U.S. patent application number 14/505667 was filed with the patent office on 2015-04-23 for ink for inkjet recording, ink container, inkjet recorder and recorded matter.
The applicant listed for this patent is Keita Katoh, Yuusuke Koizuka, Akihiko Matsuyama, Kazukiyo Nagai, Mitsuru Naruse, Masayasu Nonogaki. Invention is credited to Keita Katoh, Yuusuke Koizuka, Akihiko Matsuyama, Kazukiyo Nagai, Mitsuru Naruse, Masayasu Nonogaki.
Application Number | 20150109382 14/505667 |
Document ID | / |
Family ID | 52825822 |
Filed Date | 2015-04-23 |
United States Patent
Application |
20150109382 |
Kind Code |
A1 |
Naruse; Mitsuru ; et
al. |
April 23, 2015 |
INK FOR INKJET RECORDING, INK CONTAINER, INKJET RECORDER AND
RECORDED MATTER
Abstract
An ink for inkjet recording includes water; a hydrosoluble
organic solvent; a pigment; and a polymer including a first
structural unit represented by the following formula (1):
##STR00001## wherein R1 represents a hydrogen atom or a methyl
group; and M.sup.+ represents at least one member selected from the
group consisting of alkali metal ions, organic amine ions and
hydrogen ions; and a second structural unit represented by the
following formula (2) or (3): ##STR00002## wherein each of R.sub.2
and R.sub.3 represents a methyl group or a hydrogen atom; n
represents an integer of 18; x represents 0 or an integer of 2.
Inventors: |
Naruse; Mitsuru; (Shizuoka,
JP) ; Nonogaki; Masayasu; (Shizuoka, JP) ;
Matsuyama; Akihiko; (Shizuoka, JP) ; Katoh;
Keita; (Shizuoka, JP) ; Nagai; Kazukiyo;
(Shizuoka, JP) ; Koizuka; Yuusuke; (Shizuoka,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Naruse; Mitsuru
Nonogaki; Masayasu
Matsuyama; Akihiko
Katoh; Keita
Nagai; Kazukiyo
Koizuka; Yuusuke |
Shizuoka
Shizuoka
Shizuoka
Shizuoka
Shizuoka
Shizuoka |
|
JP
JP
JP
JP
JP
JP |
|
|
Family ID: |
52825822 |
Appl. No.: |
14/505667 |
Filed: |
October 3, 2014 |
Current U.S.
Class: |
347/86 ;
524/547 |
Current CPC
Class: |
C08F 220/1818 20200201;
B41J 29/13 20130101; C08F 220/1807 20200201; C08F 220/1818
20200201; C08F 220/1807 20200201; C09D 11/107 20130101; C08F 230/02
20130101; C08F 230/02 20130101; C08F 230/02 20130101; C08F 230/02
20130101; C09D 133/08 20130101; C09D 11/322 20130101 |
Class at
Publication: |
347/86 ;
524/547 |
International
Class: |
C09D 11/106 20060101
C09D011/106; C09D 11/322 20060101 C09D011/322; C09D 133/08 20060101
C09D133/08; B41J 2/175 20060101 B41J002/175 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 21, 2013 |
JP |
2013-218279 |
Oct 25, 2013 |
JP |
2013-222472 |
Sep 2, 2014 |
JP |
2014-177775 |
Claims
1. An ink for inkjet recording, comprising water; a hydrosoluble
organic solvent; a pigment; and a polymer, comprising: a first
structural unit represented by the following formula (1):
##STR00018## wherein R1 represents a hydrogen atom or a methyl
group; and M.sup.+ represents at least one member selected from the
group consisting of alkali metal ions, organic amine ions and
hydrogen ions; and a second structural unit represented by the
following formula (2) or (3): ##STR00019## wherein each of R.sub.2
and R.sub.3 represents a methyl group or a hydrogen atom; n
represents an integer of 18; x represents 0 or an integer of 2.
2. The ink for inkjet recording of claim 1, wherein the second
structural unit represented by the formula (2) is a structural unit
represented by the following formula (2a) having a straight-chain
alkyl group having 18 carbon atoms or a structural unit represented
by the following formula (2b) having a straight-chain alkenyl group
having 18 carbon atoms: ##STR00020## wherein R.sub.2 represents a
methyl group or a hydrogen atom.
3. The ink for inkjet recording of claim 1, wherein the polymer
comprises the first structural unit represented by the formula (1)
in an amount of from 10 to 60% by weight.
4. The ink for inkjet recording of claim 1, wherein the first
structural unit represented by the formula (1) is a structural unit
represented by the following formula (4): ##STR00021## wherein
M.sup.+ represents at least one member selected from the group
consisting of alkali metal ions, organic amine ions and hydrogen
ions.
5. The ink for inkjet recording of claim 2, wherein the structural
unit represented by the formula (2a) is a structural unit
represented by the following formula (5): ##STR00022##
6. The ink for inkjet recording of claim 2, wherein the structural
unit represented by the formula (2b) is a structural unit
represented by the following formula (6): ##STR00023##
7. The ink for inkjet recording of claim 1, wherein the second
structural unit represented by the formula (3) is a structural unit
represented by the following formula (7): ##STR00024##
8. The ink for inkjet recording of claim 1, wherein M.sup.+ in the
formula (1) is a potassium ion.
9. An ink for inkjet recording, comprising water; a hydrosoluble
organic solvent; a pigment; and a polymer obtained from a first
compound represented by the following formula (8) and a second
compound represented by the following formula (9) or (10):
##STR00025## wherein each of R1, R.sub.2 and R.sub.3 represents a
hydrogen atom or a methyl group; n represents an integer of 18; and
x represents 0 or an integer of 2.
10. The ink for inkjet recording of claim 1, wherein the polymer
has a weight-average molecular weight of from 4,000 to 50,000.
11. The ink for inkjet recording of claim 9, wherein the polymer
has a weight-average molecular weight of from 4,000 to 50,000.
12. The ink for inkjet recording of claim 1, wherein the polymer is
a pigment dispersant.
13. The ink for inkjet recording of claim 9, wherein the polymer is
a pigment dispersant.
14. An ink container, comprising an ink containing member
containing the ink for inkjet recording of claim 1.
15. An ink container, comprising an ink containing member
containing the ink for inkjet recording of claim 9.
16. An inkjet recorder, comprising: an inkjet head configured to
record information or images on a recording medium; and the ink
container according to claim 14.
17. An inkjet recorder, comprising: an inkjet head configured to
record information or images on a recording medium; and the
container according to claim 15.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This patent application is based on and claims priority
pursuant to 35 U.S.C. .sctn.119 to Japanese Patent Applications
Nos. 2013-218279, 2014-177775 and 2013-222472, filed on Oct. 21,
2013, Sep. 2, 2014 and Oct. 25, 2013 respectively in the Japan
Patent Office, the entire disclosure of which is hereby
incorporated by reference herein.
BACKGROUND
[0002] 1. Technical Field
[0003] The present invention relates to an ink for inkjet recording
(hereinafter referred to as an "ink"), an ink container, an inkjet
recorder and a recorded matter.
[0004] 2. Description of the Related Art
[0005] Inkjet recording methods have been popular as image forming
methods because of having advantages of having simpler process and
easier full-colorization than other recording methods, and
producing high-resolution images even with an apparatus having
simple composition. The inkjet recording methods have a small
amount of ink soar and adhere to recording media such as papers to
form images thereon with an inkjet recorder, and applications
thereof are expanding, e.g., personal and industrial printers and
printings.
[0006] In the inkjet recording methods, an aqueous ink using a
hydrosoluble dye is mostly used as a colorant. However, the ink has
disadvantages of having poor weatherability and water resistance.
Therefore, a pigment ink using a pigment instead of the
hydrosoluble dye has been studied recently. However, the pigment
ink is still inferior to the dye ink in colorability, ink discharge
stability and preservation stability.
[0007] In company with improvement of higher-quality image
technology of OA printers, even when recorded on plain papers as
recording media with the pigment ink, image density equivalent to
that of the dye ink is required. However, the pigment ink
penetrates into a plain paper as a recording medium and pigment
density at the surface of the paper lowers, resulting in lower
image density.
[0008] High-speed printing is desired because demands for
industrial applications have particularly been increasing recently.
Inkjet printers equipped with line heads are suggested for the
high-speed printing. In order to dry the ink adhering to the
recording medium quicker to print quicker, a penetrant is added to
the ink for water to penetrate into the recording medium. Then, not
only water but also pigment penetrates deeper into the recording
medium, resulting in lower image density.
[0009] When a plain paper is used as a recording medium, the
surface of the plain paper swells due to water which is a solvent
of the ink and a difference of extension rate between the front
side and the back side of the paper becomes large, resulting in
curl. This has not been a problem in low-speed printing because of
being solved as the paper is dried. However, in high-speed
printing, paper jam may occur because a recording medium is fed
with curl unsolved. An organic solvent in the ink is effectively
increased to solve curl. However, it becomes difficult to assure
storage stability of the ink because of being more hydrophobic.
[0010] In order to solve this problem, PCT Japanese published
national phase application No. 2009-513802 discloses an inkjet
composition including a liquid vehicle, a colorant, and a polymer
having at least one functional group having a specific calcium
index value. Monomers forming the polymer include
4-methacrylamide-1-hydroxybutane-1,1-diphosphonic acid. The
colorant is destabilized by the diphosphonic acid group and Ca salt
in a paper when contacting the paper, and the resultant printed
image improves in quality.
[0011] Japanese published unexamined application No.
JP-2012-51357-A discloses an inkjet recording method of applying a
receiving liquid including a Ca salt; and an ink including a
pigment combined with a group having phosphorus, a resin emulsion
and a surfactant thereon. It is disclosed that a bisphosphonic acid
is preferably used as the group having phosphorus, which is reacted
with the Ca salt in the receiving liquid to improve feathering and
fixability. However, a polymer including phosphonic acid group is
not used as dispersant or an additive in a pigment dispersion, and
a pigment combined with a phosphoric acid is used.
