Title of Invention

REFILL INK AND INK CARTRIDGE

Abstract A refill ink with which a used ink cartridge is to be refilled, including: a colorant, a wetting agent, and a surfactant, wherein in a mixed ink formed by mixing a residual ink remaining in the used ink cartridge and the refill ink at a volume ratio (residual ink : refill ink) of 1:1, the number A of coarse particles of 0.5µm or greater in diameter measured immediately after the mixing and the number B of coarse particles of 0.5µm or greater in diameter measured after the mixed ink has been left to stand at 25°C and at RH of 50% for 24 hours satisfy the relationship B/A≤2.
Full Text DESCRIPTION
REFILL INK AND INK CARTRIDGE
Technical Field
The present invention relates to a refill ink for ink-jet
recording, which is excellent in storage stability and jet stability
even when mixed with a residual ink that remains in an ink
cartridge, and an ink cartridge refilled with the refill ink.
Background Art
Ink-jet printers have been rapidly becoming commonplace
in recent years for their capability of recording onto plain paper
and realizing easy color printing, compactness, inexpensiveness,
and low running costs, etc. Along with such a rapid distribution
of ink-jet printers, there is a rapid increase in the number of ink
cartridges used. Since most of the ink cartridges are single-use
ink cartridges, they present a serious problem that they cast a
grave impact on the environment as wastes. Accordingly,
makers have been searching for an efficient ink recovery method,
but have enjoyed little success in terms of ink recovery rate.
Thus, the current situation is that little progress is made in
recycling collected cartridges.
Amongst such ink cartridges, those that have ink
absorbers inside for forming negative pressure have a problem

that since ink is poorly absorbed into the ink absorbers when
refilled, uniform negative pressure cannot be obtained or ink
spills out of the ink inlet. Also, there is a little ink remaining in
the used ink cartridge, and when the remaining ink is not to be
reused, it is necessary to provide an additional step of washing
out the remaining ink.
Hitherto, there have been various proposals concerning
refilling of an ink cartridge having an ink absorber inside.
For example, in Patent Literature 1, there is proposed a
refilling method which focuses upon an ink remaining in an ink
absorber inside an ink cartridge that is condensed by evaporation
of a solvent. This proposal supposes refilling with an ink having
the same composition.
In Patent Literature 2, as a method for recycling an ink
tank, a process of washing an internal portion thereof is
presented, and also a process of efficiently reusing a cartridge by
judging whether or not the negative pressure retaining force of an
ink absorber on the inside can be recycled is proposed. However,
this proposal is not very advisable in view of the fact that a
residual ink is not reused and a larger number of washing steps is
required.
In Patent Literature 3, there is proposed a method of
refilling an ink cartridge without causing ink to spill out of a
filling opening, by curbing the occurrence of bubbles from an ink

absorber inside the cartridge," however, this, too, merely solves a
problem typical of a cartridge provided with an ink absorber.
In Patent Literature 4, there is proposed a refilling
method which prevents a residual ink in a cartridge from being
useless. In this proposal, a time-consuming step is required
that involves measurements of the remaining amount of ink,
constituents of a residual ink and the like by absorption
spectroscopy and chromatography.
In Patent Literature 5, changes in quality or color are
prevented by keeping in a certain range the difference in physical
properties between a residual ink and a refill ink; however, the
range of the difference is narrow, and so this disclosure is lacking
in versatility.
As opposed to the proposals concerning dye-based inks,
Patent Literatures 6, 7 and 8 can, for example, be mentioned as
proposals which make it possible to replace dye inks with
pigment inks. These proposals focus upon the pH or viscosity of
both of dye-based and pigment inks, but the ranges of pH and
viscosity are limited and so these proposals are lacking in
versatility as well.
As described above, many refill inks are directed to dye
inks, but refilling using pigment inks that are becoming popular
these days has not yet been studied thoroughly, and in reality no
effective measures have been taken as to how to reuse cartridges

which have been used.
[Patent Literature l] Japanese Patent Application
Laid-open (JPA) No. 09248919
[Patent Literature 2] JP-A No. 07323560
[Patent Literature 3] Japanese Patent (JP-B) No. 3473253
[Patent Literature 4] JPA No. 07-309017
[Patent Literature 5] JP-A No. 2002-121435
[Patent Literature 6] JP-A No. 2002-60665
[Patent Literature 7] JP-A No. 2005-320509
[Patent Literature 8] JPA No. 2005-320531
Disclosure of Invention
An object of the present invention is to provide a refill ink
which is excellent in storage stability and jet stability even when
mixed with a residual ink remaining in an ink cartridge, and an
ink cartridge which makes it possible to decrease the number of
ink cartridges discarded in huge numbers and reduce an
environmental load by being refilled with the refill ink.
As a result of carrying out a series of earnest examinations
in order to solve the problems, the present inventors found the
following: regarding a refill ink which is reused in an ink-jet
recording apparatus as a used ink cartridge is refilled with the
refill ink, the refill ink can be excellent in storage stability and
jet stability and used as a refill ink even when mixed with a

residual ink that remains in the used ink cartridge, provided that
the number of coarse particles in the mixed ink does not increase
much.
The present invention is based upon the knowledge of the
present inventors, and means for solving the problems are as
follows.
≤1> 1. A refill ink with which a used ink cartridge is to be
refilled, including- a colorant,
a wetting agent, and
a surfactant,
wherein in a mixed ink formed by mixing a residual ink
remaining in the used ink cartridge and the refill ink at a volume
ratio (residual ink * refill ink) of 1-1, the number A of coarse
particles of 0.5µm or greater in diameter measured immediately
after the mixing and the number B of coarse particles of 0.5μm or
greater in diameter measured after the mixed ink has been left to
stand at 25°C and at RH of 50% for 24 hours satisfy the
relationship B/A≤2.
As to the refill ink according to ≤1>, it is hoped that an ink
having properties made as similar as possible to those of the
residual ink remaining in the cartridge to be refilled will be used
so as to match a recording system and to secure image quality,
storage stability and jet stability. However, in order to produce
refill inks that can correspond with recording systems of a wide

variety of printers commonly used today, it is necessary to
analyze constituents of residual inks and so forth, which is rather
difficult.
What is most important about a refill ink is that it
prevents clogging in a printer. To achieve this it is important to
prevent the number of coarse particles from increasing at the
time when the refill ink is mixed with a residual ink, and this can
be achieved by preparing the mixed ink such that the number of
coarse particles of 0.5μm or greater in diameter measured after
the mixed ink has been left to stand at 25°C and at RH of 50% for
24 hours is not over twice as large as the number of coarse
particles measured immediately after the mixing.
≤2> The refill ink according to ≤1>, wherein the viscosity
(C) of the mixed ink at 25°C before stored and the viscosity (D) of
the mixed ink at 25°C after stored at 25°C and at RH of 50% for
one week satisfy the relationship D/C≤2.
As to the refill ink according to ≤2>, since the jet amount
and jet velocity of the mixed ink vary according to the viscosity
thereof, it is thought probable that the larger the difference in
property between the refill ink and the residual ink becomes, the
lower image quality becomes. Accordingly, it is desirable that
the properties of the refill ink be also made as similar as possible
to those of the residual ink; however, provided that the mixed ink
is not thickened when left to stand for one week after the mixing,

