater is not normally
performed, resulting in weaken its ejection force, in the
worst case, causing no ejection of the recording liquid.
As the anti-kogation agent, polyphosphoric acids,
polyaminocarboxylic acids, aldonic acids,
hydroxycarboxylic acids, polyol phosphate esters, and salts
thereof, or acids having an amino group and/or salts
thereof, or ammonium salts of acids having a methyl group
or a methylene group and carboxyl group are exemplified.
Examples of the polyphosphoric acids include
pyrophosphoric acids, tripolyphosphoric acids, and
hexametaphosphoric acids.
Examples of the polyaminocarboxylic acids include
dicarboxylic acids such as oxalic acid, malonic acid,
succinic acid, and glutaric acid; ethylenediamine
tetraacetic acids, iminodiacetic acids, and nitrilotriacetic
acids.
Examples of the aldonic acids include glycolic acids,
glyceric acids, gluconic acids, galactonic acids, and
glucoheptonic acids.
Examples of the hydroxycarboxylic acids (sometimes
called oxycarboxylic acids) include citric acids, malic acids,
lactic acids, glycolic acids, glyceric acids, mandelic acids,
and tartaric acids.
Examples of the polyol phosphate ester include
a-glycerophosphoric acids, and ß-glycerophosphoric acids.
Among these, hydroxycarboxylic acids
(oxycarboxylic acids) such as citric acids, lactic acids,
gluconic acids (when gluconic acids are in the form of
solids, they exist as d-gluconolactone or ?- gluconolactone),
and tartaric acids; and a-glycerophosphoric acids and
ß-glycerophosphoric acids etc. are preferable because they
are highly soluble in water. Further, citric acids and
gluconic acids are particularly preferable. Note that
these compounds may be used in the form of acids or salts.
More specifically, these compounds may be used in the form
of alkali metal salts, ammonium salts or organic amine
salts such as triethanolamine, dimethanolamine,
monoethanolamine, and triisopropanolamine.
When any of these compounds are used,
commercially available compounds in the form of salts may
be directly used or may be used after adding thereto an
alkali agent so as to be in the form of salts of organic acids.
As the alkali agent used on that occasion, lithium,
hydroxide, sodium hydroxide, potassium hydroxide,
ammonia water (ammonium hydroxide), and organic
amines (e.g. triethanolamine, diethanolamine,
monoethanolamine, diisopropanolamine,
triisopropanolamine, tetramethylammonium hydroxide,
tetraethylammonium hydroxide, and
tetra-n-propylammonium hydroxide) are exemplified.
Among the alkali agents described above, it is preferred to
use ammonium salts.
When an ink according to the present invention is
produced, the above-mentioned anti-kogation agents may
be used alone or in combination. It is preferable to use
the anti-kogation agent in a total amount of 0.005% by
mass to 20% by mass to the total amount of the resultant
recording liquid. The total amount of the anti-kogation
agent is more preferably in the range of 0.05% by mass to
12% by mass. By adjusting the total amount of the
anti-kogation agent to the resultant recording liquid to
fall within the above range, it is possible to yield an ink
which has an advantageous effect of reducing kogation and
is least likely to cause nozzle clogging in recording heads.
Examples of the acids having an amino group and/or
salts thereof include acids having an amino group such as
amidosulfuric acid (sometimes called sulfaminic acid),
aminomethanesulfonic acid, taurine (sometimes called
2-aminoethanesulfonic acid), carbamic acid, glycin,
alanine, asparaginic acid, glutamic acid, phenylalanine,
leucine, isoleucine, threonine, triptophan,
valinemethionine, and lysine. Among these, compounds
having a sulfone group are preferable in terms that they
are highly soluble in water and have an advantageous
effect of prolonging the operating life of recording heads,
as mentioned above. Specific examples of the compounds
having a sulfone group include amidosulfuric acid
(sulfaminic acid), aminomethanesulfonic acid, and taurine
(2-aminoethanesulfonic acid). Among these, taurine
(2-aminoethanesulfonic acid) is particularly preferable in
terms of availability.
Meanwhile, when the above-mentioned acid having
an amino group and/or salts thereof are used; commercially
available compounds in the form of salts may be directly
used or may be used after adding thereto the following
alkali agents so as to be in the form of salts of organic
acids. Examples of the alkali agents include lithium
hydroxide, sodium hydroxide, potassium hydroxide,
ammonia water (ammonium hydroxide), and organic