[0012] Japanese published unexamined application No.
JP-2004-123904-A discloses an aqueous ink including a colorant,
water, hydrosoluble organic solvent, a surfactant and a chelate
agent. A low-molecular-weight hydroxy ethylidenediphosphonic acid
or its salt is used as the chelate agent. The chelate agent removes
calcium included in a pigment dispersion to improve discharge
stability and storage stability of the ink. However, only the
low-molecular-weight hydroxyethylidenediphosphonic acid is
disclosed, and a polymer including a phosphonic acid is not
disclosed. A relation between the chelate agent and improvement of
the image density of an image when recorded on a plain paper is not
disclosed, either.
SUMMARY
[0013] Accordingly, one object of the present invention is to
provide an ink for inkjet recording, forming an image having high
image density, and good storage stability even when including a
hydrosoluble organic solvent in a large amount.
[0014] Another object of the present invention is to provide an ink
container containing the ink.
[0015] A further object of the present invention is to provide an
inkjet recorder using the ink.
[0016] These objects and other objects of the present invention,
either individually or collectively, have been satisfied by the
discovery of an ink for inkjet recording, including water; a
hydrosoluble organic solvent; a pigment; and a polymer including a
first structural unit represented by the following formula (1):
##STR00003##
wherein R1 represents a hydrogen atom or a methyl group; and
M.sup.+ represents at least one member selected from the group
consisting of alkali metal ions, organic amine ions and hydrogen
ions; and a second structural unit represented by the following
formula (2) or (3):
##STR00004##
wherein each of R.sub.2 and R.sub.3 represents a methyl group or a
hydrogen atom; n represents an integer of 18; and x represents 0 or
an integer of 2.
[0017] These and other objects, features and advantages of the
present invention will become apparent upon consideration of the
following description of the preferred embodiments of the present
invention taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Various other objects, features and attendant advantages of
the present invention will be more fully appreciated as the same
becomes better understood from the detailed description when
considered in connection with the accompanying drawings in which
like reference characters designate like corresponding parts
throughout and wherein:
[0019] FIG. 1 is a schematic view illustrating an embodiment of the
ink container of the present invention;
[0020] FIG. 2 is a schematic view illustrating the ink container of
the present invention including a case in FIG. 1;
[0021] FIG. 3 is a perspective view illustrating an embodiment of
the whole inkjet recorder of the present invention;
[0022] FIG. 4 is a schematic view illustrating an inner structure
of an embodiment of the inkjet recorder of the present invention;
and
[0023] FIG. 5 is a schematic view illustrating an embodiment of
inkjet head of the inkjet recorder of the present invention.
DETAILED DESCRIPTION
[0024] The present invention provides an ink for inkjet recording,
forming an image having high image density, and good storage
stability even when including a hydrosoluble organic solvent in a
large amount.
<Ink for Inkjet Recording>
[0025] The ink of the present invention includes water, a
hydrosoluble organic solvent, a polymer (hereinafter referred to as
polymer Q) including a structural unit represented by the formula
(1) and another structural unit represented by the formula (2) or
(3), and other components further when necessary.
(Polymer Q)
[0026] The polymer Q has a dibasic acid structure including
adjacent phosphonic acid groups as a structural unit represented by
the formula (1), and includes many diphosphonic acid groups in its
molecule differently from low-molecular-weight compounds. As a
result, the polymer Q has more hydrophilic groups in its molecule
than a monobasic acid and has goo hydrophilicity. The phosphonic
acid groups are easy to react with Ca ions and chelates the Ca ions
because of being dibasic acid groups, and combine with the Ca ions
more tightly to be hydrophobized.
[0027] The structural unit represented by the formula (2) or (3)
prevents phosphonic acid groups from gathering in the polymer Q for
unknown reasons to further improve storage stability of the ink. In
addition, the structural unit represented by the formula (2) or (3)
improves adsorbability of the polymer Q to a pigment for unknown
reasons. Therefore, the polymer Q can be used as a dispersant of a
pigment as well.
[0028] Therefore, an ink including the polymer Q not only improves
in dispersion and storage stability, but also is capable of
producing images having higher image density even on a plain paper
including less Ca ions because Ca ions dissolved out from the paper
to the ink hydrophobize the structural unit represented by the
formula (1), and the structural unit represented by the formula (2)
or (3) having high adsorbability to a pigment agglutinates together
with a pigment to retain the pigment on the paper.
[0029] The ink preferably includes the polymer Q, but are not
limited to, in an amount of from 0.05 to 10% by weight, more
preferably from 0.5 to 5% by weight, and furthermore preferably
from 1 to 3% by weight. The ink does not substantially improve in
image density until including the polymer Q not less than 0.05% by
weight, and has suitable viscosity in discharging from head when
including the polymer Q not greater than 10% by weight.
[0030] The polymer Q used as a pigment dispersant further improves
image density on a plain paper and storage stability of an ink
including a hydrosoluble organic solvent in a large amount.
[0031] When the polymer Q is used as a pigment dispersant, besides
the structural unit represented by the formula (1) and the
structural unit represented by the formula (2) or (3), the ink
preferably includes a structural unit coming from a hydrophobic
polymerizable monomer. The hydrophobic polymerizable monomer is
mentioned later.
[0032] The ink preferably includes the polymer Q when used as a
pigment dispersant, but are not limited to, in an amount of from 1
to 100 parts by weight, more preferably from 5 to 80 parts by
weight, and furthermore preferably from 10 to 50 parts by weight
per 100 parts by weight of the pigment. When 5 to 80 parts by
weight, the ink produces images having high image density, and
improves in pigment dispersion stability and storage stability.
[0033] Specific examples of the alkali metal in the alkali metal
ion of M.sup.+ in the formula (1) include, but are not limited to,
lithium, sodium and potassium.
[0034] Specific examples of the organic amine in the organic
ammonium ion of M.sup.+ include, but are not limited to, alkyl
amines such as mono, di or trimethylamine and mono, di or
triethylamine; alcohol amines such as ethanol amine,
diethanolamine, triethanolamine, methylethanolamine
(2-(methylamine)ethanol), methyldiethanolamine,
dimethylethanolamine, monopropanolamine, dipropanolamine,
tripropanolamine, isopropanolamine, trishydroxymethylaminomethane
and 2-amino-2-ethyl-1,3propanedil (AEPD); and cyclic amine such as
choline, morpholine, N-methylmorpholine, N-methyl-2-pyrrolidone and
2-pyrrolidone.
[0035] Particularly, the potassium ion is preferably used in terms
of image density and storage stability.
[0036] Not less than half or all of M.sup.+ are preferably alkali
metal ions or organic ammonium ions, and the rest is preferably a
hydrogen ion (proton).
[0037] The structural unit represented by the formula (1) is
preferably a structural unit represented by the following formula
(4):
##STR00005##
wherein M.sup.+ represents at least one member selected from the
group consisting of alkali metal ions, organic amine ions and
hydrogen ions.
[0038] The structural unit represented by the formula (2) is
preferably a structural unit represented by the following formula
(5).
##STR00006##
[0039] The structural unit represented by the formula (3) is
preferably a structural unit represented by the following formula
(7).
##STR00007##
[0040] Specific examples of the structural unit represented by the
formula (2) include compounds represented by the following formulae
(2a) and (2b):
##STR00008##
wherein R.sub.2 represents a methyl group or a hydrogen atom.
[0041] Both of these have a straight-chain aliphatic hydrocarbon
group (C18). Namely, the former structural unit includes a stearyl
group and the latter structural unit includes an oleyl group. The
former structural unit can easily be introduced in a polymer using
a stearylmethacrylate or stearylacrylate, and the latter structural
unit can easily be introduced in a polymer using oleyl methacrylate
or oleyl acrylate,
[0042] The structural unit represented by the formula (4), and a
member selected from the group consisting of the structural unit
represented by the formula (5), a structural unit represented by
the following formula (6) and the structural unit represented by
the formula (7) further improve image density and storage stability
of a pigment dispersion.
##STR00009##
[0043] The polymer Q can include a structural unit coming from a
polymerizable monomer besides the structural unit represented by
the formula (1) and the structural unit represented by the formula
(2) or (3).
[0044] Specific examples of the polymerizable monomer include, but
are not limited to, polymerizable hydrophobic monomers and
polymerizable hydrophilic monomers.
[0045] Specific examples of the polymerizable hydrophobic monomers
include, but are not limited to, unsaturated ethylene monomers
having an aromatic ring such as styrene, .alpha.-methylstyrene,
4-t-butylstyrene and 4-chloromethylestyrene; alkyl(meth)acrylate
such as methyl(meth)acrylate, ethyl(meth)acrylate,
n-butyl(meth)acrylate, dimethyl maleate, dimethyl itaconate,
dimethyl fumarate, lauryl(meth)acrylate (C12),
tridecyl(meth)acrylate (C13), tetradecyl(meth)acrylate (C14),
pentadecyl(meth)acrylate (C15), hexadecyl(meth)acrylate (C16),
heptadecyl(meth)acrylate (C17), nonadecyl(meth)acrylate (C19),
eicosyl(meth)acrylate (C20), heneicosyl(meth)acrylate (C21) and
docosyl(meth)acrylate (C22); unsaturated ethylene monomers having
an alkyl group such as 1-heptene, 3,3-dimethyl-1-pentene,
4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene,
5-methyl-1-hexene, 1-octene, 3,3-dimethyl-1-hexene,
3,4-dimethyl-1-hexene, 4,4-dimethyl-1-hexene, 1-nonene,
3,5,5-trimethyl-1-hexene, 1-decene, 1-undecene, 1-dodecene,
1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,
1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and
1-docosene. These can be used alone or in combination.