there is a low risk of causing clogging, and so the refill ink can be used as a refill
ink without causing changes in its properties.
≤3> The refill ink according to any one of claims ≤1> and ≤2>,
wherein the volume average particle diameter (E) of the mixed ink before stored
and the volume average particle diameter (F) of the mixed ink after stored at 25°C
and at RH of 50% for one week satisfy the relationship F/E≤1.5.
As to the refill ink according to ≤3>, since the jet amount and jet
velocity of the mixed ink vary according to the volume average particle diameter
thereof, it is thought probable that the larger the difference in property between
the refill ink and the residual ink becomes, the lower image quality becomes.
Accordingly, it is desirable that the properties of the refill ink be also made as
similar as possible to those of the residual ink; however, provided that the average
particle diameter of the mixed ink is not increased when the mixed ink is left to
stand for one week after the mixing, there is a low risk of causing clogging, and so
the refill ink can be used as a refill ink without its properties being altered.
≤4> The refill ink according to any one of ≤1> to ≤3>, wherein the
content X of divalent metal ions in the refill ink and the content Y of divalent
metal ions in the residual ink satisfy the relationship 1≤X/Y^5.
As to the refill ink according to ≤4>, there are various mechanisms by
which pigment ink particles aggregate, but they are difficult to identify; one
possible cause for this is the amount of multivalent metal ions. As the degree of


purification of ink increases, so too does its reliability, but costs thereby increase.
In the present invention, jet reliability is secured by adjusting the amount of
multivalent metal ions contained in the refill ink in such a manner as to become
greater than one time and not over five times the amount of multivalent metal ions
contained in the residual ink; in particular, it is important to adjust the amount of
divalent metal ions contained in the refill ink.
≤5> An ink cartridge including: a container; and the refill ink
according to any one of ≤1> to ≤4>, with which the container is refilled.
The ink cartridge according to ≤5> makes it possible to prevent ink
cartridges from being discarded in huge numbers and reduce an environmental
load by being refilled with the refill ink of the present invention.
≤6> The ink cartridge according to ≤5>, wherein the ink cartridge
includes no ink absorber therein.
Brief Description of Drawings
FIG. 1 shows one example of an ink cartridge of the present invention.

FIG. 2 shows the ink cartridge of FIG. 1 with the inclusion
of a case.
Best Mode for Carrying Out the Invention
(Refill Ink)
A refill ink of the present invention is a refill ink with
which a used ink cartridge is to be refilled, containing at least a
colorant, a wetting agent and a surfactant, also containing a
penetrant, and further containing additional constituents
according to necessity.
According to the present invention, in a mixed ink formed
by mixing a residual ink remaining in the used ink cartridge and
the refill ink at a volume ratio (residual ink - refill ink) of 1:1, the
number A of coarse particles of 0.5μm or greater in diameter
measured immediately after the mixing and the number B of
coarse particles of 0.5um or greater in diameter measured after
the mixed ink has been allowed to stand at 25°C and at RH of 50%
for 24 hours satisfy the relationship B/A≤2, preferably B/A≤1.5,
more preferably 0.5≤B/A≤1.2. When B/A exceeds 2, a filter
becomes liable to clogging, and thus the jet stability of the mixed
ink may be impaired.
As used herein the phase "immediately after the mixing"
means within 30 minutes after the residual ink and the refill ink
have been mixed.

It is desirable that there be a small number of coarse
particles in the refill ink, more desirably the number of coarse
particles is in the range of 30,000 to 500,000.
Here, the number of coarse particles of 0.5μm or greater in
diameter can be measured using ACCUSIZER 780 (manufactured
by Particle Sizing Systems, Inc.), for example.
Also, in a mixed ink formed by mixing a residual ink
remaining in a used ink cartridge and a refill ink at a volume
ratio (residual ink : refill ink) of 1-1, the viscosity (C) of the
mixed ink at 25°C before stored and the viscosity (D) of the mixed
ink at 25°C after stored at 25°C and at RH of 50% for one week
preferably satisfy the relationship D/C≤2, more preferably
D/C≤1.5, even more preferably 0.8≤D/C≤1.2. When D/C exceeds
2, the viscosity becomes so high that the jet force of a head
becomes insufficient, for this reason, jet stability may be
impaired or droplets jetted may decrease in amount, and thus
there may be a decrease in image density.
As used herein the phrase "before stored" means within 30
minutes after the residual ink and the refill ink have been mixed.
The viscosity (C) of the refill ink at 25°C preferably stands
at the viscosity of a residual (exclusively made) ink ± 2mPa-s,
more preferably the viscosity of the residual (exclusively made)
ink ± ImPa-s.
Here, the viscosity can be measured using RL-500

manufactured by Toki Sangyo Co., Ltd, for example.
Also, in a mixed ink formed by mixing a residual ink
remaining in a used ink cartridge and a refill ink at a volume
ratio (residual ink : refill ink) of 1-1, the volume average particle
diameter (E) of the mixed ink at 25°C before stored and the
volume average particle diameter (E) of the mixed ink at 25°C
after stored at 25°C and at RH of 50% for one week preferably
satisfy the relationship F/E≤1.5, more preferably F/E≤1.3, even
more preferably 0.9≤F/E≤1.2. When F/E exceeds 1.5, there may
be a decrease in jet stability.
As used herein the phrase "before stored" means within 30
minutes after the residual ink and the refill ink have been mixed.
It is desirable that the volume average particle diameter of
the refill ink be 10nm to 200nm, more desirably 30nm to 150nm.
Here, the volume average particle diameter can be
measured using MICROTRAC UPA150 manufactured by Nikkiso
Co., Ltd., for example.
The content X of divalent metal ions in the refill ink and
the content Y of divalent metal ions in a residual ink preferably
satisfy the relationship 1≤X/Y≤5, more preferably 1≤X/Y≤3, even
more preferably 1≤X/Y≤2. When X/Y exceeds 5, the colorant
flocculates, and thus jet failure may be caused.
The content of divalent metal ions in the refill ink
preferably amounts to 1ppm to 50ppm. Additionally, examples

of the divalent metal ions include Ca2+, Mg2+ and Ba2+.
Here, the content of divalent metal ions in the ink can be
measured by ion chromatography or the like, for example.
The refill ink of the present invention is not particularly
limited and can be suitably selected according to the purpose as
long as it is furnished with the aforesaid characteristics; however,
as described above, the refill ink contains at least a colorant, a
wetting agent and a surfactant, also contains a penetrant, and
further contains additional constituents according to necessity.
The following explains constituents of the ink.
- Colorant —
Pigments can be suitably used for the colorant. The
pigments may be inorganic pigments or organic pigments.
Examples of the inorganic pigments include titanium oxide,
iron oxide, calcium carbonate, barium sulfate, aluminum
hydroxide, barium yellow, cadmium red, chrome yellow, carbon
blacks, Prussian blue and metal powder. Amongst these, carbon
blacks and the like are preferable. Examples of the carbon
blacks include a carbon black produced by a known process such
as a contact process, furnace process or thermal process.
Examples of the organic pigments include azo pigment,
polycyclic pigment, dye chelate, nitro pigment, nitroso pigment
and aniline black. Amongst these, azo pigment, polycyclic
pigment and the like are preferable. Examples of the azo

pigment include azo lake, insoluble azo pigment, condensed azo
pigment and chelate azo pigment. Examples of the polycyclic
pigment include phthaloeyanine pigment, perylene pigment,
perinone pigment, anthraquinone pigment, quinacridone pigment,
dioxazine pigment, indigo pigment, thioindigo pigment,
isoindolinone pigment, quinophthalone pigment,
azomethine based pigment and Rhodamine B Lake pigment.
Examples of the dye chelate include basic dye chelate and acid
dye chelate.
The colors of the pigments are not particularly limited and
can be suitably selected according to the purpose." examples of the
pigments in relation to colors include pigments for black and
pigments for colors other than black. These pigments may be
used alone or in combination.
Examples of the pigments for black include carbon blacks
(C. I. Pigment Black 7) such as furnace black, lamp black,
acetylene black and channel black; metals such as copper, iron (C.
I. Pigment Black 11) and titanium oxide; and organic pigments
such as aniline black (C. I. Pigment Black l).
Carbon blacks used for the black pigment inks are
preferably carbon blacks produced by a furnace process or a
channel process.
Such carbon blacks are not particularly limited and can be
suitably selected according to the purpose." examples thereof