amines (e.g. triethanolamine, diethanolamine,
monoethanolamine, diisopropanolamine,
triisopropanolamine, tetramethylammonium hydroxide,
tetraethylammonium hydroxide, and
tetra-n-propylammonium hydroxide). Among these, it is
preferred to use ammonium salts of organic acids having
an amino group.
These compounds may he used alone or in
combination. The total amount of the acids having an
amino group and/or salts thereof contained in the total
amount of the resultant recording liquid is preferably
0.005% by mass to 20% by mass, and more preferably 0.05%
by mass to 12% by mass. By adjusting the total amount of
the acids having an amino group and/or salts thereof to the
resultant recording liquid to fall within the above range
provided that the acids and/or salts are present with any of
the above-mentioned polyphosphoric acids,
polyaminocarboxylic acids, aldonic acids,
hydroxycarboxylic acids, polyol phosphate esters or salts
thereof, it is possible to yield an ink which has an
advantageous effect of reducing kogation and is least
likely to cause nozzle clogging in recording heads.
In the ink of the present invention, a mass ratio of
the total amount of the polyphosphoric acid,
polyaminocarboxylic acid, aldonic acid, hydroxycarboxylic
acid, polyol phosphate ester or salts thereof contained in
the ink relative to the total amount of the acids having an
amino group and/or salts thereof in the ink preferably falls
within the range of 20-1 to 1:20. When the mass ratio
falls within the above range, it is possible to sufficiently
exert the effect of reducing kogation on heater surfaces
and to effectively prevent damage to outermost surfaces of
protective layers.
The above-mentioned ammonium salts having a
methyl group or a methylene group and a carboxyl group
preferably have visually little effect on the color tone of
ink. In other words, an aqueous solution itself composed
of the acids is preferably colorless. Also, it is preferable
that the number of atoms per molecule of the acids be 10 or
less and the number of oxygen atoms per molecule of the
acids be 3 to 6. Specific examples of such acids include
malonic acids, succinic acids, glutaric acids, adipic acids,
lactic acids, malic acids, asparaginic acids, and glutamic
acids.
These ammonium salts having a methyl group or a
methylene group and a carboxyl group may be used alone or
in combination. Further, the total amount of at least one
compound selected from the ammonium salts of acids
having a methyl group or a methylene group and a carboxyl
group is, in view of sufficient effect of reducing kogation
and causing less clogging of inkjet recording heads, 0.005%
by mass to 20% by mass to the total amount of the
resultant ink, with the range of 0.05% by mass to 15% by
mass being more preferable.
Also, in order to prevent kogation from occurring, it
is effective to adjust phosphorous concentration of the
recording liquid. By adjusting the phosphorous
concentration to 500 ppm or less, it is possible to
effectively prevent occurrence of kogation even after
long-time storage of the ink, and the ink exhibits stable
ejection properties, making it possible to obtain
high-quality images.
The mechanism that an ink having high phosphorous
concentration promotes formation of kogation on a heater
and rapidly reduces the ink ejection amount can be
considered as follows. Inorganic phosphorous compounds
in an ink are heated in nozzles by a heater, create
compounds together with calcium which is eluted from
wetted materials in the ink and/or in the nozzles or tank
etc., and the compounds adhere to the heater surface.
Compounds derived from phosphorous and calcium
(calcium phosphate, hydroxyapatite, etc.) are very hard,
poorly soluble and are neither re-dispersed nor peeled off.
Therefore, it is considered that once the compounds adhere
onto a heater, burnt deposits of the pigment ink which have
been peeled off or re-dispersed by the effect of cavitation
increasingly adhere onto the heater, and whereby burnt
deposits of carbon, which would be unlikely to occur when
the burnt phosphorus residues do not exist, are produced
at an accelerating pace to inhibit foaming of the recording
liquid, resulting in a rapid reduction in ejection amount of
the recording liquid. The reason why the adhesion of
burnt carbon deposits is promoted by a small amount of
burnt calcium deposits is not clear, but it is presumed
because minute convexo-concave portions are caused on a
surface of a heater by the adhesion of burnt deposits of
phosphorous and calcium, and burnt carbon deposits get
into the concave portions.