[0046] Specific examples of the polymerizable hydrophilic monomers
include, but are not limited to, anionic unsaturated ethylene
monomers such as a (meth)acrylic acid or its salt, a maleic acid or
its salt, monomethyl maleate, an itaconic acid, monomethyl
itaconate, a fumaric acid, 4-styrenesulfonic acid and
2-acrylamide-2-methylpropane sulfonic acid; and nonionic
unsaturated ethylene monomers such as (meth)acrylic
acid-2-hydroxyethyl, diethyleneglycol mono(meth)acrylate,
triethyleneglycol mono(meth)acrylate, tetraethyleneglycol
mono(meth)acrylate, polyethyleneglycol mono(meth)acrylate,
(meth)acrylamide, N-methylol (meth)acrylamide, N-vinyl formamide,
N-vinyl acetoamide, N-vinyl pyrrolidone, acrylamide,
N,N-dimethylacrylamide, N-t-butylacrylamide, N-octyl acrylamide and
N-t-octyl acrylamide.
[0047] The polymer Q preferably includes the structural unit
represented by the formula (1), but are not limited to, in an
amount of from 5 to 80% by weight, more preferably from 10 to 60%
by weight, and furthermore preferably from 20 to 40% by weight.
When 10 to 60% by weight, the ink produces images having high image
density, and improves in pigment dispersion stability and storage
stability.
[0048] The polymer Q preferably includes the structural unit
represented by the formula (2) or (3), but are not limited to, in
an amount of from 20 to 95% by weight, and more preferably from 40
to 70% by weight. When 40 to 70% by weight, the ink produces images
having high image density, and improves in pigment dispersion
stability and storage stability.
(Method of Preparing Polymer Q)
[0049] The polymer Q can be prepared by the following method.
[0050] Namely, after compounds represented by the following
formulae (8) and (9) or (10) are polymerized, or after the
compounds represented by the formulae (8), (9) or (10) and the
polymerizable monomer are copolymerized, the resultant polymerized
or the copolymerized product is neutralized with an alkali metal
base or an organic amine base:
##STR00010##
wherein each of R1, R.sub.2 and R.sub.3 represents a hydrogen atom
or a methyl group; n represents an integer of 18; and x represents
0 or an integer of 2.
[0051] Alternatively, the compound represented by the formulae (8)
previously neutralized with an alkali metal base or an organic
amine base may be copolymerized with the compound represented by
the formula (9) or (10).
[0052] Specifically, after a solvent, the compounds represented by
the formulae (8), (9) or (10) and the polymerizable monomer when
necessary are reacted with a polymerization initiator under a
nitrogen gas stream at 60 to 150.degree. C. in a flask equipped
with a stirrer, a thermometer and a nitrogen introduction pipe, the
reactant is neutralized with the alkali metal base or the organic
amine base.
[0053] Specific examples of the compound represented by the formula
(8) include 1-methacryloxyethane-1,1-diphosphonic acid represented
by the following formula (11) when R1 is a methyl group and
1-acryloxyethane-1,1-diphosphonic acid represented by the following
formula (12) when R1 is a hydrogen atom.
##STR00011##
These compounds can be synthesized by a method disclosed in
Japanese published unexamined application No. JP-S58-222095-A.
[0054] Specific examples of the compound represented by the formula
(9) include stearylmethacrylate represented by the following
formula (13), stearylacrylate represented by the following formula
(14), oleyl methacrylate represented by the following formula (15)
and oleyl acrylate represented by the following formula (16).
##STR00012##
[0055] Specific examples of the compound represented by the formula
(10) include benzyl methacrylate represented by the following
formula (17) when R.sub.3 is a methyl group and benzyl acrylate
represented by the following formula (18) when R.sub.3 is a
hydrogen atom.
##STR00013##
[0056] The polymer Q is preferably synthesized by a method using a
radical polymerization initiator because the polymerization
operation and the molecular weight control are simple. A solution
polymerization method polymerizing in an organic solvent is more
preferably used. Specific examples of the solvent include, but are
not limited to, ketone solvents such as methanol, ethanol, acetone,
methyl ethyl ketone and methyl isobutyl ketone; ester acetate
solvents such as ethyl acetate and butyl acetate; aromatic
hydrocarbon solvents such as benzene, toluene and xylene;
isopropanol; ethanol; cyclohexane; tetrahydrofuran;
dimethylformamide; dimethylsulfoxide; and hexamethyl phosphoamide.
Among these, ketone solvents, ester acetate solvents and alcohol
solvents are preferably used.
[0057] Specific examples of radical polymerization initiators
include, but are not limited to, such as peroxyketal,
hydroperoxide, dialkylperoxide, diacylperoxide, peroxydicarbonate,
peroxyester, cyano azobisisobutylonitrile,
azobis(2,2'-isovaleronitrile), and non-cyano
dimethyl-2,2'-azobisisobutylate. Organic peroxides and azo
compounds having an easily-controllable molecular weight and a low
decomposition temperature are preferably used, and the azo
compounds are more preferably used. The polymerization initiators
are preferably used in an amount of from 1 to 20% by weight based
on total weight of polymerizable monomers.
[0058] The polymer Q may include a chain-transfer agent in a proper
amount to control its molecular weight. Specific examples thereof
include, but are not limited to, mercapto acetic acid, mercapto
propionic acid, 2-propanethiol, 2-mercaptoethanol, thiophenol,
dodecylmercaptan, 1-dodecanethiol and thioglycerol.
[0059] The polymerization temperature is preferably, but are not
limited to, from 50 to 150.degree. C., and more preferably from 60
to 100.degree. C. The polymerization time is preferably, but is not
limited to, from 3 to 48 hrs.
[0060] The phosphonic acid groups of the polymer Q are partially or
all neutralized with the alkali metal base or the organic amine
base. The neutralization can be made while a pigment and the
polymer Q are mixed with each other in the process of preparing an
ink.
[0061] In the present invention, the neutralization index of the
phosphonic acid groups in the neutralized polymer Q is defined by
the following formulae. This is different from a ratio of a proton
in the copolymer actually substituted with a metallic ion or an
organic amine ion.
[0062] When the compound represented by the formula (7) is monomer
1,
Neutralization index (%)=(molar number of base added.times.valence
of cation of base)/(molar number of monomer 1 included in polymer
Q.times.4).times.100
Molar number of base added=added amount of base Yg/molecular weight
of base
Molar number of monomer 1 included in polymer Q=charge-in quantity
of monomer 1/molecular weight of monomer 1
[0063] Therefore, base quantity needed to obtain neutralization
index (%) is determined by the following formula.
Added amount of base Yg=neutralization index (%).times.(molar
number of monomer 1 included in polymer Q.times.4).times.molecular
weight of base/(valence of cation of
base.times.100.times./molecular weight of monomer 1).
[0064] The polymer Q preferably has a weight-average molecular
weight of, but are not limited to, from 2,000 to 70,000, more
preferably from 4,000 to 50,000 and furthermore preferably from
6,000 to 30,000. The weight-average molecular weight can be
measured by gel permeation chromatography (GPC).
[0065] The weight-average molecular weight of the polymer Q is
somewhat controllable by the polymerization temperature, an amount
of the polymerization initiator and the monomer concentration in
the reaction.
[0066] The polymer Q tends to have a low molecular weight when
polymerized at high temperature for a short time, and a high
molecular weight when polymerized at low temperature for a long
time.
[0067] The polymer Q tends to have a low molecular weight when
including the polymerization initiator in a large amount, and a
high molecular weight when including the polymerization initiator
in a small amount
[0068] The polymer Q tends to have a low molecular weight when the
concentration of the monomer is high and a high molecular weight
when the concentration thereof is low.
<Water>
[0069] As the water, ion-exchanged water, ultrafiltrated water,
Mill Q water, pure water such as distilled water or ultrapure water
can be used.
[0070] The content of the water used in the ink for inkjet
recording is not particularly limited.
<Pigment>
[0071] Inorganic pigments and organic pigments can be used as the
pigment. These can be used alone or in combination.
[0072] Specific examples of the inorganic pigments include, but are
not limited to, titanium oxide, iron oxide, calcium carbonate,
barium sulfate, aluminum hydroxide, barium yellow, cadmium red,
chrome yellow and carbon black. Among them, the carbon black is
preferably used. The carbon black is produced by known methods such
as a contact method, a furnace method, and a thermal method.
[0073] Specific examples of the organic pigment include, but are
not limited to, azo pigments, azomethine pigments, polycyclic
pigments, dye chelate, a nitro pigment, a nitroso pigment, and
aniline black. Among them, the azo pigments and the polycyclic
pigments are preferably used.
[0074] Specific examples of the azo pigments include, but are not
limited to, azo lake, an insoluble azo pigment, a condensed azo
pigment, and a chelate azo pigment. Specific examples of the
polycyclic pigments include, but are not limited to, a
phthalocyanine pigment, a perylene pigment, a perinone pigment, an
anthraquinone pigment, a quinacridon pigment, a dioxazine pigment,
an indigo pigment, a thioindigo pigment, an iso-indolinone pigment,
and a quinophtharone pigment. Specific examples of the dye chelate
include, but are not limited to, basic dye chelate, and an acid dye
chelate.
[0075] Specific examples of the pigment for black ink include
carbon black (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); metal oxides such as titanium oxide;
and organic pigments such as aniline black (C.I. Pigment Black
1).
[0076] The carbon black preferably has an average primary particle
diameter of from 15 to 40 nm, a BET specific surface area of from
50 to 300 m.sup.2/g, a DBP oil absorption of from 40 to 150 mL/100
g, a volatile matter content of from 0.5 to 10%, and a pH of from 2
to 9.
[0077] Marketed products can be used as carbon black. Specific
examples thereof include, but are not limited to, No. 2300, No.
900, MCF-88, No. 3, No. 40, No. 45, No. 52, MA7, MA8, MA100 and No.
2200n from Mitsubishi Chemical Corp.; Raven 700, 5750. 5250, 5000,
3500 and 1255 from Columbian Chemicals Company; Regal 400R, 330R,
660R, Mogul L, Monarch 700, 800, 880, 900, 1000, 1100, 1300,
Monarch 1400 from Cabot Corp.; Color Black FW1, FW2, FW2V, FW18,
FW200, S150, S160, S170 from Degussa AG; Printex 35, U, V, 140U,
140V from Degussa AG; and Special Black 6, 5, 4A and 4 from Degussa
AG.