include No. 2,300, No. 900, MCF-88, No. 33, No. 40, No. 45, No. 52,
MA7, MA8, MA100 and No. 2,200B (all of which are produced by
Mitsubishi Chemical Corporation); RAVEN 700, RAVEN 5,750,
RAVEN 5,250, RAVEN 5,000, RAVEN 3,500 and RAVEN 1,255 (all
of which are produced by Columbian Chemicals Company); REGA
1.400R, REGA 330R, REGA 660R, MOGUL L, MONARCH 700,
MONARCH 800, MONARCH 880, MONARCH 900, MONARCH
1,000, MONARCH 1,100, MONARCH 1,300 and MONARCH 1,400
(all of which are produced by Cabot Corporation); COLOR BLACK
FW1, COLOR BLACK FW2, COLOR BLACK FW2V, COLOR
BLACK FW18, COLOR BLACK FW200, COLOR BLACK S150,
COLOR BLACK S160, COLOR BLACK S170, PRINTEX 35,
PRINTEX U, PRINTEX V, PRINTEX 140U, PRINTEX 140V,
SPECIAL BLACK 6, SPECIAL BLACK 5, SPECIAL BLACK 4A
and SPECIAL BLACK 4 (all of which are produced by Evonik
Degussa GmbH); and BONJET CWl (produced by Orient
Chemical Industries, Ltd.).
Amongst the pigments for colors other than black,
pigments for yellow inks are not particularly limited and can be
suitably selected according to the purpose; examples thereof
include C. I. Pigment Yellows 1 (Fast Yellow G), 2, 3, 12 (Disazo
Yellow AAA), 13, 14, 16, 17, 23, 24, 34, 35, 37, 42 (yellow iron
oxide), 53, 55, 73, 74, 75, 81, 83 (Disazo Yellow HR), 93, 95, 97, 98,
100, 101, 104, 108, 109, 110, 114, 117, 120, 128, 129, 138, 150, 151,

153 and 154.
Pigments for magenta are not particularly limited and can
be suitably selected according to the purpose; examples thereof
include C. I. Pigment Reds 1, 2, 3, 5, 7, 12, 17, 22 (Brilliant Fast
Scarlet), 23, 31, 38, 48:2 (Permanent Red 2B(Ba)), 48:2
(Permanent Red 2B (Ca)), 48:3 (Permanent Red 2B (Sr)), 48:4
(Permanent Red 2B (Mn)), 49-1, 52:2, 53:1, 57:1 (Brilliant
Carmine 6B), 60:1, 63:1, 63:2, 64:1, 81 (Rhodamine 6G Lake), 83,
88, 92, 101 (red ochre), 104, 105, 106, 108 (cadmium red), 112, 114,
122 (dimethylquinacridone), 123, 146, 149, 166, 168, 170, 172,
177, 178, 179, 184, 185, 190, 193, 202, 209 and 219.
Pigments for cyan are not particularly limited and can be
suitably selected according to the purpose; examples thereof
include C. I. Pigment Blues 1, 2, 3, 15 (Copper Phthalocyanine
Blue R), 15:1, 15:2, 15:3 (Phthalocyanine Blue G), 15:4, 15:6
(Phthalocyanine Blue E), 15:34, 16, 17:1, 22, 56, 60 and 63; and C.
1. vat blues 4 and 60.
Pigments for neutral colors are not particularly limited
and can be suitably selected according to the purpose; examples
of pigments for red, green and blue include C. I. Pigment Reds
177, 194 and 224; C. I. Pigment Orange 43; C. I. Pigment Violets 3,
19, 23 and 37," and C. I. Pigment Greens 7 and 36.
Also, suitable examples of the pigments include a pigment
whose surface is modified such that at least one kind of

hydrophilic group is bonded to the surface of the pigment directly
or via another atom group (sometimes referred to as
"self-dispersing pigment"). In this case, a method of chemically
bonding a certain functional group (a functional group such as a
sulfone group or carboxyl group) to the surface of pigment, or a
method of subjecting the surface to wet oxidation with the use of
at least either a hypohalous acid or a salt thereof is employed, for
example. In particular, the form in which a carboxyl group is
bonded to the surface of a pigment dispersed in water is
particularly favorable. Since the surface of the pigment is
modified such that a carboxyl group is bonded thereto, not only
does dispersion stability improve, but also high printing quality
can be obtained and the water resistance of a recording medium
after printing improves further.
Superior in redispersibility after dried, an ink containing
the self-dispersing pigment does not cause clogging even when
printing has stopped being conducted for a long time and a water
content of the ink in the vicinity of a nozzle of an ink-jet head has
evaporated, and thus the ink easily enables favorable printing
with a simple cleaning operation. Such a self-dispersing
pigment creates a particularly great synergy effect and makes it
possible to obtain high-quality images that are even more reliable,
when combined with the after-mentioned surfactants and
penetrants.

Besides pigments of the above-mentioned form, it is also
possible to use a polymer emulsion in which a color material that
is insoluble or sparingly soluble in water is contained in polymer
particles. As used herein the phrase "a polymer emulsion in
which a color material is contained" means a polymer emulsion in
which a color material is encapsulated in polymer particles
and/or a polymer emulsion in which a color material is adsorbed
onto the surface of polymer particles. In this case, it is not that
the whole color material needs to be encapsulated or adsorbed,
but that the color material may be dispersed in the emulsion to
such an extent that the effects of the present invention are not
impaired. The color material is not particularly limited and can
be suitably selected according to the purpose as long as it is
insoluble or sparingly soluble in water and able to be contained in
the polymer; examples thereof include dyes such as oil-soluble
dyes and dispersive dyes, and the pigments mentioned as the
specific examples. Amongst these, use of the pigments is
preferable in terms of the light resistance of recorded materials
to be obtained.
Examples of the polymer which forms the polymer
emulsion include vinyl polymers, polyester polymers and
polyurethane polymers! amongst these, vinyl polymers and
polyester polymers are particularly preferable.
Further, a pigment dispersed into an aqueous medium by

means of a dispersant can be additionally used. A known
dispersant used to prepare a conventionally known pigment
dispersion solution can be applied to the dispersant; examples
thereof include polyacrylic acid, polymethacrylic acid, acrylic
acid-acrylonitrile copolymer, vinyl acetate-acrylic acid ester
copolymer, acrylic acid-acrylic acid alkyl ester copolymer,
styrene-acrylic acid copolymer, styrene-methacrylic acid
copolymer, styrene-acrylic acid-acrylic acid alkyl ester copolymer,
styrene-methacrylic acid-acrylic acid alkyl ester copolymer,
styrene-a-methylstyrene-acrylic acid copolymer,
styrene-a-methylstyrene-acrylic acid copolymeracrylic acid alkyl
ester copolymer, styrene-maleic acid copolymer,
vinylnaphthalene-maleic acid copolymer, vinyl acetate-ethylene
copolymer, vinyl acetate-fatty acid vinylethylene copolymer, vinyl
acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid
copolymer and vinyl acetate-acrylic acid copolymer.
It is desirable that the mass-average molecular mass of the
dispersant be 3,000 to 50,000, more desirably 5,000 to 30,000,
even more desirably 7,000 to 15,000.
The dispersant is suitably added to such an extent that a
pigment is stably dispersed and other effects of the present
invention are not lost, and it is desirable that the additive
amount thereof be 1:0.06 to 1:3 in mass ratio (pigment :
dispersant), more desirably 1:0.125 to 1:3.