Hereinbelow, a recording liquid cartridge housing a
recording liquid of the present invention, and an inkjet
recording apparatus equipped with a recording liquid
cartridge will be described with reference to the
accompanying drawings. However, the following
describes a configuration of an inkjet recording apparatus
and a configuration of a recording liquid cartridge, and
should not be construed as limiting the present invention,
in any way.
FIG. 1 is a schematic front view exemplarily showing
a configuration of a mechanical unit of a serial type inkjet
recording apparatus mounted with an ink cartridge
accommodating therein a recording liquid of the present
invention.
The mechanical unit of the inkjet recording
apparatus has side plates (1) and (2) at both sides thereof,
and a main guide rod (3) and a secondary support guide rod
(4) substantially horizontally extend between the side
plates (1) and (2) and slidably support a carriage unit (5)
in a main scanning direction. The carriage unit (5) has
four heads (6) so that their ejection surfaces (nozzle
surfaces) (6a) face downward. The four heads (6)
discharge a yellow (Y) ink, magenta (M) ink, cyan (C) ink
and black (Bk) ink, respectively. Further, the carriage
unit (5) is loaded with four ink cartridges (7y), (7m), (7c)
and (7k) above the heads (6) in an exchangeable manner,
the ink cartridges serving as ink suppliers for feeding each
of the color inks to the four heads (6).
The carriage unit (5) is connected to a timing belt
(11) which is spanned between a driving pulley (driving
timing pulley) (9) and a driven pulley (idler pulley) (10),
and the driving pulley (9) is rotated by a main scanning
motor (8). The carriage unit (5), namely the four heads
(6), is designed to move in the main scanning direction by
driving and controlling the main scanning motor (8).
Subframes (13) and (14) are vertically arranged on a
base plate (12) connecting between the side plates (1) and
(2). Between the Subframes (13) and (14) is rotatably
held a conveyance roller (15) for conveying a paper (16) in
a secondary scanning direction perpendicular to the main
scanning direction. A secondary scanning motor (17) is
arranged on the side of the Subframe (14). To transmit
the rotation of the secondary scanning motor (17) to the
conveyance roller (15), a gear (18) is fixed to the rotation
shaft of the secondary scanning motor (17), and another
gear (19) is fixed to the shaft of the conveyance roller (15).
Further, a mechanism (21) for maintaining and
improving reliability of the heads (6) (hereinafter referred
to as "subsystem") is arranged between the side plate (1)
and the subframe (13). The subsystem (21) is configured
in the following manner. Four'cap means (22) for capping
ejection surfaces of the heads (6) is held by a holder (23).
The holder (23) is rockably held by a link member (24).
When the carriage unit (5) moves in the main scanning
direction and comes in contact with a catching part (25)
arranged on the holder (23), the holder (23) is lifted up to
thereby allow the capping means (22) to cap the ejection
surfaces (6a) of the ink-jet heads (6). When the carriage
unit (5) moves toward a printing area, the holder (23) is
lifted down to thereby allow the cap means (22) to depart
from the ejection surfaces (6a) of the ink-jet heads (6).
Each of the cap means (22) is connected to a suction
pump (27) via a suction tube (26), has an air release port
and hereby communicates to the air via an air release tube
and an air release valve. The suction pump (27) aspirates
a waste liquid and discharges the same to a waste reservoir
(not shown) typically via a drain tube.
A wiper blade (28) is fixed to a blade arm (29) at the
side of the holder (23). The wiper blade (28) is wiping
means for wiping the ejection surfaces (6a) of the ink-jet
heads (6) and is composed of a fibrous material, foaming
material or elastic material such as rubber. The blade
arm (29) is rockably pivoted and is rocked by the rotation
of a cam which is rotated by a driving means (not shown).
The ink cartridge (7) will be illustrated below with
reference to FIGS. 2 and 3. FIG. 2 is an external
perspective view of an ink cartridge before loaded to a
recording apparatus, and FIG. 3 is a front cross-sectional
view of the ink cartridge.
With reference to FIG. 3, an ink cartridge (7) has a
cartridge main body (41) housing an ink absorber (42)
which absorbs an ink of predetermined color. The
cartridge main body (41) is made of typically a resinous
molded article and is composed of a case (43) having a wide
opening on its top and an upper lid member (44) bonded or
melt-fixed to the top opening. The ink absorber (42) is
composed of a porous material such as a urethane foam, is
compressed and inserted into the cartridge main body (41)
before absorbing the ink.
The case (43) of the cartridge main body (41) has an
ink supply port (45) at its bottom for supplying the ink to
the recording head (6), and a sealing ring (46) is engaged
to the inner wall of the ink supply port (45). The upper
lid member (44) has an air release port (47).
The cartridge main body (41) has a capping member
(50). The capping member (50) serves to cover the ink
supply port (45) before loading of the cartridge and to
prevent the inside ink from leaking when the cartridge is
handled typically in loading, transporting or
vacuum-packaging and a pressure is applied to the wide
side walls to thereby compress and deform the case (43).
With reference to FIG. 2, the air release port (47)
has a film sealing member (55) having an oxygen
permeability of 100 mL/m2or more affixed to the upper lid
member (44) to seal the same. The sealing member (-55)
has such a size as to cover and seal the air release port (47)
as well as plural grooves (48) arranged around the air
release port (47). The air release port (47) is thus sealed
by the sealing member (55) having an oxygen permeability
of 100 mL/m2 or more, and in addition, the ink cartridge (7)
is packaged under reduced pressure with a packaging
member such as a gas-impermeable aluminum laminated
film. This configuration can increase the deaeration of
the ink even if the ink contains dissolved gas due to the air
contaminated during ink charging or the air in a space (A)
(FIG. 3) formed between the ink absorber (42) and the
cartridge main body (41), since the air in the ink is
exhausted to a highly vacuum space between the cartridge
main body (41) and the outer packaging member via the
sealing member (55).
FIG. 4 illustrates a configuration of a recording
cartridge having a recording liquid container housing the
recording liquid of the present invention, and a head unit
for ejecting droplets of the recording liquid.
More specifically, a recording unit (30) is a serial
type recording unit and mainly consists of an ink-jet head
(6), an ink tank (41) housing the recording liquid to be
supplied to the ink-jet head (6), and a lid member sealing
the ink tank (41). The ink-jet head (6) has a plurality of
nozzles (32) for ejecting the recording liquid. The
recording liquid is fed from the ink tank (41) via an ink
supply tube (not shown) to a common chamber (not shown)
and is ejected from the nozzles (32) according to an electric
signal inputted through an electrode (31) from the
recording apparatus main body. The recording unit of this
type has a structure suitable for a "thermal" or "bubble"
head driven by action of heat energy. This type of head
can be prepared at low cost.
The serial ink-jet recording apparatus is taken as an
example in the above description, but the recording liquid
of the present invention can also be applied to a recording
apparatus having a "line head", in which nozzles and other
components are integrated at a density of equal to or one
severa.lths the resolution of the target image in an optional
arrangement such as staggered arrangement and in a
width larger than that of a recording medium used.
The "recording apparatus" used herein may be an
output printer for personal computers or digital cameras,
as well as an apparatus having composite functions in
combination with, for example, facsimile, scanner and/or
telephone.
EXAMPLES
Hereinafter, the present invention will be described
in detail referring to specific Examples and Comparative
Examples, however, the present invention is not
limited to the disclosed Examples. On the contrary, the
present invention is intended to cover various
modifications and equivalent arrangements included
within the spirit and scope of the appended claims.
(Preparation of Pigment Dispersoid)