[0078] Specific examples of the pigment for yellow ink include, but
are not limited to, C.I. Pigment Yellow 1, C.I. Pigment Yellow 2,
C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow
13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 16, C.I. Pigment
Yellow 17, C.I. Pigment Yellow 73, C.I. Pigment Yellow 74, C.I.
Pigment Yellow 75, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93,
C.I. Pigment Yellow 95, C.I. Pigment Yellow 97, C.I. Pigment Yellow
98, C.I. Pigment Yellow 114, C.I. Pigment Yellow 120, C.I. Pigment
Yellow 128, C.I. Pigment Yellow 129, C.I. Pigment Yellow 138, C.I.
Pigment Yellow 150, C.I. Pigment Yellow 154, C.I. Pigment Yellow
155, C.I. Pigment Yellow 174 and C.I. Pigment Yellow 180.
[0079] Specific examples of the pigment for magenta ink include,
but are not limited to, C.I. Pigment Red 5, C.I. Pigment Red 7,
C.I. Pigment Red 12, C.I. Pigment Red 48 (Ca), C.I. Pigment Red 48
(Mn), C.I. Pigment Red 57 (Ca), C.I. Pigment Red 57:1, C.I. Pigment
Red 112, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment
Red 146, C.I. Pigment Red 168, C.I. Pigment Red 176, C.I. Pigment
Red 184, C.I. Pigment Red 185, C.I. Pigment Red 202 and Pigment
Violet 19.
[0080] Specific examples of the pigment for cyan ink include, but
are not limited to, C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I.
Pigment Blue 3, C.I. Pigment Blue 15, C.I. Pigment Blue 15:3, C.I.
Pigment Blue 15:4, C.I. Pigment Blue 15:34, C.I. Pigment Blue 16,
C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 63,
C.I. Pigment Blue 66, Bat Blue 4 and Bat Blue 60.
[0081] New pigments may be used in the present invention. The above
pigments may be used together therewith as long as the effect is
not impaired.
[0082] When Pigment Yellow 74 as a yellow pigment, Pigment Red 122
or a Pigment Violet 19 as a magenta pigment and a Pigment Blue 15:3
as a cyan pigment are used, a well-balanced ink having good color
tone and light resistance can be obtained.
[0083] The pigment preferably has a volume-average particle
diameter (D50) not greater than 150 nm, and more preferably not
greater than 100 nm to improve discharge stability and prevent the
nozzle from clogging and the ink from discharge in a curve.
[0084] The volume-average particle diameter (D50) of the pigment us
measured by Microtrac UPA from NIKKISO CO., LTD. in an environment
of 23.degree. C. and 55% RH.
[0085] The ink preferably includes the pigment in an amount of from
0.1 to 20% by weight, and more preferably from 1 to 20% by
weight.
[0086] It is preferable that water, a pigment, a dispersant and
other optional components are mixed and dispersed by a disperser to
prepare a pigment dispersion in which a particle diameter thereof
is adjusted and that the dispersion is included in the ink.
[0087] The pigment dispersion is preferably filtered to remove
coarse particles and deaerated when necessary.
[0088] The pigment dispersion preferably includes a pigment in an
amount of from 0.1 to 50% by weight, and more preferably from 0.1
to 30% by weight.
[0089] The polymer Q is preferably used as the pigment dispersion.
Specific examples of other dispersants include to, surfactants such
as anionic surfactants, cationic surfactant, ampholytic surfactants
and nonionic surfactants; sodium naphthalenesulfonate formalin
condensates; and polymeric dispersants. These can be used alone or
in combination.
[0090] Specific examples of the anionic surfactant include, but are
not limited to, alkylsulfocarboxylic acid salts,
.alpha.-olefinsulfonic acid salts, polyoxyethylene alkyl ether
acetic acid salts, N-acylamino acids or salts thereof,
N-acylmethyltaurine salts, alkylsulfuric acid salts, polyoxyalkyl
ether sulfuric acid salts, alkylsulfuric acid salts,
polyoxyethylene alkyl ether phosphoric acid salts, rosin acid soap,
castor oil sulfate ester salts, lauryl alcohol sulfate ester salts,
alkylphenolic phosphate esters, alkylated phosphate esters,
alkylarylsulfonic acid salts, diethyl sulfosuccinic acid salts,
diethylhexyl sulfosuccinic acid salts, and dioctyl sulfosuccinic
acid salts.
[0091] Specific examples of the cationic surfactant include, but
are not limited to, 2-vinylpyridine derivatives and
poly4-vinylpyridine derivatives.
[0092] Specific examples of the amphoteric surfactant include, but
are not limited to, betaine lauryldimethylamino acetate,
2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine,
betaine coconut oil fatty acid amidopropyldimethylamino acetate,
polyoctylpolyaminoethylglycine, and imidazoline derivatives.
[0093] Specific examples of the nonionic surfactant include, but
are not limited to, ether based surfactants such as polyoxyethylene
nonylphenyl ether, polyoxyethylene octylphenyl ether,
polyoxyethylene dodecyl phenyl ether, polyoxyethylene octylphenyl
ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether
and polyoxyethylene alkyl ether; ester based surfactants such as
polyoxyethylene oleate esters, polyoxyethylene distearate esters,
sorbitan laurate, sorbitan monostearate, sorbitan monooleate,
sorbitan sesquioleate, polyoxyethylene monooleate and
polyoxyethylene stearate; acetylene glycol (alcohol) based
surfactants such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol,
3,6-dimethyl-4-octyne-3,6-diol and 3,5-dimethyl-1-hexine-3-ol.
[0094] Among these, sodium naphthalenesulfonate formalin
condensates are preferably used.
[0095] The sodium naphthalenesulfonate formalin condensates
preferably include dimeric, trimeric and tetrameric
naphthalenesulfonate in an amount of from 20 to 80% by weight such
that the resultant ink has good viscosity and dispersibility, and
improves in storage stability, which prevents the nozzle from
clogging.
<Hydrosoluble Organic Solvent>
[0096] The hydrosoluble organic solvent has at least an effect of a
wetter or s penetrant.
[0097] Specific examples thereof include, but are not limited to,
polyols such as glycerin, ethylene glycol, diethylene glycol,
isopropylidene glycerol, 1,3-butane diol, 3-methyl-1,3-butane diol,
triethylene glycol, propylene glycol, dipropylene glycol,
trimethylol propane, trimethylol ethane, ethylene glycol,
diethylene glycol, dipropylene glycol, tripropylene glycol,
tetraethylene glycol, hexylene glycol, polyethylene glycol,
polypropylene glycol, 1,5-pentane diol, 1,6-hexane diol, glycerol,
1,2,6-hexane triol, 1,2,4-butane triol, 1,2,3-butane triol, and
petriol; polyol 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; polyol aryl ethers such as
ethylene glycol monophenyl ether, and ethylene glycol monobenzyl
ether; nitrogen-containing heterocyclic compounds such as
2-pyrolidone, N-methyl-2-pyrolidone, N-hydroxyethyl-2-pyrrolidone,
1,3-dimethyl imidazolidinone, .epsilon.-caprolactone, and
.gamma.-butyllactone; amides such as formamide, N-methylformamide,
N,N-dimethylformamide, N,N-dimethyl-.beta.-methoxy propion amide,
and N,N-dimethyl-.beta.-butoxy propion amide; amines such as
monoethanol amine, diethanol amine, triethanol amine, monoethyl
amine, diethyl amine, and triethyl amine; sulfur-containing
compounds such as dimethyl sulfoxide, sulfolane, and thiodiethanol;
3-ethyl-3-hydroxymethyl oxetane, propylene carbonate, and ethylene
carbonate. These can be used alone or in combination.
[0098] Among these solvents, 3-ethyl-3-hydroxymethyloxetane,
isopropylidene glycerol, N, N-dimethyl-.beta.-methoxy propion
amide, and N, N-dimethyl-.beta.-butoxy propion amide are
particularly preferable. These effectively prevent plain papers
from curling.
[0099] In addition, 1,3-butane diol, diethylene glycol,
2,2,4-trimethyl-1,3-pentanediol, triethyleneglycol and glycerin are
effectively used to prevent defective discharge due to moisture
evaporation.
[0100] Specific examples of the hydrosoluble organic solvent having
penetrance more than wettability include, but are not limited to,
2-ethyl-1,3-hexanediol [solubility: 4.2%)(25.degree. ] and
2,2,4-trimethyl-1,3-pentanediol [solubility: 2.0%
(25.degree.)].
[0101] Specific examples of other polyol compounds include
aliphatic diols such as 2-ethyl-2-methyl-1,3-propanediol,
3,3-dimethyl-1,2-butanediol, 2,2-diethyl-1,3-propanediol,
2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol,
2,5-dimethyl-2,5-hexanediol, and 5-hexene-1,2-diol.
[0102] Other penetrants can be used in combination with the
above-mentioned penetrants as long as the penetrants can be
dissolved in the ink, and the properties of the ink can be
controlled so as to fall in the desired ranges. Specific examples
thereof include alkyl or aryl ethers of polyalcohols such as
diethylene glycol monophenyl ether, ethylene glycol monophenyl
ether, ethylene glycol monoallyl ether, diethylene glycol monobutyl
ether, propylene glycol monobutyl ether, and tetraethylene glycol
chlorophenyl ether; and lower alcohols such as ethanol.
[0103] Saccharides are also preferable as other solid hydrosoluble
organic materials.
[0104] Specific examples of the saccharides include, but are not
limited to, monosaccharides, disaccharides, oligosaccharides
(including trisaccharides and tetrasaccharides), and
polysaccharides. Specific examples thereof include, but are not
limited to, glucose, mannose, fructose, ribose, xylose, arabinose,
galactose, maltose, cellobiose, lactose, saccharose, trehalose, and
maltotriose. Polysaccharides represent sugar in a broad sense and
are materials that are present widely in nature, for example,
.alpha.-cyclodextrine and cellulose. In addition, specific examples
of derivatives of these saccharides include, but are not limited
to, reducing sugars (for example, sugar alcohols (represented by
HOCH.sub.2(CHOH).sub.nCH.sub.2OH, where n represents an integer of
from 2 to 5) of the sugar groups specified above, oxidized sugars
(e.g., aldonic acid and uronic acid), amino acid, and thio acid.