It is desirable that a carboxyl group be bonded to the
dispersant. When a carboxyl group is bonded to a dispersant,
not only does dispersion stability improve, but also high printing
quality can be obtained and the water resistance of a recording
medium after printing improves further. Moreover, the effect of
preventing offsetting of the printed letters/characters can be
obtained. In particular, when a pigment dispersed by means of a
dispersant to which a carboxyl group is bonded is used together
with a penetrant, a sufficient drying rate can be obtained and
such an effect can be obtained that offsetting is reduced, even in
the case where a recording medium which is relatively large in
size such as plain paper is printed. It is inferred that this is due
to the fact that since the dissociation constant of carboxylic acids
is smaller than that of other acid radicals, the solubility of the
dispersant itself lowers as the pH value of the ink lowers and the
carboxylic acids interact with multivalent metal ions such as a
calcium ion that are present in the vicinity of the recording
medium surface, after the pigment has been attached to the
recording medium, and thus the dispersant itself and the pigment
flocculate.
Besides the pigments, the following dyes can be employed
as the colorant.
The water-soluble dyes are dyes classified into acid dyes,
direct dyes, basic dyes, reactive dyes and edible dyes according to

the color index, preferably ones which are superior in water
resistance and light resistance.
Examples of the acid dyes and the edible dyes include C. I.
Acid Yellows 17, 23, 42, 44, 79 and 142; C. I. Acid Reds 1, 8, 13, 14,
18, 26, 27, 35, 37, 42, 52, 82, 87, 89, 92, 97, 106, 111, 114, 115, 134,
186, 249, 254 and 289," C. I. Acid Blues 9, 29, 45, 92 and 249; C. I.
Acid Blacks 1, 2, 7, 24, 26 and 94; C. I. Food Yellows 3 and 4; C. I.
Food Reds 7, 9 and 14; and C. I. Food Blacks 1 and 2.
Examples of the direct dyes include C. I. Direct Yellows 1,
12, 24, 26, 33, 44, 50, 86, 120, 132, 142 and 144; Direct Reds 1, 4,
9, 13, 17, 20, 28, 31, 39, 80, 81, 83, 89, 225 and 227; C. I. Direct
Oranges 26, 29, 62 and 102; C. I. Direct Blues 1, 2, 6, 15, 22, 25,
71, 76, 79, 86, 87, 90, 98, 163, 165, 199 and 202; and C. I. Direct
Blacks 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168 and 171.
Examples of the basic dyes include C. I. Basic Yellows 1, 2,
11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51,
53, 63, 64, 65, 67, 70, 73, 77, 87 and 91; C. I. Basic Reds 2, 12, 13,
14, 15, 18, 22, 23, 24, 27, 29, 35, 36, 38, 39, 46, 49, 51, 52, 54, 59,
68, 69, 70, 73, 78, 82, 102, 104, 109 and 112; C. I. Basic Blues 1, 3,
5, 7, 9, 21, 22, 26, 35, 41, 45, 47, 54, 62, 65, 66, 67, 69, 75, 77, 78,
89, 92, 93, 105, 117, 120, 122, 124, 129, 137, 141, 147 and 155;
and C. I. Basic Blacks 2 and 8.
Examples of the reactive dyes include C. I. Reactive Blacks
3, 4, 7, 11, 12 and 17; C. I. Reactive Yellows 1, 5, 11, 13, 14, 20, 21,

22, 25, 40, 47, 51, 55, 65 and 67; C. I. Reactive Reds 1, 14, 17, 25,
26, 32, 37, 44, 46, 55, 60, 66, 74, 79, 96 and 97; and C. I. Reactive
Blues 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80 and 95.
It is desirable that the average particle diameter of a
pigment used in the ink be in the range of 10nm to 200nm. As
used herein the term "average particle diameter" denotes a value
of average particle diameter measured at a cumulative
percentage of 50% in the volume-based particle size distribution.
To measure a value of average particle diameter at a cumulative
percentage of 50% in the volume-based particle size distribution,
it is possible to use, for example, a method referred to as
"dynamic light scattering method (Doppler scattered light
analysis)" in which a particle undergoing Brownian motion in an
ink is irradiated with laser light, and the particle diameter is
calculated from the variation of the frequency (light frequency) of
the light (backscattered light) returning from the particle.
When the average particle diameter is smaller than 10nm,
dispersion stability in the ink is impaired, and the image density
at the time of printing becomes inferior as a result. In addition,
there will be another problem in which microparticulation of the
pigment to that level is costly. Conversely, when the average
particle diameter is greater than 200nm, the fixation properties
of images become inferior, flocculation is liable to arise during a
long period of storage, and thus clogging is liable to arise.

The content of the colorant in the ink is not particularly
limited and can be suitably selected according to the purpose,"
however, it is preferably 0.5% by mass to 15% by mass, more
preferably 5% by mass to 12% by mass.
- Wetting Agent -
The wetting agent is not particularly limited and can be
suitably selected according to the purpose? examples thereof
include multivalent alcohols, multivalent alcohol alkyl ethers,
multivalent alcohol aryl ethers, nitrogen-containing heterocyclic
compounds, amides, amines, sulfur-containing compounds,
propylene carbonate and ethylene carbonate. These may be used
alone or in combination. Amongst these, multivalent alcohol
alkyl ethers and multivalent alcohol aryl ethers are particularly
preferable. Inclusion of such wetting agents makes it possible to
prevent a water content of an ink from evaporating, more
favorably prevent curb deposition of a colorant at an ink-jet
orifice and jet failure caused by a rise in viscosity, and thus
provide a pigment ink which is high in jet reliability.
Examples of the multivalent alcohols include ethylene
glycol, diethylene glycol, triethylene glycol, polyethylene glycol,
polypropylene glycol, 1,3-propanediol, 1,3-butanediol,
1,4-butanediol, 3-methyl-l,3-butanediol, 1,5-pentanediol,
1,6-hexanediol, glycerol, 1,2,6-hexanetriol, l,2,4butanetriol,
l,2,3butanetriol and petriol.

Examples of the multivalent alcohol alkyl ethers include
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.
Examples of the multivalent alcohol aryl ethers include
ethylene glycol monophenyl ether and ethylene glycol monobenzyl
ether.
Examples of the nitrogen-containing heterocyclic
compounds include N-methyl-2-pyrrolidone,
N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone,
1,3-dimethylimidazolidinone and e-caprolactam.
Examples of the amides include formamide,
N-methylformamide and N,N-dimethylformamide.
Examples of the amines include monoethanolamine,
diethanolamine, triethanolamine, monoethylamine, diethylamine
and triethylamine.
Examples of the sulfur-containing compounds include
dimethylsulfoxide, sulfolane and thiodiethanol.
Amongst these, glycerin, ethylene glycol, diethylene glycol,
triethylene glycol, propylene glycol, dipropylene glycol,
tripropylene glycol, 1,3-butanediol, 2,3-butanediol,
l,4butanediol, 3methyl-1,3-butanediol, 1,3-propanediol,
l,5pentanediol, tetraethylene glycol, 1,6-hexanediol,