• CINQUASIA Scarlet RT-766 [C.I. Pigment Red 207]
(a solid solution formed between an unsubstituted
quinacridone [C.I. Pigment Violet 19] and
4,11-dichloroquinacridone produced by Chiba Specialty
Chemicals K.K.)..................................... 15 parts by mass
• DISPERBYK-2010 (acrylic polymer dispersant
produced by BYK Japan K.K.) ................... 5 parts by mass
• ion exchanged water ................... 80 parts by mass
A DYNO MILL KDL A-model (manufactured by WAB
Co., Ltd.) serving as a kneader was charged with a zirconia
bead of 0.5 mm in diameter. The above materials were
mixed and agitated, and the mixture was poured into the
kneader, followed by kneading for 90 minutes at 2,000 rpm
to obtain a mill base. The mill base thus obtained was
taken out from the kneader and filtrated through a filter
having a pore size of 1 urn, thereby obtaining a solid
solution pigment-containing dispersoid A1.

A lake pigment dispersoid B1 was prepared in a
similar manner to that used for the solid solution
pigment-containing dispersoid A1 except that the pigment
was replaced with FANAL Violet 6060 (methyl violet
phosphomolybdic-tungstic acid lake [C.I. Pigment Violet 3]
produced by BASF Japan Co., Ltd.).

A solid solution pigment-containing dispersoid A2
was prepared in a similar manner to that used for the solid
solution pigment-containing dispersoid Al except that the
pigment was replaced with CROMOPHTAL Jet Magenta
2BC (a solid solution formed between an unsubstituted
quinacridone [C.I. Pigment Violet 19] and a
dimethylquinacridone [C.I. Pigment Red 122] produced by
Chiba Specialty Chemicals K.K.).

A lake pigment dispersoid B2 was prepared in a
similar manner to that used for the solid solution
pigment-containing dispersoid Al except that the pigment
was replaced with FANAL Violet 4830 (Rhodamine 6G
sulfur/molybdenum acid lake [C.I. Pigment Red 81:2]
produced by BASF Japan Co., Ltd.).

• CINQUASIA Scarlet RT-766 [C.I. Pigment Red 207]
(a solid solution formed between an unsubstituted
quinacridone [C.I. Pigment Violet 19] and
4,11-dichloroquinacridone produced by Chiba Specialty
Chemicals K.K.) ..................................... 15 parts by mass
• JONCRYL 586 (styrene acrylic polymer produced
by BASF Japan Co., Ltd.) ....................... 15 parts by mass
• 2-amino-2-methyl-l,3 propanediol 1 part by mass
• ion exchanged water ................... 69 parts by mass
JONCRYL 586 and 2-amino-2-methyl-l,3
propanediol were added to ion exchanged water so as to be
dissolved to obtain a mixture solution, CINQUASIA Scarlet
RT-766 was added to the mixture solution and sufficiently
wetted. Into a DYNO MILL KDL A-model (manufactured
by WAB Co., Ltd.) serving as a kneader which had been
charged with a zirconia bead of 0.5 mm in diameter, the
wetted components were kneaded for 40 minutes at 2,000
rpm to obtain a mill base. To the obtained mill base, 3
parts by mass of 1N hydrochloric acid were added and
agitated, and 400 parts by mass of ion exchanged water
were added thereto and sufficiently agitated. The
mixture solid solution thus obtained was subjected to
centrifugal separation using a centrifuge to separate a
pigment paste from water, and then supernatant liquid was
removed from the pigment paste. This procedure was
repeated several times. To the resultant pigment paste,
1.0 part by mass of 2-amino-2-methyl-l,3 propanediol was
added as a basic compound, and the pigment paste was
kneaded again using DYNO MILL KDL A model to obtain a
mill base. The mill base thus obtained was taken out from
the kneader and filtrated through a filter having a pore
size of 1 µm, thereby obtaining a solid solution
pigment-containing dispersoid A3.

A lake pigment dispersoid B3 was prepared in a
similar manner to that used for the solid solution
pigment-containing dispersoid A1 except that the pigment
was replaced with FANAL Violet 5460 (Rhodamine B
phosphomolybdic-tungstic acid lake [C.I. Pigment Violet 2]
produced by BASF Japan Co., Ltd.).