Among these, sugar alcohols are preferable and specific examples
thereof include, but are not limited to, maltitol and sorbit.
[0105] The blend ratio of the pigment and the wetter has a large
impact on the discharging stability of ink injected from a head. If
the blending amount of the wetter is too small while the ratio of
the solid pigment portion is high, water evaporation around ink
meniscus of nozzles tends to be accelerated, resulting in bad
discharging performance.
[0106] The blending ratio of the wetter is preferably from 10 to
60% by weight and more preferably from 20 to 60% by weight based on
the ink. The ink having such a content ratio is extremely good
about the test for drying, preservation, and reliability.
<Other Components>
[0107] The ink of the present invention can include other
components when necessary. Specific examples thereof include, but
are not limited to, a dispersant, a pH adjuster, a hydrodispersible
resin, an antiseptic and antifungal agent, a chelate reagent, an
antirust agent, an antioxidant, an UV absorber, an oxygen absorber,
and a light stabilizer.
--Surfactant--
[0108] Specific examples the surfactant include, but are not
limited to, anionic surfactants, cationic surfactants, nonionic
surfactants, ampholytic surfactants and fluorine-containing
surfactants. Among these, the nonionic surfactants and the
fluorine-containing surfactants are preferably used.
[0109] Specific examples of the anionic surfactants include, but
are not limited to, alkyl allyl, alkylnaphthalene sulfonate, alkyl
phosphate, alkyl sulfate, alkyl sulfonate, alkylether sulfate,
alkylsulfosuccinate, alkyl ester sulfate, alkylbenzene sulfonate,
alkyl diphenylether disulfonate, alkyl aryl ether phosphate, alkyl
aryl ether sulfate, alkyl aryl ether ester sulfate, olefin
sulfonate, alkane olefin sulfonate, polyoxyethylenealkylether
phosphate, polyoxyethylenealkylether ester salt sulfate, ether
carboxylate, sulfosuccinate, .alpha.-sulfofatty acid ester, fatty
acid salts, condensates of higher fatty acid and amino acid, and
naphthenate.
[0110] Specific examples of the cationic surfactants include, but
are not limited to, alkylamine salts, dialkylamine salts, aliphatic
amine salts, benzalkonium salts, quaternary ammonium salts, alkyl
pyridinium slats, imidazolinium salts, sulfonium salts, and
phosphonium salts.
[0111] Specific examples of the nonionic surfactants include, but
are not limited to, acetylene glycol surfactants,
polyoxyethylenealkylether, polyoxyethylenealkylphenylether,
polyoxyethylenealkylester, and polyoxyethylene sorbitan fatty acid
ester.
[0112] Specific examples of the ampholytic surfactants include, but
are not limited to, imidazoline derivatives such as imidazolinium
betaine, dimethyl alkyl lauryl betaine, alkyl glycine, and alkyl
di(aminoethyl)glycin.
Specific examples of the fluorine-containing surfactants include,
but are not limited to, surfactants having the following formulae
(I) to (III):
CF.sub.3CF.sub.2(CF.sub.2CF.sub.2).sub.m--CH.sub.2CH.sub.2O(CH.sub.2CH.s-
ub.2O).sub.nH
wherein each of m represents 0 or an integer of from 1 to 10 and n
represents 0 or an integer of from 1 to 40.
##STR00014##
wherein Rf represents a fluorine-containing group; m, n and p
represent integers of from 6 to 25, 1 to 4 and 1 to 4,
respectively.
[0113] The fluorine containing group is preferably a perfluoroalkyl
group. The perfluoroalkyl group preferably has 1 to 10, and more
preferably 1 to 3 carbon atoms. Specific examples thereof include,
but are not limited to, --C.sub.nF.sub.2n-1 (n is an integer of
from 1 to 10) such as --CF.sub.3, --CF.sub.2CF.sub.3,
--C.sub.3F.sub.7 and --C.sub.4F.sub.9. Among these, --CF.sub.3 and
--CF.sub.2CF.sub.3 are preferable.
##STR00015##
wherein Rf represents a fluorine-containing group; R.sub.2.sup.+
represents a cationic group; R.sub.1 represents an anionic group;
and q is an integer of form 1 to 6.
[0114] The fluorine containing group is preferably a perfluoroalkyl
group such as --CF.sub.3, --CF.sub.2CF.sub.3, --C.sub.3F.sub.7 and
--C.sub.4F.sub.9. Specific examples of the cationic group include,
but are not limited to, a quaternary ammonium group, alkali metal
ions such as sodium and potassium, triethylamine and
triethanolamine. Among these, the quaternary ammonium group is
preferable. Specific examples of the anionic group include, but are
not limited to, COO.sup.-. SO.sub.3.sup.-, SO.sub.4.sup.- and
PO.sub.t.sup.-.
[0115] The ink preferably includes the surfactant in an amount of,
but are not limited to, from 0.01 to 5.0% by weight, and more
preferably from 0.5 to 3% by weight. When not greater than 5.0% by
weight, deterioration of the image density and penetration of the
ink through a substrate are prevented.
--pH Adjuster--
[0116] The pH adjuster is not particularly limited as long as it
may adjust a pH of the aqueous ink being prepared to 8.5 to 11
without adversely affecting the ink. Specific examples of the pH
adjuster include, but are not limited to, alcohol amines,
hydroxides of an alkali metal element, hydroxides of ammonium,
hydroxides of phosphonium, and carbonates of an alkali metal.
[0117] Specific examples the alcohol amines include, but are not
limited to, diethanolamine, triethanolamine, and
2-amino-2-ethyl-1,3-propanediol.
[0118] Specific examples the hydroxides of an alkali metal element
include, but are not limited to, lithium hydroxide, sodium
hydroxide and potassium hydroxide.
[0119] Specific examples of the hydroxides of ammonium include, but
are not limited to, ammonium hydroxide and quaternary ammonium
hydroxide.
[0120] Specific examples of the hydroxides of phosphonium include,
but are not limited to, quaternary phosphonium hydroxide.
[0121] Specific examples of the carbonates of an alkali metal
include, but are not limited to, lithium carbonate, sodium
carbonate and potassium carbonate.
--Hydrodispersible Resin--
[0122] The hydrodispersible resin preferably has good film
formability (image formability), high repellency and high
weatherablity to form an image having high repellency and high
image density (high colorability).
[0123] Specific examples of the hydrodispersible resin include, but
are not limited to, condensed synthetic resins such as polyester
resins, polyurethane resins, epoxy resins, polyamide resins,
polyether resins, (meth)acrylic resins, acrylic-silicone resins and
fluorine-containing resins; additional synthetic resins such as
polyolefin, polystyrene resins, polyvinylalcohol resins, polyvinyl
ester resins, polyacrylic resins and unsaturated carboxylic resins;
and natural polymers such as celluloses, rosins and natural
rubbers.
[0124] Among these, polyurethane resin fine particles,
acrylic-silicone resin fine particles and fluorine-containing resin
fine particles are preferably used.
[0125] An average particle diameter (D50) of the hydrodispersible
resin is related with a viscosity of a dispersion liquid. The
smaller the particle diameter, the larger the viscosity when the
composition is the same. The average particle diameter (D50) of the
hydrodispersible resin is preferably not less than 50 nm so that
the ink may not have too high a viscosity. When the particle
diameter is some ten .mu.m, the resin cannot be used because of
being larger than the nozzle of inkjet head. Even when smaller than
the nozzle, the large-size particles in the ink deteriorates
discharge stability thereof. Therefore, the average particle
diameter (D50) of the hydrodispersible resin is more preferably not
greater than 200 nm so as not to impair discharge stability of the
ink.
[0126] The hydrodispersible resin preferably fixes a pigment
dispersion on a paper and films it at normal temperature to improve
fixability of the pigment.
[0127] Therefore, the hydrodispersible resin preferably has a
minimum filming temperature (MFT) not greater than 30.degree.
C.
[0128] The hydrodispersible resin preferably has a glass transition
temperature not less than -30.degree. C. because the resin film has
higher viscosity otherwise, which causes tack of the printed
matter.
[0129] The ink preferably includes the hydrodispersible resin in an
amount of from 1 to 15% by weight, and more preferably from 2 to 7%
by weight.
--Antiseptic and Antifungal Agent--
[0130] Specific examples the antiseptic and antifungal agent
include, but are not limited to, sodium dehydroacetate, sodium
sorbate, 2-pyridinethiol 1-oxide sodium, sodium benzoate, and
sodium pentachlorophenol.
--Antirust Agent--
[0131] Specific examples the antirust agent include, but are not
limited to, acid sulfite, sodium thiosulfate, ammonium
thiodiglycolate, diisopropyl ammonium nitrite, pentaerythritol
tetranitrate, and dicyclohexylammonium nitrite.
--Antioxidant--
[0132] Specific examples of the antioxidant include, but are not
limited to, a phenol-based antioxidant (including a hindered
phenol-based antioxidant), an amine-based antioxidant, a
sulfur-based antioxidant, and a phosphorus-based antioxidant.
--UV Absorber--
[0133] Specific examples of the UV absorber include, but are not
limited to, a benzophenone-based UV absorber, a benzotriazole UV
absorber, a salicylate-based UV absorber, a cyanoacrylate-based UV
absorber, and a nickel complex salt-based UV absorber.
<Method of Preparing Ink for Inkjet Recording>
[0134] A method of preparing the ink for inkjet recording of the
present invention includes dispersing or dissolving water, a
hydrosoluble organic solvent, a pigment, the polymer Q, and other
optional components in an aqueous medium to prepare a mixture; and
stirring the mixture.
[0135] The ink is preferably filtered to remove coarse particles by
a filter or a centrifugal separator and deaerated when
necessary.