2methyl-2,4-pentanediol, polyethylene glycol, 1,2,4-butanetriol,
1,2,6-hexanetriol, thiodiglycol, 2pyrrolidone,
Nmethyl-2-pyrrolidone and Nhydroxyethyl-2-pyrrolidone are
preferable, with glycerin, 3-methyl-l,3-butanediol and
2-pyrrolidone being particularly preferable, in that it is possible
to obtain superior effects on solubility and prevention of jet
characteristic failure caused by evaporation of a water content.
It is desirable that the content of the wetting agent in the
ink be 5% by mass to 30% by mass, more desirably 10% by mass to
30% by mass. When the content is less than 5% by mass, the
effects given by adding the wetting agent are insufficient; when
the content is greater than 30% by mass, the viscosity of the
aqueous ink becomes high, thus possibly affecting jet stability.
- Surfactant -
The surfactant is not particularly limited and can be
suitably selected according to the purpose", examples thereof
include anionic surfactants, nonionic surfactants, ampholytic
surfactants, fluorine-based surfactants and silicone "based
surfactants. Addition of such surfactants makes it possible to
obtain high-quality images with enhanced penetrativeness to
paper and rapid drying properties, in which the bleeding of
letters/characters and boundaries is further reduced.
Examples of the anionic surfactants include
polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate,

laurate and salts of polyoxyethylene alkyl ether sulfate.
Examples of the nonionic surfactants include acetylene
glycol-based surfactants, polyoxyethylene alkyl ether,
polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester
and polyoxyethylene sorbitan fatty acid ester.
Examples of the acetylene glycol-based surfactants include
2,4,7,9-tetramethyl-5-decyne-4,7-diol,
3,6-dimethyl-4octine-3,6-diol and 3,5-dimethyl-l-hexyne-3ol.
Examples of the acetylene glycol-based surfactants as
commercially-supplied products include SURFYNOLs 104, 82,
465, 485 and TG produced by Air Products and Chemicals, Inc.
(USA).
Examples of the ampholytic surfactants include
laurylamino propionate, lauryldimethylbetaine,
stearyldimethylbetaine and lauryldihydroxyethylbetaine.
Specific examples thereof include lauryl dimethyl amine oxide,
myristyl dimethyl amine oxide, stearyl dimethyl amine oxide,
dihydroxy ethyl lauryl amine oxide, polyoxyethylene coconut oil
alkyldimethyl amine oxide, dimethylalkyl (coconut) betaine and
dimethyllaurylbetaine.
Amongst the surfactants, nonionic surfactants and anionic
surfactants are preferable, and polyoxyethylene alkyl
ether-based surfactants and polyoxyethylene alkyl ether
acetate-based surfactants are particularly preferable. These

may be used alone or in combinaiton. When a single surfactant
is sparingly soluble in a recording solution, it can be made
soluble by being mixed with other surfactant(s) to exist stably.
Additionally, it is desirable that inorganic salts produced as
byproducts when surfactants are synthesized be purified by an
ion-exchange resin and removed.
Suitable examples of commercially-supplied surfactants
include the BT series obtainable from Nikko Chemicals Co., Ltd.,
the SOFTANOL series obtainable from Nippon Shokubai Co., Ltd.,
DISPANOL obtainable from NOF Corporation, the NIKKOL ETC
series and the NIKKOL AKYPO series obtainable from Nikko
Chemicals Co., Ltd. and the BEAULIGHT series obtainable from
Sanyo Chemical Industries, Ltd.
In order to improve image quality further, it is desirable to
use fluorinebased surfactants or silicone-based surfactants with
great penetrativeness, with fluorine-based surfactants being
particularly desirable.
The silicone-based surfactants are not particularly limited
and can be suitably selected according to the purpose, preferably
ones that do not decompose even at high pH values; examples
thereof include side-chain-modified polydimethylsiloxane,
bothterminalmodified polydimethylsiloxane,
either-terminal-modified polydimethylsiloxane and
side-chain-both-terminal-modified polydimethylsiloxane.

Amongst these, ones having polyoxyethylene groups or
polyoxyethylenepolyoxypropylene groups as modification groups
are particularly preferable in that they exhibit favorable
characteristics as aqueous surfactants.
As such surfactants, suitably synthesized surfactants or
commercially-supplied surfactants may be used. The
commercially-supplied surfactants can be easily obtained from
BYK Additives & Instruments, Shin-Etsu Chemical Co., Ltd. and
Dow Corning Toray Co., Ltd., for example.
Examples of the fluorine-based surfactants include
perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic
compounds, perfluoroalkyl phosphoric acid ester compounds,
perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether
polymer compounds having perfluoroalkylether groups as side
chains. Amongst these, polyoxyalkylene ether polymer
compounds having perfluoroalkylether groups as side chains are
particularly preferable because they are low in foaming property
and also in the bioaccumulation potential of fluorine compounds
that is deemed to be a problem these days and are therefore safe.
Examples of the perfluoroalkyl sulfonic acid compounds
include perfluoroalkyl sulfonic acids and perfluoroalkyl
sulfonates.
Examples of the perfluoroalkyl carboxylic compounds
include perfluoroalkyl carboxylic acids and perfluoroalkyl

carboxylates.
Examples of the perfluoroalkyl phosphoric acid ester
compounds include perfluoroalkyl phosphoric acid esters and
salts of perfluoroalkyl phosphoric acid esters.
Examples of the polyoxyalkylene ether polymer compounds
having perfluoroalkylether groups as side chains include
polyoxyalkylene ether polymers having perfluoroalkylether
groups as side chains, sulfuric acid ester salts of polyoxyalkylene
ether polymers having perfluoroalkylether groups as side chains,
and salts of polyoxyalkylene ether polymers having
perfluoroalkylether groups as side chains.
Examples of counterions for salts in these fluorine-based
surfactants include Li, Na, K, NH4, NH3CH2CH2OH,
NH2(CH2CH20H)2 and NH(CH2CH2OH)3.
As the fluorine-based surfactants, suitably synthesized
surfactants or commercially-supplied surfactants may be used.
Examples of the commercially-supplied surfactants
include SURFLONs Sill, S112, S113, S121, S-131, S-132,
S-141 and S-145 (all of which are produced by Asahi Glass Co.,
Ltd.), FLUORADs FC-93, FC-95, F098, FC129, FC135,
FC-170C, FC-430 and F0431 (all of which are produced by
Sumitomo 3M Limited), MEGAFACs F-470, F-1405 and F-474 (all
of which are produced by Dainippon Ink And Chemicals,
Incorporated), ZONYLs TBS, FSP, FSA, FSN100, FSN, FSO100,

FSO, FS-300 and UR (all of which are produced by E. I. du Pont
de Nemours and Company), FT-110, FT-250, FT-251, FT-400S,
FT-150 and FT-400SW (all of which are produced by Neos
Company Limited), and PF-151N (produced by OMNOVA
Solutions Inc.). Amongst these, ZONYLs FS-300, FSN, FSN-100
and FSO (all of which are produced by E. I. du Pont de Nemours
and Company) are particularly preferable in that they are
excellent in reliability and coloring improvement.
It is desirable that the content of the surfactant in the ink
be 0.01% by mass to 5.0% by mass, more desirably 0.5% by mass
to 3% by mass. When the content is less than 0.01% by mass, the
addition of the surfactant is not effective; when the content is
greater than 5.0% by mass, penetrativeness to a recording
medium becomes greater than necessary, and so there may be a
decrease in image density or offsetting may arise.
- Penetrant -
For the penetrant, a polyol compound, a glycol ether
compound or the like is used; in particular, at least either a polyol
compound or glycol ether compound having eight or more carbon
atoms is suitable.
When the polyol compound has fewer than eight carbon
atoms, a recording medium may be stained at the time of
double-side printing because of insufficient penetrativeness, and
an image may be poorly filled with image elements or dots

because ink does not sufficiently spread over the recording
medium, so that there may be a decrease in letter/character
quality and image density.
Suitable examples of the polyol compound having eight or
more carbon atoms include 2ethyll,3-hexanediol and
2,2,4-trimethyl-l,3-pentanediol.
The glycol ether compound is not particularly limited and
can be suitably selected according to the purpose. Examples
thereof include multivalent 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"> and
multivalent alcohol aryl ethers such as ethylene glycol
monophenyl ether and ethylene glycol monobenzyl ether.
The additive amount of the penetrant to the ink is not
particularly limited and can be suitably selected according to the
purpose; however, it is preferably 0.1% by mass to 20% by mass,
more preferably 0.5% by mass to 10% by mass.
- Antifoaming Agent -
An antifoaming agent may be added to the ink of the
present invention. Siliconebased antifoaming agents, many of
which are particularly superior in foam-breaking effect, are
classified into oil type, compound type, self-emulsification type,