A solid solution pigment-containing dispersoid A4
was prepared in a similar manner to that used for the solid
solution pigment-containing dispersoid Al except that the
pigment was replaced with CROMOPHTAL Jet Magenta
2BC (a solid solution formed between an unsubstituted
quinacridone [C.I. Pigment Violet 19] and a
dimethylquinacridone [C.I. Pigment Red 122] produced by
Chiba Specialty Chemicals K.K.), and the dispersant was
replaced with a dispersant represented by Formula (2A).

A lake pigment dispersoid B4 was prepared in a
similar manner to that used for the solid solution
pigment-containing dispersoid Al except that the pigment
was replaced with FANAL Violet 5480 (Rhodamine B
phosphomolybdic acid lake [C.I. Pigment Violet 1]
produced by BASF Japan Co., Ltd.) and the dispersant was
replaced with a dispersant represented by Formula (2A).

A solid solution pigment-containing dispersoid A5
was prepared in a similar manner to that used for the solid
solution pigment-containing dispersoid Al except that the
pigment was replaced with CROMOPHTAL Jet Magenta
2BC (a solid solution formed between an unsubstituted
quinacridone [C.I. Pigment Violet 19] and a
dimethylquinacridone [C.I. Pigment Red 122] produced by
Chiba Specialty Chemicals K.K.), and the dispersant was
replaced with a dispersant represented by Formula (2B).

A lake pigment dispersoid B5 was prepared in a
similar manner to that used for the solid solution
pigment-containing dispersoid A1 except that the pigment
was replaced with FANAL Violet 5480 (Rhod amine B
phosphomolybdic acid lake [C.I. Pigment Violet 1]
produced by BASF Japan Co., Ltd.) and the dispersant was
replaced with a dispersant represented by Formula (2B).

A solid solution pigment-containing dispersoid A6
was prepared in a similar manner to that used for the solid
solution pigment-containing dispersoid A1 except that the
pigment was replaced with CINQUASIA Scarlet RT-766
[C.I. Pigment Red 207] (a solid solution formed between an
unsubstituted quinacridone [C.I. Pigment Violet 19] and
4,11-dichloroquinacridone produced by Chiba Specialty
Chemicals K.K.), and the dispersant was replaced with a
dispersant represented by Formula (1A).

A lake pigment dispersoid B6 was prepared in a
similar manner to that used for the solid solution
pigment-containing dispersoid Al except that the pigment
was replaced with FANAL Violet 5460 (Rhodamine B
phosphomolybdic-tungstic acid lake [C.I. Pigment Violet 2]
produced by BASF Japan Co., Ltd.), and the dispersant was
replaced with a dispersant represented by Formula (1A).

A solid solution pigment-containing dispersoid A7
was prepared in a similar manner to that used for the solid
solution pigment-containing dispersoid A1 except that the
pigment was replaced with CROMOPHTAL Jet Magenta
2BC (a solid solution formed between an unsubstituted
quinacridone [C.I. Pigment Violet 19] and a
dimethylquinacridone [CI. Pigment Red 122] produced by
Chiba Specialty Chemicals K.K.), and the dispersant was
replaced with a dispersant represented by Formula (1B).

A lake pigment dispersoid B7 was prepared in a
similar manner to that used for the solid solution
pigment-containing dispersoid A1 except that the pigment
was replaced with FANAL Violet 5480 (Rhodamine B
phosphomolybdic acid lake [C.I. Pigment Violet 1]
produced by BASF Japan Co., Ltd.) and the dispersant was
replaced with a dispersant represented by Formula (1B).

A pigment dispersoid C1 containing no solid solution
pigment and having no visible light absorption peak at a
wavelength between 510 nm to 530 nm and between 540 nm
to 560 nm was prepared in a similar manner to that used
for the solid solution pigment-containing dispersoid A1
except that the pigment was replaced with INK JET
Magenta E02 VP2621 (dimethylquinacridone [C.I. Pigment
Red 122] produced by Clariant Japan K.K.), and the
dispersant was replaced with a dispersant represented by
Formula (1A).

A pigment dispersoid C2 containing no lake pigment
(B) was prepared in a similar manner to that used for the
solid solution pigment-containing dispersoid A1 except
that the pigment was replaced with INK JET Magenta
E5B02 VP2984 (an unsubstituted quinacridone y-phase
[C.I. Pigment Violet 19] produced by Clariant Japan K.K.),
and the dispersant was replaced with a dispersant
represented by Formula (1B).
(Example 1)