[0136] Dispersion can be made by using a sand mill, a homogenizer,
a ball mill, a paint shaker, an ultrasonic disperser, and the
stirring and mixing can be made by using ordinary stirring blades,
a magnetic stirrer, and a high-speed disperser, for example.
<Ink Properties>
[0137] Physical properties of the ink of the present invention are
not particularly limited and may be appropriately selected
according to purpose.
[0138] A viscosity of the aqueous ink at 25.degree. C. is
preferably 3 to 20 mPas. An effect of improved print density and
letter quality may be obtained with the viscosity being 3 mPas or
greater. At the same time, discharge property may be ensured with
the viscosity suppressed to 20 mPas or less. The viscosity is
measured by a viscometer RE-500L from Toki Sangyo Co., Ltd. at
25.degree. C.
[0139] The ink preferably has a surface tension not greater than 40
mN/m at 25.degree. C.
<Ink Container>
[0140] The ink container of the present invention contains the
inkjet ink of the present invention and may include any other
suitable members in combination. There is no specific limit to the
container. Any form, any structure, any size, and any material can
be suitably selected. For example, an ink bag formed of aluminum
laminate film, a resin film, etc. can be suitably used as a
container.
[0141] FIG. 1 is a schematic plain view illustrating an embodiment
of the ink container 200 of the present invention. FIG. 2 is a
schematic plain view illustrating the embodiment of the ink
container 200 including a case (outer package) in FIG. 1.
[0142] As illustrated in FIG. 1, an ink bag 241 is filled with the
ink from an ink inlet 242. Subsequent to evacuation of air, the ink
inlet 242 is closed by fusion. When in use, the ink is supplied by
piercing the needle attached to the inkjet recorder into an ink
outlet 243 made of rubber. The ink bag 241 is formed of a packaging
material such as aluminum laminate film having no air permeability.
The ink bag 241 is accommodated in a cartridge case 244 made of
plastic and detachably attached to various inkjet recorders.
(Inkjet Recorder and Inkjet Recording Method)
[0143] The inkjet recorder of the present invention records
information or an image on a recording medium with the ink of the
present invention using an inkjet head. An embodiment thereof is
explained, referring to the drawings.
[0144] An inkjet recorder 101 illustrated in FIG. 3 has a sheet
feeder tray 102 to feed recording media placed in the inkjet
recorder 101, a discharging tray 103 installed in the inkjet
recorder 101, which stores the recording media on which images are
recorded (formed), and an ink cartridge installation unit 104. On
the upper surface of the ink cartridge installation unit 104 is
arranged an operating portion 105 including operation keyboard, a
display, etc. The ink cartridge installation unit 104 has a front
cover 115 that is openable and closable to detach and attach an ink
container 200. 111 represents the upper cover of the inkjet
recorder 101 and 112 represents the front surface thereof.
[0145] Inside the inkjet recorder 101, as illustrated in FIGS. 4
and 5, a guide rod 131 and a stay 132 serving as guiding members
that laterally bridge side plates provided on the right side and
left side hold a carriage 133 slidably movable in the main scanning
direction. A main scanning motor moves the carriage 133 for
scanning in an arrow direction in FIG. 5. The carriage 133 has a
recording head 134 having four inkjet recording heads that
discharge ink droplets of each color of yellow (Y), cyan (C),
magenta (M), and black (Bk) while multiple ink discharging mouths
are arranged in the direction crossing the main scanning direction
with the ink droplet discharging direction downward.
[0146] As the heads for inkjet recording that form the recording
head 134, it is possible to use a device having an
energy-generating device to discharge ink such as a piezoelectric
actuator such as a piezoelectric element, a thermal actuator that
utilizes the phase change caused by film boiling of liquid using an
electric heat conversion element such as a heat element, a
shape-memory alloy actuator that uses the metal phase change due to
the temperature change, and an electrostatic actuator that uses an
electrostatic force.
[0147] The carriage 133 has a sub tank 135 for each color to supply
each color ink to the recording head 134. The ink is supplied and
replenished to the sub-tank 135 from the ink container 200 mounted
onto the ink cartridge inserting installation unit 104 via a tube
for supplying ink.
[0148] A sheet feeding unit to feed a sheet 142 loaded on a sheet
loader (pressure plate) 141 of the sheet feeder tray 103 includes a
roller (sheet feeding roller 143) having a half-moon like form to
separate and feed the sheet 142 one by one from the sheet loader
141 and a separation pad 144 that is made of a material having a
large friction index and arranged facing the sheet feeding roller
143 while biased to the side of the sheet feeding roller 143.
[0149] A transfer unit to transfer the sheet 142 fed from the sheet
feeding unit on the lower side of the recording head 134 includes a
transfer belt 151 to electrostatically adsorb and transfer the
sheet 142, a counter roller 152 to transfer the sheet 142 fed from
the sheet feeding unit via a guide 145 while pinching the sheet 142
with the transfer belt 151, a transfer guide 153 to make the sheet
142 track on the transfer belt 151 by changing the transfer
direction of the sheet 142 being sent substantially vertically
upward by substantially 90.degree., a front head pressure roller
155 biased towards the transfer belt 151 by a pressure member 154,
and a charging roller 156 to charge the surface of the transfer
belt 151.
[0150] The transfer belt 151 is an endless form belt, stretched
between a transfer roller 157 and a tension roller 158 and
rotatable in the belt transfer direction. This transfer belt 151
include, for example, a top layer serving as a sheet adsorption
surface made of a resin material such as a copolymer (ETFE) of
tetrafluoroethylene and ethylene with no resistance control
treatment while having a thickness about 40 .mu.m, and a bottom
layer (moderate resistance layer, earth layer) made of the same
material as the top layer with resistance control treatment with
carbon. On the rear side of the transfer belt 151, a guiding member
161 is arranged corresponding to the printing area by the recording
head 134. A discharging unit to discharge the sheet 142 on which
images are recorded by the recording head 134 includes a separation
claw 171 to separate the sheet 142 from the transfer belt 151, a
discharging roller 172, and a discharging roller 173. A discharging
tray 103 is arranged below the discharging roller 172.
[0151] A duplex printing sheet feeding unit 181 is detachably
attached to the rear side of the inkjet recorder 101. The duplex
printing sheet feeding unit 181 takes in and reverses the sheet 142
that is returned by the reverse rotation of the transfer belt 151
and feeds it again between the counter roller 152 and the transfer
belt 151. A manual sheet feeding unit 182 is provided on the upper
surface of the duplex printing sheet feeding unit 181.
[0152] In this inkjet recorder, the sheet 142 is separated and fed
from the sheet feeding unit one by one substantially vertically
upward, guided by the guide 145, and transferred while being
pinched between the transfer belt 151 and the counter roller 152.
Furthermore, the front end of the sheet 142 is guided by the
transfer guide 153 and pressed against the transfer belt 151 by the
front head pressure roller 155 to change the transfer direction by
substantially 90.degree..
[0153] Since the transfer belt 151 is charged by the charging
roller 156 at this point in time, the sheet 142 is
electrostatically adsorbed to the transfer belt 151 and
transferred. By driving the recording head 134 according to the
image signal while moving the carriage 133, the ink droplet is
discharged to the sheet 142 not in motion to record an image for an
amount corresponding to one line and thereafter the sheet 142 is
transferred in a predetermined amount to conduct recording for the
next line. On receiving a signal indicating that the recording has
completed or the rear end of the sheet 142 has reached the image
recording area, the recording operation stops and the sheet 142 is
discharged to the discharging tray 103.
[0154] When the amount of ink for inkjet recording remaining in the
sub-tank 135 is detected as "approaching to empty", a predetermined
amount of the ink is replenished to the sub tank 135 from the ink
container 200.
[0155] In this inkjet recorder, it is possible to dissemble the
chassis of the ink container 200 and replace the ink bags therein
when the ink for inkjet is used up in the ink container 200. In
addition, the ink cartridge 200 stably supplies the ink even when
the ink cartridge 200 is placed upright (on its side) and installed
by front loading. Therefore, even when the upside of the main part
101 is blocked, for example, it is accommodated in a rack or
something is placed on the upper surface of the main part 101, the
ink cartridge 200 is easily exchanged.
[0156] A serial type (shuttle type) in which the carriage scans is
used in this description but this is true in a line-type inkjet
recorder having a line type head.
[0157] The inkjet recorder is applicable to various inkjet
recordings such as inkjet recording printers, facsimiles, copiers
and their combination machines.
(Recorded Matter)
[0158] The recorded matter of the present invention is a recorded
matter which is a recording medium information or images are
recorded on with the ink of the present invention, and is prepared
by discharging the ink of the present invention from an inkjet head
to record on the recording medium.
[0159] The recorded matter of the present invention has
high-quality images without bleeding, and good stability preferably
usable for various applications.
[0160] Specific examples of recording media recorded by the inkjet
recorder include, but are not limited to, plain papers, coated
papers for printing, glossy papers, special papers, clothes, films
and OHP sheets.
[0161] Among these, the plain papers and the coated papers for
printing are preferably used. The plain paper has an advantage of
being inexpensive. The coated paper for printing has an advantage
of being less expensive than the glossy paper providing smooth and
glossy images. The plain papers and the coated papers for printing
have poor dryability and have been difficult to use for inkjet, but
have improved in dryability and can be used with the ink of the
present invention.
[0162] The ink of the present invention is effectively used on a
paper eluting Ca ion in an amount of from 1.0.times.10.sup.-4 to
5.0.times.10.sup.-4 g/g. When less than 1.0.times.10.sup.-4 g/g,
improvement of the image density due to reaction agglomeration with
the pigment dispersant deteriorates. When greater than
5.0.times.10.sup.-4 g/g, an ink noticeably becomes difficult to
penetrate a paper and poorly dried, resulting in deterioration of
scratch resistance and marker resistance.
[0163] Ca ion amount eluted from a paper is calculated by the
following method.