emulsion type and the like; when use thereof in an aqueous
system is considered, use of the selfemulsification type or the
emulsion type is preferable in that reliability is secured. Also,
modified silicone-based antifoaming agents such as
amino-modified antifoaming agents, carbinol-modified
antifoaming agents, methacryl-modified antifoaming agents,
polyether-modified antifoaming agents, alkyl-modified
antifoaming agents, higher fatty acid ester modified antifoaming
agents and alkylene oxide modified antifoaming agents may be
used.
The additive amount of the antifoaming agent is not
particularly limited and can be suitably selected according to the
purpose; however, it is preferably 0.001% by mass to 3% by mass,
more preferably 0.05% by mass to 0.5% by mass.
Examples of available commercially-supplied antifoaming
agents include silicone antifoaming agents (such as KS-508,
KS-531, KM-72 and KM-85) produced by ShinEtsu Chemical Co.,
Ltd., silicone antifoaming agents (such as Q2-3183A and SH5510)
produced by Dow Corning Toray Co.,Ltd., silicone antifoaming
agents (such as SAG30) produced by Nippon Unicar Company
Limited, and antifoaming agents (such as the ADEKANATE
series) produced by Adeka Corporation.
— Additional Constituents —
The additional constituents are not particularly limited

and can be suitably selected according to necessity." examples
thereof include a pH adjuster, a preservative/antimold agent, an
anticorrosive, an antioxidant, an ultraviolet absorber, an oxygen
absorber and a light stabilizer.
Examples of the preservative/antimold agent include
l,2-benzisothiazolin-3-one, sodium dehydroacetate, sodium
sorbate, 2-pyridinethiol-l-sodium oxide, sodium benzoate and
sodium pentachlorophenol.
The pH adjuster is not particularly limited as long as it
can adjust the pH of the prepared ink to 7 or greater without
adversely affecting it, and any compound can be employed
according to the purpose. Examples of the pH adjuster include
amines such as diethanolamine and triethanolamineJ hydroxides
of alkali metal elements such as lithium hydroxide, sodium
hydroxide and potassium hydroxide; ammonium hydroxide,
quaternary ammonium hydroxide and quaternary phosphonium
hydroxide; and carbonates of alkali metals such as lithium
carbonate, sodium carbonate and potassium carbonate.
Examples of the anticorrosive include acid sulfite, sodium
thiosulfate, ammonium thiodiglycolate, diisopropylammonium
nitrite, pentaerythritol tetranitrate and dicyclohexylammonium
nitrite.
Examples of the antioxidant include phenol antioxidants
(including hindered phenol antioxidants), amine antioxidants,

sulfur antioxidants and phosphorus antioxidants.
The refill ink of the present invention used in an ink-jet
recording process is produced by dispersing or dissolving at least
a colorant, a wetting agent and a surfactant, with additional
constituents included according to necessity, in an aqueous
solvent, and further, mixing the ingredients by means of
agitation according to necessity. The dispersion can, for
example, be conducted by means of a sand mill, a homogenizer, a
ball mill, a paint shaker, an ultrasonic disperser, etc., and the
agitation/mixing can be conducted by means of a typical agitator
with an agitating blade, a magnetic stirrer, a high-speed
disperser, etc.
The coloring of the ink is not particularly limited and can
be suitably selected according to the purpose; for example, the
ink is colored yellow, magenta, cyan or black. When recording is
conducted using an ink set in which two or more of the colors are
used together, it is possible to form a multicolor image, and when
recording is conducted using an ink set in which all the colors are
used together, it is possible to form a full-color image.
(Ink Cartridge)
The ink cartridge of the present invention includes a
container, and the refill ink of the present invention with which
the container is refilled, and further includes additional members
and the like suitably selected according to necessity. It is

possible to prevent massive disposal of ink cartridges and thus to
reduce an environmental load by refilling the ink cartridge with
the refill ink of the present invention.
The ink cartridge does not have an ink absorber therein.
This makes it easier to refill the ink cartridge with the refill ink.
The container is not particularly limited, and the shape,
structure, size, material and the like thereof can be suitably
selected according to the purpose; suitable examples thereof
include a container having at least an ink bag or the like formed
of an aluminum laminated film, resinous film, etc.
Next, the ink cartridge will be explained with reference to
FIGS. 1 and 2. Here, FIG. 1 is a figure showing one example of
an ink cartridge of the present invention, and FIG. 2 is a figure
showing the ink cartridge 10 of FIG. 1 with the inclusion of a case
(external cover).
As shown in FIG. 1, the ink cartridge 10 fills up as the
refill ink flows from an ink inlet 42 into an ink bag 41, and the
ink inlet 42 is closed by fusion after air is discharged. When the
ink cartridge 10 is used, an ink outlet 43 formed of a rubber
member is penetrated by a needle of an apparatus main body, and
the ink cartridge 10 is thus installed in the apparatus.
The ink bag 41 is formed of an air-impermeable packing
member such as an aluminum laminated film. As shown in FIG.
2, this ink bag 41 is normally housed in a cartridge case 44 made

of plastic, and used in such a manner as to be detachably
mounted on a variety of ink-jet recording apparatuses.
EXAMPLES
The following explains Examples of the present invention,'
however, it should be noted that the present invention is not
confined to these Examples in any way. Note that "%" means "%
by mass" unless otherwise indicated.
- Preparation of Residual Inks Nos. 1 to 4 -
Printing was carried out using a black ink, a yellow ink, a
magenta ink and a cyan ink, which are made exclusively for a
GEL JET printer (iPSiO G717 produced by Ricoh Company, Ltd.)
and contained in their respective ink cartridges. Thus a
residual ink No. 1 (black, BK), a residual ink No. 2 (yellow, Y), a
residual ink No. 3 (magenta, M) and a residual ink No. 4 (cyan, C)
remaining in the respective used ink cartridges were prepared.
(Production Example l)
- Preparation of Refill Ink No. 1 (Black Ink) -
An ink composition with the following formulation was
produced and sufficiently agitated at room temperature, then it
was filtered through a membrane filter of 0.8μm in average pore
diameter, and refill ink No. 1 was thus produced.
• carbon black (BONJET CW-1 produced by Orient
Chemical Industries, Ltd.) •-• 30%