N-meth.yl-2-pyrrolidone, 3-methyl-2,4-heptanediol, the
surfactant represented by General Formula (7),
triethanolamine and PROXEL LV were dissolved in ion
exchanged water to prepare a vehicle, the vehicle was
mixed with the solid solution pigment-containing
dispersoid A1 and the lake pigment dispersoid B1, and the
mixture liquid was filtrated through a filter having a pore
size of 1 µm, thereby obtaining a magenta recording ink.
(Example 2)
The above ink formulation was used in. a similar
manner to that of Example 1, thereby obtaining a magenta
recording ink of Example 3.
(Example 9)
A magenta recording ink of Example 9 was produced
using a similar ink formulation to that used in Example 7
and in a similar manner to that of Example 7 except that
the same coloring materials as used in Example 1 (the solid
solution pigment-containing dispersoid Al and lake
pigment dispersoid Bl) were used.
(Example 10)
A magenta recording ink of Example 10 was
produced using a similar ink formulation to that used in
Example 7 and in a similar manner to that of Example 7
except that the same coloring materials as used in Example
3 (the solid solution pigment-containing dispersoid A3 and
lake pigment dispersoid B3) were used.
(Example 11)
A magenta recording ink of Example 11 was
produced using a similar ink formulation to that used in
Example 7 and in a similar manner to that of Example 7
except that the same coloring materials as used in Example
6 (the solid solution pigment-containing dispersoid A5 and
lake pigment dispersoid B6) were used.
(Comparative Example 1)
A magenta recording ink of Comparative Example 1
was produced in a similar manner to that of Example 2
except that the solid solution pigment-containing
dispersoid A2 was used in an amount of 5 parts by mass,
and the lake pigment dispersoid B2 was used in an amount
of 40 parts by mass.
(Comparative Example 2)
A magenta recording ink of Comparative Example 2
was produced in a similar manner to that of Example 8
except that the solid solution pigment-containing
dispersoid A7 was used in an amount of 42 parts by mass,
and the lake pigment dispersoid B7 was used in an amount
of 3 parts by mass.
(Comparative Example 3)
A magenta recording ink of Comparative Example 3
was produced in a similar manner to that of Example 7
except that the solid solution pigment-containing
dispersoid A6 was replaced with the pigment dispersoid
C1.
(Comparative Example 4)
A magenta recording ink of Comparative Example 4
was produced in a similar manner to that of Example 7
except that the solid solution pigment-containing
dispersoid A6 was replaced with the pigment dispersoid C2
and the lake pigment dispersoid was not added in the ink
formulation.
A mass ratio (B/A) of the lake pigment (B) to the
solid solution pigment (A) and visible light absorption
peak values (at a wavelength 1 and a wavelength 2) of the
solid solution pigment (A) in Examples and Comparative
Examples are shown in Table 1. The visible light
absorption spectrum was measured using a
spectrophotometer (U-3310, manufactured by Hitachi Ltd.)
was used. Since the concentration of the undiluted
solution pigment dispersoid used in the present invention
is excessively high, the solution pigment dispersoid is
diluted 4,000 times with pure water and then put it in a
measurement cell of the spectrophotometer. Meanwhile,
pure water is put in a reference cell. Then, the cells were
scanned with visible light of at least a wavelength range of
from 340 nm to 800 nm at sampling intervals of 5 nm or
less to obtain a light absorption spectrum of the undiluted
solution pigment dispersoid. FIG. 5 shows visible light
absorption spectrum of the solid solution
pigment-containing dispersoid A7 and the pigment
dispersoid C2. The resulting spectrum shows that the
solid solution pigment-containing dispersoid A7 had major
light absorption peaks at wavelengths of 525 nm and 555
nm and the pigment dispersoid C2 had major light
absorption peaks at wavelengths of 540 nm and 565 nm.
(Comparative Example 5)
A magenta recording ink of Comparative Example 5
was produced in a similar manner to that of Example 7
except that the solid solution pigment-containing
dispersoid A6 was not added to the ink formulation, and
the lake pigment dispersoid B4 was used in an amount of
45 parts by mass.
Measurement results of viscosity, surface tension
and pH value of the inks produced in Examples and
Comparative Examples are described in Table 2. These
physical property values were measured by the following
methods, respectively.
(1) Viscosity
The viscosity of each of the inks was measured using
a viscometer, RC-500 manufactured by TOKI SANGYO CO.,
LTD., at a temperature of 25°C.
(2) Surface Tension
The surface tension of each of the inks was
measured using a surface tensiometer, CBVP-Z model
manufactured by Kyowa Interface Science Co., LTD., at a
temperature of 25°C.
(3) PH
The pH value of each of the inks was measured using
a pH measuring device, BOY-P2 manufactured by
Shindengen Electric Manufacturing Co., Ltd., at a
temperature of 25°C.
(Evaluation of Ejection Stability)
Each of the recording inks produced in Examples
and Comparative Examples was charged to an inkjet
printer, IPSIO GX5000 manufactured by Ricoh Company
Ltd., and the printer was set to a sleep mode where
primarily capping and cleaning functions were inoperable
during the printing operation to determine how long time,
in seconds, had elapsed since a deviation of the direction of
jetting liquid droplets from a predetermined direction
occurred or how long time, in seconds, had elapsed since
the weight of ejection liquid droplets had changed. Based
on the time length results, the reliability of ejection
stability of each of the inks was evaluated in accordance
with the following criteria. Table 3 shows the evaluation
results.