[0164] Namely, a paper is cut to paper slips of 2.5 cm (.+-.0.5
cm).times.3.5 cm (.+-.0.5 cm), and 16 g thereof are dipped in 200 g
of high-purity water (25.degree. C.) for 40 hrs. The high-purity
water after the paper slips are dipped therein is filtered with a
0.8 cellulose acetate filter (from Advantech Co., Ltd.) to remove
foreign particles such as paper dusts, and Ca ion included therein
is determined by an ICP emission spectrometer. The resultant Ca ion
concentration [ppm] is multiplied by 200 g which is the weight of
the high-purity water, and further divided by 16 g which is the
weight of the paper dipped to determine an amount of Ca ion [g/g]
eluted from the paper.
[0165] For example, My Paper from Ricoh Company, Ltd. includes Ca
ion in an amount of 4.3.times.10.sup.-4 g/g, and Xerox 4024 from
Fuji Xerox Co, Ltd. includes Ca ion in an amount of
1.7.times.10.sup.-4 g/g.
EXAMPLES
[0166] Having generally described this invention, further
understanding can be obtained by reference to certain specific
examples which are provided herein for the purpose of illustration
only and are not intended to be limiting. In the descriptions in
the following examples, the numbers represent weight ratios in
parts, unless otherwise specified.
<Measurement of Weight-Average Molecular Weight of
Polymer>
[0167] GPC method was used with a column constant temperature
reservoir CTO-20A from Shimadzu Corp., a detector RID-10A from
Shimadzu Corp., an eluent duct pump LC-20AD from Shimadzu Corp., a
degasser DGU-20A from Shimadzu Corp., and an auto-sampler SIL-20A
from Shimadzu Corp.
[0168] Aqueous SEC columns TSKgel3000PWXL (elimination limit
molecular weight 2.times.105), TSKgel5000PWXL (elimination limit
molecular weight 2.5.times.106) and TSKgel6000PWXL (elimination
limit molecular weight 5.times.107) from Tosoh Corp. were connected
with each other to form the column. A sample was placed in an
eluent to have a concentration of 2 g/100 mL. An aqueous solution
including an acetic acid and sodium acetate having 0.5 mol/litter,
respectively was used as the eluent. The column had a temperature
of 40.degree. C. and a flow velocity was 1.0 mL/min.
[0169] As standard samples, 9 polyethylene glycols having molecular
weights of 1065, 5050, 24000, 50000, 107000, 140000, 250000, 540000
and 920000, respectively were used to determine a calibration
curve. Based on the calibration curve, a weight-average molecular
weight of the copolymer was measured.
<Synthesis of Polymer>
[0170] The following polymers 1 to 31 were prepared. Constituents,
contents thereof, a weight-average molecular weight, and M in the
formula (1) of each of the polymers are shown in Table 1.
Synthesis Example 1
Synthesis of Polymer 1
[0171] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 70.0 parts of benzylacrylate represented by the
formula (18) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 15 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 1. Potassium hydroxide was added
to the polymer 1 while diluted with water to obtain an aqueous
solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 1 had a weight-average molecular
weight of 31,000.
Synthesis Example 2
Synthesis of Polymer 2
[0172] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of 1-acryloxyethane-1,1-diphosphonic
acid represented by the formula (12), 70.0 parts of benzylacrylate
and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 15 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 2. Potassium hydroxide was added
to the polymer 2 while diluted with water to obtain an aqueous
solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 2 had a weight-average molecular
weight of 28,000.
Synthesis Example 3
Synthesis of Polymer 3
[0173] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 70.0 parts of benzyl
methacrylate represented by the formula (17) and 4.0 parts of a
polymerization initiator (azobisisobutylonitrile), and the mixture
was heated to have a temperature of 65.degree. C. Next, after the
mixture was polymerized for 15 hrs under a nitrogen stream, about a
half of the solvent in the reactant was removed. The resultant
reactant was injected in acetone to extract a polymer, and the
polymer is further dried to prepare a polymer 3. Potassium
hydroxide was added to the polymer 3 while diluted with water to
obtain an aqueous solution thereof, in which the phosphonic acid
groups were neutralized by 100%. The polymer 3 had a weight-average
molecular weight of 31,000.
Synthesis Example 4
Synthesis of Polymer 4
[0174] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 70.0 parts of
stearylacrylate represented by the formula (14) and 4.0 parts of a
polymerization initiator (azobisisobutylonitrile), and the mixture
was heated to have a temperature of 65.degree. C. Next, after the
mixture was polymerized for 15 hrs under a nitrogen stream, about a
half of the solvent in the reactant was removed. The resultant
reactant was injected in acetone to extract a polymer, and the
polymer is further dried to prepare a polymer 4. Potassium
hydroxide was added to the polymer 4 while diluted with water to
obtain an aqueous solution thereof, in which the phosphonic acid
groups were neutralized by 100%. The polymer 4 had a weight-average
molecular weight of 32,000.
Synthesis Example 5
Synthesis of Polymer 5
[0175] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of 1-acryloxyethane-1,1-diphosphonic
acid, 70.0 parts of stearylacrylate and 4.0 parts of a
polymerization initiator (azobisisobutylonitrile), and the mixture
was heated to have a temperature of 65.degree. C. Next, after the
mixture was polymerized for 15 hrs under a nitrogen stream, about a
half of the solvent in the reactant was removed. The resultant
reactant was injected in acetone to extract a polymer, and the
polymer is further dried to prepare a polymer 5. Potassium
hydroxide was added to the polymer 5 while diluted with water to
obtain an aqueous solution thereof, in which the phosphonic acid
groups were neutralized by 100%. The polymer 5 had a weight-average
molecular weight of 33,000.
Synthesis Example 6
Synthesis of Polymer 6
[0176] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 70.0 parts of
stearylmethacrylate represented by the formula (13) and 4.0 parts
of a polymerization initiator (azobisisobutylonitrile), and the
mixture was heated to have a temperature of 65.degree. C. Next,
after the mixture was polymerized for 15 hrs under a nitrogen
stream, about a half of the solvent in the reactant was removed.
The resultant reactant was injected in acetone to extract a
polymer, and the polymer is further dried to prepare a polymer 6.
Potassium hydroxide was added to the polymer 6 while diluted with
water to obtain an aqueous solution thereof, in which the
phosphonic acid groups were neutralized by 100%. The polymer 6 had
a weight-average molecular weight of 32,000.
Synthesis Example 7
Synthesis of Polymer 7
[0177] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 70.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 15 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 7. Potassium hydroxide was added
to the polymer 7 while diluted with water to obtain an aqueous
solution thereof, in which the phosphonic acid groups were
neutralized by 50%. The polymer 7 had a weight-average molecular
weight of 30,000.
Synthesis Example 8
Synthesis of Polymer 8
[0178] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 70.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 15 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 8. Ethanolamine was added to the
polymer 8 while diluted with water to obtain an aqueous solution
thereof, in which the phosphonic acid groups were neutralized by
100%. The polymer 8 had a weight-average molecular weight of
31,000.
Synthesis Example 9
Synthesis of Polymer 9
[0179] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 70.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 75.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 9. Potassium hydroxide was added
to the polymer 9 while diluted with water to obtain an aqueous
solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 9 had a weight-average molecular
weight of 2,100.
Synthesis Example 10
Synthesis of Polymer 10
[0180] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 70.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 10. Potassium hydroxide was
added to the polymer 10 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 10 had a weight-average molecular
weight of 4,200.
Synthesis Example 11
Synthesis of Polymer 11
[0181] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 70.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 24 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 11. Potassium hydroxide was
added to the polymer 11 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 11 had a weight-average molecular
weight of 50,000.
Synthesis Example 12
Synthesis of Polymer 12
[0182] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 70.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 48 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 12. Potassium hydroxide was
added to the polymer 12 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 12 had a weight-average molecular
weight of 70,000.
Synthesis Example 13
Synthesis of Polymer 13
[0183] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 5.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 95.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 75.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 13. Potassium hydroxide was
added to the polymer 13 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 13 had a weight-average molecular
weight of 2,000.
Synthesis Example 14
Synthesis of Polymer 14
[0184] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 5.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 95.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 5 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 14. Potassium hydroxide was
added to the polymer 14 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 14 had a weight-average molecular
weight of 2,000.
Synthesis Example 15
Synthesis of Polymer 15
[0185] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 5.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 95.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 24 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 15. Potassium hydroxide was
added to the polymer 15 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 15 had a weight-average molecular
weight of 49,000.
Synthesis Example 16
Synthesis of Polymer 16
[0186] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 5.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 95.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 48 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 16. Potassium hydroxide was
added to the polymer 16 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 16 had a weight-average molecular
weight of 69,000.
Synthesis Example 17
Synthesis of Polymer 17
[0187] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 10.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 90.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 75.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 17. Potassium hydroxide was
added to the polymer 17 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 17 had a weight-average molecular
weight of 2,200.
Synthesis Example 18
Synthesis of Polymer 18
[0188] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 10.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 90.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 18. Potassium hydroxide was
added to the polymer 18 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 18 had a weight-average molecular
weight of 4,300.
Synthesis Example 19
Synthesis of Polymer 19
[0189] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 10.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 90.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 24 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 19. Potassium hydroxide was
added to the polymer 19 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 19 had a weight-average molecular
weight of 50,000.
Synthesis Example 20
Synthesis of Polymer 20
[0190] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 10.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 90.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 48 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 20. Potassium hydroxide was
added to the polymer 20 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 20 had a weight-average molecular
weight of 68,000.
Synthesis Example 21
Synthesis of Polymer 21
[0191] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 60.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 40.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 75.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 21. Potassium hydroxide was
added to the polymer 21 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 21 had a weight-average molecular
weight of 68,000.
Synthesis Example 22
Synthesis of Polymer 22
[0192] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 60.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 40.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 22. Potassium hydroxide was
added to the polymer 22 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 22 had a weight-average molecular
weight of 4,000.
Synthesis Example 23
Synthesis of Polymer 23
[0193] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 60.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 40.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 24 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 23. Potassium hydroxide was
added to the polymer 23 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 23 had a weight-average molecular
weight of 48,000.