• glycerin ... 7.5%
• diethylene glycol -•- 22.5%
• 2-pyrrolidone --• 2%
• surfactant (ECTD-3NEX produced by Nikko Chemicals
Co., Ltd., polyoxyethylene alkyl ether acetate) -•• 1%
• silicone antifoaming agent (KS-508 produced by
Shin-Etsu Chemical Co., Ltd., self-emulsifying type) •••
0.1%
• ion-exchange water ••- the rest of the amount
(Production Example 2)
Preparation of Refill Ink No, 2 (Yellow Ink)>
— Production of Yellow Pigment Dispersion Solution 1 -
The following constituents were mixed together, then the
mixture was dispersed by means of a wet sand mill and
centrifuged to remove coarse particles, and a yellow pigment
dispersion solution 1 was thus produced.
• C. I. Pigment Yellow 97 - 30%
• polyoxyethylene oleyl ether ammonium sulfate ••• 15%
by mass
• ethylene glycol --- 30% by mass
• deionized water •-- the rest of the amount
- Production of Yellow Ink -
An ink composition with the following formulation was
produced and sufficiently agitated at room temperature, then it

was filtered through a membrane filter of 1.2μm in average pore
diameter, and refill ink No. 2 was thus produced.
• yellow pigment dispersion solution 1 — 10%
• glycerin ••- 8%
• polyethylene glycol -•• 20%
• acetylene glycol-based surfactant (SURFYNOL 465
produced by Air Products and Chemicals, Inc.) •■• 1%
• silicone antifoaming agent (KS-531 produced by
Shin-Etsu Chemical Co., Ltd.) — 0.1%
• ion-exchange water ••• the rest of the amount
(Production Example 3)
≤Preparation of Refill Ink No. 3 (Magenta Ink)>
- Production of Magenta Pigment Dispersion Solution 2 -
The following constituents were mixed together, then the
mixture was dispersed by means of a three-roll mill, and a
magenta pigment dispersion solution 2 was thus produced.
• C. I. Pigment Red 122 - 30%
• polyoxyethylene oleyl ether ammonium sulfate — 15%
• glycerin — 30%
• deionized water ••• the rest of the amount
- Production of Magenta Ink -
An ink composition with the following formulation was
produced and sufficiently agitated at room temperature, then it
was filtered through a membrane filter of 1.2μm in average pore

diameter, and refill ink No. 3 was thus produced.
• magenta pigment dispersion solution 2 ... 10%
• glycerin ••- 8%
• diethylene glycol ••• 22%
• 2,2,4-trimethyl-l,3-pentanediol — 2%
• surfactant (ECTD-3NEX produced by Nikko Chemicals
Co., Ltd., polyoxyethylene alkyl ether acetate) -•• 1%
• silicone antifoaming agent (KS-531 produced by
Shin-Etsu Chemical Co., Ltd.) - 0.1%
• ion-exchange water ••- the rest of the amount
(Production Example 4)
≤Preparation of Refill Ink No. 4 (Cyan Ink)>
- Production of Cyan Pigment Dispersion Solution 3 —
The following constituents were mixed together, then the
mixture was dispersed by means of a wet sand mill, and a cyan
pigment dispersion solution 3 was thus produced.
• C. I. Pigment Blue 15:3 - 30%
• polyoxyethylene oleyl ether ammonium sulfate ••• 15%
• ethylene glycol ••• 30%
• deionized water --- the rest of the amount
- Production of Cyan Ink -
An ink composition with the following formulation was
produced and sufficiently agitated at room temperature, then it
was filtered through a membrane filter of 1.2μm in average pore

diameter, and refill ink No. 4 was thus produced.
• cyan pigment dispersion solution 3 --- 15%
• glycerin ... 8%
• diethylene glycol ••• 22%
• 2,2,4-trimethyl-l,3pentanediol ... 2%
• surfactant (ECTD-3NEX produced by Nikko Chemicals
Co., Ltd., polyoxyethylene alkyl ether acetate) ••• 1%
• silicone antifoaming agent (KS-531 produced by
Shin-Etsu Chemical Co., Ltd.) — 0.1%
• ion-exchange water ••• the rest of the amount
(Production Example 5)
- Preparation of Refill Ink No. 5 (Cyan Ink) -
An ink composition according to the following formulation
was produced and sufficiently agitated at room temperature, then
it was filtered through a membrane filter of 1.2jim in average
pore diameter, and refill ink No. 5 was thus produced.
• C. I. Direct Blue 199 — 5%
• glycerin -•- 7%
• diethylene glycol — 23%

• surfactant (ECTD-3NEX produced by Nikko Chemicals
Co., Ltd., polyoxyethylene alkyl ether acetate) ... 1%
• silicone antifoaming agent (KS-531 produced by
Shin-Etsu Chemical Co., Ltd.) - 0.1%
• ion-exchange water ••• the rest of the amount

(Production Example 6)
- Preparation of Refill Ink No. 6 (Magenta Ink) -
An ink composition according to the following formulation
was produced and sufficiently agitated at room temperature, then
it was filtered through a membrane filter of 1.2um in average
pore diameter, and refill ink No. 6 was thus produced.
• C. I. Direct Red 227 •- 5%
• glycerin •-- 7.5%
• diethylene glycol ••• 22.5%
• surfactant (ECTD3NEX produced by Nikko Chemicals
Co., Ltd., polyoxyethylene alkyl ether acetate) ••• 1%
• silicone antifoaming agent (KS-531 produced by
Shin-Etsu Chemical Co., Ltd.) - 0.1%
• ion-exchange water ■-• the rest of the amount
(Production Example 7)
- Preparation of Refill Ink No. 7 (Black Ink) -
An ink composition with the following formulation was
produced and sufficiently agitated at room temperature, then it
was filtered through a membrane filter of 0.8^im in average pore
diameter, and refill ink No. 7 was thus produced.
• carbon black (CABOJET 200 produced by Cabot
Corporation) - 30%
• glycerin ••• 8%
• diethylene glycol ••• 22%

• 2-pyrrolidone --• 2%
• surfactant (ECTD-3NEX produced by Nikko Chemicals
Co., Ltd., polyoxyethylene alkyl ether acetate) ••• 1%
• silicone antifoaming agent (KS531 produced by
Shin-Etsu Chemical Co., Ltd.) ... 0.1%
• ion-exchange water ••• the rest of the amount
(Production Example 8)
- Preparation of Refill Ink No. 8 (Magenta Ink) -
An ink composition according to the following formulation
was produced and sufficiently agitated at room temperature, then
it was filtered through a membrane filter of 0.8µm in average
pore diameter, and refill ink No. 8 was thus produced.
• magenta pigment dispersion solution 2 -•- 20%
• glycerin -•- 10%
• diethylene glycol — 20%
• 2-pyrrolidone ... 2%

• surfactant (ECTD-3NEX produced by Nikko Chemicals
Co., Ltd., polyoxyethylene alkyl ether acetate) ... 1%
• diethylene glycol monobutyl ether ... 1.5%
• silicone antifoaming agent (KS-531 produced by
Shin-Etsu Chemical Co., Ltd.) ... 0.1%
• ion-exchange water ... the rest of the amount
Next, the residual inks Nos. 1 to 4 and the refill inks Nos.
1 to 8 were measured for their respective properties in the

following manner. The results are shown in Table 1.

Each ink (5µl) was measured for the number of coarse
particles of 0.5µm or greater in diameter using ACCUSIZER 780
(produced by Particle Sizing Systems, Inc.).

The amount of divalent metal ions (Ca2+ and Mg2+)
contained in each ink solution prepared by filtering a tenfold
dilution of ink through a filter of 0.2µm in average pore diameter
was measured using ICA-5222 (ion chromatography) produced by
DKKTOA CORPORATION.

The viscosity of each ink was measured at 25°C using
RL-500 produced by Toki Sangyo Co., Ltd.

The volume average particle diameter of each ink was
measured using MICROTRAC UPA150 produced by Nikkiso Co.,
Ltd., by using an ink solution diluted to a pigment concentration
of 0.01% by mass.


Judging from the results of Table 1, it was found that the
content X of divalent metal ions in the refill ink and the content Y
of divalent metal ions in the residual ink satisfied the
relationship
Next, Evaluations 1, 2 and 3 were carried out on mixed
inks each formed by combining any of the residual inks Nos. 1 to 4
and any of the refill inks Nos. 1 to 8.

in Inks>
Mixed inks formed by combining the residual inks Nos. 1 to
4 and the refill inks Nos. 1 to 8 as in Table 2 at a volume ratio of
1-1 were measured for the number of coarse particles of 0.5µm or
greater in diameter immediately after mixing and also after being
allowed to stand at 25°C and at RH of 50% for 24 hours
subsequent to mixing. The results are shown in Table 2.
Additionally, as to the number of coarse particles, each
mixed ink (5µl) was measured for the number of coarse particles
of 0.5pm or greater in diameter using ACCUSIZER 780 (produced
by Particle Sizing Systems, Inc.).