A: 600 seconds or longer
B: 300 seconds or longer and shorter than 600
seconds
C: 60 seconds or longer and shorter than 300 seconds
D: shorter than 60 seconds

Each of the recording inks produced in Examples
and Comparative Examples was charged to an inkjet
printer, IPSIO GX5000 manufactured by Ricoh Company
Ltd., and a solid image was printed in one pass. As
printing test papers, the following regular papers and
exclusive recording papers were used.
Eegular paper:
• MY PAPER SA (manufactured by NBS Ricoh Co.,
Ltd.)
• XEROX4024 (manufactured by FUJI XEROX
OFFICE SUPPLY CO., LTD.)
• PB Paper (manufactured by Canon Inc.)
Exclusive Recording Paper:
• PROFESSIONAL PHOTO PAPER PR-101
(manufactured by Canon Inc.)
• PREMIUM PLUS PHOTO PAPER (gloss paper)
(manufactured by Hewlett-Packard Co.)
(Evaluation of Hue Angle)
After drying the printed image, a hue angle of each
of the ink printed was measured using a reflective/color
spectrophotometric densitometer (manufactured by X-Rite
Co.). More specifically, a value of hue angle of the printed
image on each printing test paper was measured, and an
average value obtained from hue angle values on the three
types of regular paper for the printing test and an average
value obtained from hue angle values on the two types of
gloss paper for the printing test were calculated.
Afterward, a difference between each of the average values
to the value of hue angle (Magenta color: 356.31°) of the
standard color (Japan color Ver. 2) was determined. Table
3 shows the resultant hue angle grades obtained from the
absolute values according to the following evaluation
criteria.

A: The difference was 2° or less.
B: The difference was 2° or more and less than 5°.
C: The difference was 5° or more and less than 10°.
D: The difference was 10° or more.
(Evaluation of Chroma)
A chroma value of each of the ink image printed
above was measured using the reflective/color
spectrophotometric densitometer (manufactured by X-Rite
Co.). More specifically, a chroma value of the printed
image on each printing test paper was measured, and an
average value obtained from chroma values on the three
types of regular paper for the printing test and an average
value obtained from chroma values on the two types of
gloss paper for the printing test were calculated.
Afterward, the ratio of the average chroma value to the
chroma value (Magenta color:74.55) of the standard color
(Japan color Ver. 2) was determined. Table 3 shows the
resultant grades obtained according to the following
evaluation criteria.

A: 0.95 or more
B: 0.85 or more and less than 0.95
C: 0.75 or more and less than 0.85
D: less than 0.75
(Evaluation of Abrasion Resistance)
An ink printed portion of an image sample that had
been formed on each of the above-mentioned gloss papers
in a similar method to the chroma measurement was
abraded back and forth 5 times with white cotton cloth
under a load of 900g using a clock meter CM-1
(manufactured by TOYO SEIKI Co., Ltd.). The results of
the abrasion resistance (an average value obtained on the
two types of exclusive recording papers, i.e. gloss papers)
were evaluated according to the following criteria. Table
3 shows the evaluation results.

A: No image drop-out was visually observed, and no
contamination was visually observed around the formed
image.
B: Almost no image drop-outs were observed, and a
slight amount of contamination was observed around the
formed image, on visual basis.
C: The formed image had little image drop-out, but
contamination was observed around the formed image, on
visual basis.
D: The formed image had a significant amount of
image drop-outs, and a significant amount of
contamination was observed around the formed image, on
visual basis.
CLAIMS
1. A magenta recording ink composition comprising:
a solid solution pigment (A) containing
quinacridone,
a lake pigment (B) having a xanthene structure,
an aqueous solvent, and
water,
wherein the solid solution pigment (A) has visible
light absorption peaks at wavelength ranges of from 510
nm to 530 nm and from 540 nm to 560 nm, and a mass ratio
(B/A) of the lake pigment (B) to the solid solution pigment
(A) falls within the range of 0.1 to 5.
2. The magenta recording ink composition according to
claim 1, wherein the solid solution pigment (A) is a solid
solution (a) formed between an unsubstituted quinacridone
and a dimethylquinacridone, a solid solution (b) formed
between an unsubstituted quinacridone and a
dichloroquinacridone or a mixture of (a) and (b), and the
lake pigment (B) is C.I. Pigment Violet 1 and/or C.I.
Pigment Violet 2.
3. The magenta recording ink composition according to
any one of claims 1 and 2, wherein the aqueous solvent
comprises one or two or more of glycerin, 1,3-butandioi,
3-methyl-1,3-butandiol, hexylene glycol, polyethylene
glycol, polypropylene glycol, 1,5-pentanediol,
1,6-hexanediol, propylene glycol, dipropylene glycol, and
trimethylolpropane.
4. The magenta recording ink composition according to
any one of claims 1 to 3, wherein each of the solid solution
pigment (A) and the lake pigment (B) is dispersed by using
a dispersant represented by any one of the following
General Formulas (1) and (2),

where A1 is any one of an alkyl group that has 8 to
12 carbon atoms and may be branched, a benzyl group, a
styrenated phenol group, a distyrenated phenol group and
a ß-naphthyl group; k is an integer of 5 to 30; and M1
represents any one of an alkali metal, ammonium,
phosphonium, and alkanol amine;