Mixed inks each formed by combining any of the residual
inks Nos. 1 to 4 and any of the refill inks Nos. 1 to 8 as shown in
Tables 3 and 4 at a volume ratio 1-1 were stored for one week at
25°C and at RH of 50% and also at 50°C and at RH of 30% and
measured for their viscosities and average particle diameters
before and after the storage. The viscosity of each mixed ink
was measured at 25°C using RL-500 produced by Toki Sangyo Co.,

Ltd. The volume average particle diameter of each mixed ink
was measured using a MICROTRAC UPA150 produced by Nikkiso
Co., Ltd., using a mixed ink solution diluted to a pigment
concentration of 0.01% by mass. The results are shown in Tables
3 and 4.




An continuous printing evaluation was carried out on
mixed inks each formed by combining any of the residual inks Nos.
1 to 4 and any of the refill inks Nos. 1 to 8 as shown in Table at a
volume ratio of 1:1.
Using a GELJET printer (IPSiO G717 produced by Ricoh
Company, Ltd.) as an evaluation device, continuous printing was
conducted for a chart provided with solid images of respective

colors by discharging corresponding color inks in equal amounts
per printing, followed by determination of the number of print
sheets in which no image blur was generated. The numbers of
sheets that succeeded in continuous printing with no image blur
are shown in Table 5.

According to the results in Tables 2 to 5, the inks of
Examples 1 to 6, whose B/A values in Evaluation 1 were 2 or less,
proved favorable in terms of both storage stability in Evaluation
2 and jet stability in Evaluation 3.
Meanwhile, the inks of Comparative Examples 1 and 2,
whose B/A values in Evaluation 1 were greater than 2, proved

unfavorable in terms of both storage stability in Evaluation 2 and
jet stability in Evaluation 3.
Industrial Applicability
The refill ink of the present invention is excellent in jet
stability and storage stability, enables high-quality image
recording, and enables a used ink cartridge to be reused as the
used ink cartridge is refilled with the refill ink and to be thus
prevented from being discarded.

CLAIMS
1. A refill ink with which a used ink cartridge is to be refilled,
comprising:
a colorant,
a wetting agent, and
a surfactant,
wherein in a mixed ink formed by mixing a residual ink
remaining in the used ink cartridge and the refill ink at a volume
ratio (residual ink : refill ink) of 1:1, the number A of coarse
particles of 0.5µm or greater in diameter measured immediately
after the mixing and the number B of coarse particles of 0.5µm or
greater in diameter measured after the mixed ink has been left to
stand at 25°C and at RH of 50% for 24 hours satisfy the
relationship B/A≤2.
2. The refill ink according to claim 1, wherein the viscosity
(C) of the mixed ink at 25°C before stored and the viscosity (D) of
the mixed ink at 25°C after stored at 25°C and at RH of 50% for
one week satisfy the relationship D/C≤2.
3. The refill ink according to any one of claims 1 and 2,
wherein the volume average particle diameter (E) of the mixed
ink before stored and the volume average particle diameter (F) of
the mixed ink after stored at 25°C and at RH of 50% for one week

satisfy the relationship F/E≤1.5.
4. The refill ink according to any one of claims 1 to 3, wherein
the content X of divalent metal ions in the refill ink and the
content Y of divalent metal ions in the residual ink satisfy the
relationship 1 5. An ink cartridge comprising:
a container, and
the refill ink according to any one of claims 1 to 4, with
which the container is refilled.
6. The ink cartridge according to claim 5, wherein the ink
cartridge comprises no ink absorber therein.

A refill ink with which a used ink cartridge is to be refilled, including: a colorant, a wetting agent, and a surfactant, wherein in a mixed ink formed by mixing a residual ink remaining in the used ink cartridge and the refill ink at a volume ratio (residual ink : refill ink) of 1:1, the number A of coarse particles of 0.5µm or greater in diameter measured immediately after the mixing and the number B of coarse particles of 0.5µm or greater in diameter measured after the mixed ink has been left to stand at
25°C and at RH of 50% for 24 hours satisfy the relationship B/A≤2.

Documents:

2338-KOLNP-2009-(12-12-2013)-CORRESPONDENCE.pdf

2338-KOLNP-2009-(12-12-2013)-FORM-3.pdf

2338-KOLNP-2009-(13-03-2013)-ANNEXURE TO FORM-3.pdf

2338-KOLNP-2009-(13-03-2013)-CORRESPONDENCE.pdf

2338-KOLNP-2009-(18-06-2013)-CORRESPONDENCE.pdf

2338-KOLNP-2009-(18-06-2013)-OTHERS.pdf

2338-KOLNP-2009-(18-06-2013)-PA.pdf

2338-KOLNP-2009-(26-05-2014)-ANNEXURE TO FORM 3.pdf

2338-KOLNP-2009-(26-05-2014)-CORRESPONDENCE.pdf

2338-KOLNP-2009-(26-06-2013)-ABSTRACT.pdf

2338-KOLNP-2009-(26-06-2013)-CLAIMS.pdf

2338-KOLNP-2009-(26-06-2013)-CORRESPONDENCE.pdf

2338-KOLNP-2009-(26-06-2013)-DESCRIPTION (COMPLETE).pdf

2338-KOLNP-2009-(26-06-2013)-DRAWINGS.pdf

2338-KOLNP-2009-(26-06-2013)-FORM-2.pdf

2338-KOLNP-2009-(26-06-2013)-FORM-3.pdf

2338-KOLNP-2009-(26-06-2013)-OTHERS.pdf

2338-KOLNP-2009-(26-06-2013)-PETITION UNDER RULE 137.pdf

2338-KOLNP-2009-23-06-2009)-FORM 13.pdf

2338-kolnp-2009-abstract.pdf

2338-KOLNP-2009-ANEXURE TO FORM 3.pdf

2338-kolnp-2009-claims.pdf

2338-KOLNP-2009-CORRESPONDENCE 1.1.pdf

2338-kolnp-2009-correspondence.pdf

2338-kolnp-2009-description (complete).pdf

2338-kolnp-2009-drawings.pdf

2338-kolnp-2009-form 1.pdf

2338-kolnp-2009-form 13.pdf

2338-KOLNP-2009-FORM 18.pdf

2338-kolnp-2009-form 3.pdf

2338-kolnp-2009-form 5.pdf

2338-kolnp-2009-gpa.pdf

2338-kolnp-2009-international publication.pdf

2338-kolnp-2009-international search report.pdf

2338-kolnp-2009-others.pdf

2338-kolnp-2009-pct priority document notification.pdf

2338-kolnp-2009-pct request form.pdf

2338-kolnp-2009-specification.pdf

abstract-2338-kolnp-2009.jpg


Patent Number 263633
Indian Patent Application Number 2338/KOLNP/2009
PG Journal Number 46/2014
Publication Date 14-Nov-2014
Grant Date 10-Nov-2014
Date of Filing 23-Jun-2009
Name of Patentee RICOH COMPANY, LTD.
Applicant Address 3-6, NAKAMAGOME 1-CHOME, OHTA-KU, TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 GOTOH, AKIHIKO BON MEISON HONATSUGI 701, 3-14-8, NAKA-CHO, ATSUGI-SHI, KANAGAWA, 2430018
2 BANNAI, AKIKO MY CASTLE HONATSUGI 902, 1-3-14, KOTOBUKI-CHO, ATSUGI-SHI, KANAGAWA, 2430033
PCT International Classification Number C09D 11/00
PCT International Application Number PCT/JP2007/075395
PCT International Filing date 2007-12-26
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2006-354490 2006-12-28 Japan