where A1 is any one of an alkyl group that has 8 to
12 carbon atoms and may be branched, a benzyl group, a
styrenated phenol group, a distyrenated phenol group and
a p-naphthyl group; and i is an integer of 20 to 60.
5. The magenta recording ink composition according to
claim 4, further comprising a water-soluble polymer
having a weight average molecular mass of 2,000 to 50,000.
6. The magenta recording ink composition according to
any one of claims 1 to 4, further comprising polymer
microparticles having a volume average particle diameter
of 20 am to 150 nm and/or a polymer emulsion containing
the microparticles.
7. The magenta recording ink composition according to
any one of claims 1 to 6, further comprising any one of a
polyol having 8 or more carbon atoms, and glycol ether
having 8 or more carbon atoms.
8. The magenta recording ink composition according to
any one of claims 1 to 7, having a viscosity of 5 mPa-s to 30
mPa-s at 25°C and a surface tension of 20 mN/m to 35
mN/m and a pH of 7 to 11.
9. An Inkjet recording method comprising:
printing an ink on a recording medium by making
the magenta recording ink composition according to any
one of claims 1 to 8 adhere on the recording medium.
10. The inkjet recording method according to claim 9,
wherein the printing is performed in such a manner that
the ink is ejected by the action of thermal energy applied
to the ink.
11. The inkjet recording method according to claim 9,
wherein the printing is performed in such a manner that
the ink is ejected by the action of mechanical energy
transmitted to the ink.
12. A recorded.matter comprising: .
an image formed by the inkjet recording method
according to any one of claims 9 and 11.

The present invention provides a magenta recording ink composition including at least a solid solution pigment (A)
containing quinacridone, a lake pigment (B) having a xanthene structure, an aqueous solvent, and water, wherein the solid solution
pigment (A) has visible light absorption peaks at wavelength ranges of from 510 nm to 530 nm and from 540 nm to 560 nm, and a
mass ratio (B/A) of the lake pigment (B) to the solid solution pigment (A) falls within the range of 0.1 to 5.

Documents:

2372--kolnp-2010-abstract.pdf

2372--kolnp-2010-claims.pdf

2372--kolnp-2010-correspondence.pdf

2372--kolnp-2010-description (complete).pdf

2372--kolnp-2010-drawings.pdf

2372--kolnp-2010-form 1.pdf

2372--kolnp-2010-form 2.pdf

2372--kolnp-2010-form 3.pdf

2372--kolnp-2010-form 5.pdf

2372--kolnp-2010-gpa.pdf

2372--kolnp-2010-international publication.pdf

2372--kolnp-2010-international search report.pdf

2372--kolnp-2010-pct priority document notification.pdf

2372--kolnp-2010-pct request form.pdf

2372--kolnp-2010-specification.pdf

2372-KOLNP-2010-(10-11-2014)-ANNEXURE TO FORM 3.pdf

2372-KOLNP-2010-(10-11-2014)-CLAIMS.pdf

2372-KOLNP-2010-(10-11-2014)-CORRESPONDENCE.pdf

2372-KOLNP-2010-(10-11-2014)-OTHERS-1.pdf

2372-KOLNP-2010-(10-11-2014)-OTHERS.pdf

2372-KOLNP-2010-(10-11-2014)-PA.pdf

2372-KOLNP-2010-(10-11-2014)-PETITION UNDER RULE 137.pdf

2372-KOLNP-2010-(15-03-2013)-CORRESPONDENCE.pdf

2372-KOLNP-2010-(15-03-2013)-FORM 3.pdf

2372-KOLNP-2010-(16-12-2013)-CORRESPONDENCE.pdf

2372-KOLNP-2010-(16-12-2013)-FORM-3.pdf

2372-KOLNP-2010-(19-08-2013)-ANNEXURE TO FORM 3.pdf

2372-KOLNP-2010-(19-08-2013)-CORRESPONDENCE.pdf

2372-KOLNP-2010-(30-12-2014)-CORRESPONDENCE.pdf

2372-KOLNP-2010-ASSIGNMENT.pdf

2372-KOLNP-2010-CORRESPONDENCE 1.1.pdf

2372-KOLNP-2010-FORM 18.pdf

2372-KOLNP-2010-FORM 3 1.1.pdf

abstract-2372--kolnp-2010.jpg


Patent Number 264659
Indian Patent Application Number 2372/KOLNP/2010
PG Journal Number 03/2015
Publication Date 16-Jan-2015
Grant Date 14-Jan-2015
Date of Filing 29-Jun-2010
Name of Patentee RICOH COMPANY, LTD.
Applicant Address 3-6, NAKAMAGOME 1-CHOME, OHTA-KU, TOKYO, 1438555 JAPAN
Inventors:
# Inventor's Name Inventor's Address
1 NATORI, YUJI 1-9-501, SATSUKI-CHO, EBINA-SHI, KANAGAWA 2430421 JAPAN
2 MATSUYAMA, AKIHIKO GARDEN HEIGHTS SHIKOEN 102, 219-3, ISHIDA, ISEHARA-SHI, KANAGAWA 2591116 JAPAN
PCT International Classification Number C09D 11/00
PCT International Application Number PCT/JP2009/051141
PCT International Filing date 2009-01-20
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2008-011161 2008-01-22 Japan