Synthesis Example 24
Synthesis of Polymer 24
[0194] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 60.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 40.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 48 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 24. Potassium hydroxide was
added to the polymer 24 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 24 had a weight-average molecular
weight of 70,000.
Synthesis Example 25
Synthesis of Polymer 25
[0195] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 80.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 20.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 75.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 25. Potassium hydroxide was
added to the polymer 25 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 25 had a weight-average molecular
weight of 2,200.
Synthesis Example 26
Synthesis of Polymer 26
[0196] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 80.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 20.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 26. Potassium hydroxide was
added to the polymer 26 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 26 had a weight-average molecular
weight of 4,200.
Synthesis Example 27
Synthesis of Polymer 27
[0197] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 80.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 20.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 24 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 27. Potassium hydroxide was
added to the polymer 27 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 27 had a weight-average molecular
weight of 49,000.
Synthesis Example 28
Synthesis of Polymer 28
[0198] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 80.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 20.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 48 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 28. Potassium hydroxide was
added to the polymer 28 while diluted with water to obtain an
aqueous solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 28 had a weight-average molecular
weight of 70,000.
Synthesis Example 29
Synthesis of Polymer 29
[0199] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 70.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 15 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 29. Lithium hydroxide was added
to the polymer 29 while diluted with water to obtain an aqueous
solution thereof, in which the phosphonic acid groups were
neutralized by 100%. The polymer 29 had a weight-average molecular
weight of 30,000.
Synthesis Example 30
Synthesis of Polymer 30
[0200] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid, 70.0 parts of
benzylacrylate and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 15 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer 30.
2-amino-2-ethyl-1,3-propanediol (AEPD) was added to the polymer 30
while diluted with water to obtain an aqueous solution thereof, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 30 had a weight-average molecular weight of 32,000.
TABLE-US-00001 TABLE 1 Polymer Constituents Polymer Synthesis
Monomer (7) Monomer (8) Weight- Example Polymer Parts by Parts by
Average M No. No. Weight Weight M/W in (1) 1 1 1-M 30 BA 70 31000 K
2 2 1-A 30 BA 70 28000 K 3 3 1-M 30 BM 70 31000 K 4 4 1-M 30 SA 70
32000 K 5 5 1-A 30 SA 70 33000 K 6 6 1-M 30 SM 70 32000 K 7 7 1-M
30 BA 70 30000 K, H 8 8 1-M 30 BA 70 31000 EA 9 9 1-M 30 BA 70 2100
K 10 10 1-M 30 BA 70 4200 K 11 11 1-M 30 BA 70 50000 K 12 12 1-M 30
BA 70 70000 K 13 13 1-M 5 BA 95 2000 K 14 14 1-M 5 BA 95 4000 K 15
15 1-M 5 BA 95 49000 K 16 16 1-M 5 BA 95 69000 K 17 17 1-M 10 BA 90
2200 K 18 18 1-M 10 BA 90 4300 K 19 19 1-M 10 BA 90 50000 K 20 20
1-M 10 BA 90 68000 K 21 21 1-M 60 BA 40 2100 K 22 22 1-M 60 BA 40
4000 K 23 23 1-M 60 BA 40 48000 K 24 24 1-M 60 BA 40 70000 K 25 25
1-M 80 BA 20 2200 K 26 26 1-M 80 BA 20 4200 K 27 27 1-M 80 BA 20
49000 K 28 28 1-M 80 BA 20 70000 K 29 29 1-M 30 BA 70 30000 Li 30
30 1-M 30 BA 70 32000 AEPD *1-M: 1-methacrloxyethane-1,
1-diphosphonic acid 1-A: 1-acrloxyethane-1, 1-diphosphonic acid BA:
benzyl acrylate BM: benzyl methacrylate SA: stearyl acrylate SM;
stearyl methacrylate EA: ethanol amine
Synthesis Example 31
Synthesis of Polymer 31
[0201] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 70.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 15 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 31 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 31 had a weight-average molecular weight of 30,000.
Synthesis Example 32
Synthesis of Polymer 32
[0202] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of 1-acryloxyethane-1,1-diphosphonic
acid represented by the formula (12), 70.0 parts of oleyl
methacrylate represented by the formula (15) and 4.0 parts of a
polymerization initiator (azobisisobutylonitrile), and the mixture
was heated to have a temperature of 65.degree. C. Next, after the
mixture was polymerized for 15 hrs under a nitrogen stream, about a
half of the solvent in the reactant was removed. The resultant
reactant was injected in acetone to extract a polymer, and the
polymer is further dried to prepare a polymer. Potassium hydroxide
was added to the polymer while diluted with water so as to include
a solid content of 10% by weight. Thus, a polymer 32 was
synthesized, in which the phosphonic acid groups were neutralized
by 100%. The polymer 32 had a weight-average molecular weight of
27,000.
Synthesis Example 33
Synthesis of Polymer 33
[0203] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 70.0 parts of oleyl acrylate represented by the
formula (16) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 15 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 33 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 33 had a weight-average molecular weight of 32,000.
Synthesis Example 34
Synthesis of Polymer 34
[0204] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of 1-acryloxyethane-1,1-diphosphonic
acid represented by the formula (12), 70.0 parts of oleyl acrylate
represented by the formula (16) and 4.0 parts of a polymerization
initiator (azobisisobutylonitrile), and the mixture was heated to
have a temperature of 65.degree. C. Next, after the mixture was
polymerized for 15 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 34 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 34 had a weight-average molecular weight of 33,000.
Synthesis Example 35
Synthesis of Polymer 35
[0205] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 70.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 15 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 35 was synthesized, in
which the phosphonic acid groups were neutralized by 50%. The
polymer 35 had a weight-average molecular weight of 30,000.
Synthesis Example 36
Synthesis of Polymer 36
[0206] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 70.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 65.degree. C. Next, after the mixture was
polymerized for 15 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Ethanol amine was added to the
polymer while diluted with water so as to include a solid content
of 10% by weight. Thus, a polymer 36 was synthesized, in which the
phosphonic acid groups were neutralized by 100%. The polymer 36 had
a weight-average molecular weight of 31,000.
Synthesis Example 37
Synthesis of Polymer 37
[0207] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 70.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 75.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 37 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 37 had a weight-average molecular weight of 3,100.
Synthesis Example 38
Synthesis of Polymer 38
[0208] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 70.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 70.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 38 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 38 had a weight-average molecular weight of 4,100.
Synthesis Example 39
Synthesis of Polymer 39
[0209] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 70.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 24 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 39 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 39 had a weight-average molecular weight of 50,000.
Synthesis Example 40
Synthesis of Polymer 40
[0210] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 30.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 70.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 48 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 40 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 40 had a weight-average molecular weight of 69,000.
Synthesis Example 41
Synthesis of Polymer 41
[0211] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 5.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 95.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 75.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 41 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 41 had a weight-average molecular weight of 3,200.
Synthesis Example 42
Synthesis of Polymer 42
[0212] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 5.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 95.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 70.degree. C. Next, after the mixture was
polymerized for 5 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 42 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 42 had a weight-average molecular weight of 4,000.
Synthesis Example 43
Synthesis of Polymer 43
[0213] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 5.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 95.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 24 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 43 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 43 had a weight-average molecular weight of 49,000.
Synthesis Example 44
Synthesis of Polymer 44
[0214] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 5.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 95.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 48 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 44 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 44 had a weight-average molecular weight of 70,000.
Synthesis Example 45
Synthesis of Polymer 45
[0215] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 10.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 90.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 75.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 45 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 45 had a weight-average molecular weight of 3,200.
Synthesis Example 46
Synthesis of Polymer 46
[0216] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 10.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 90.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 70.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 46 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 46 had a weight-average molecular weight of 4,200.
Synthesis Example 47
Synthesis of Polymer 47
[0217] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 10.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 90.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 24 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 47 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 47 had a weight-average molecular weight of 50,000.
Synthesis Example 48
Synthesis of Polymer 48
[0218] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 10.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 90.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 48 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 48 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 48 had a weight-average molecular weight of 69,000.
Synthesis Example 49
Synthesis of Polymer 49
[0219] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 60.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 40.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 75.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 49 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 49 had a weight-average molecular weight of 3,200.
Synthesis Example 50
Synthesis of Polymer 50
[0220] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 60.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 40.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 70.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 50 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 50 had a weight-average molecular weight of 4,100.
Synthesis Example 51
Synthesis of Polymer 51
[0221] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 60.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 40.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 24 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 51 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 51 had a weight-average molecular weight of 48,000.
Synthesis Example 52
Synthesis of Polymer 52
[0222] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 60.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 40.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 48 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 52 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 52 had a weight-average molecular weight of 70,000.
Synthesis Example 53
Synthesis of Polymer 53
[0223] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 80.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 20.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 75.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 53 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 53 had a weight-average molecular weight of 3,100.
Synthesis Example 54
Synthesis of Polymer 54
[0224] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 80.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 20.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 70.degree. C. Next, after the mixture was
polymerized for 3 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 54 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 54 had a weight-average molecular weight of 4,100.
Synthesis Example 55
Synthesis of Polymer 55
[0225] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 80.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 20.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 24 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 55 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 55 had a weight-average molecular weight of 49,000.
Synthesis Example 56
Synthesis of Polymer 56
[0226] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 80.0 parts of
1-methacryloxyethane-1,1-diphosphonic acid represented by the
formula (11), 20.0 parts of oleyl methacrylate represented by the
formula (15) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 50.degree. C. Next, after the mixture was
polymerized for 48 hrs under a nitrogen stream, about a half of the
solvent in the reactant was removed. The resultant reactant was
injected in acetone to extract a polymer, and the polymer is
further dried to prepare a polymer. Potassium hydroxide was added
to the polymer while diluted with water so as to include a solid
content of 10% by weight. Thus, a polymer 56 was synthesized, in
which the phosphonic acid groups were neutralized by 100%. The
polymer 56 had a weight-average molecular weight of 71,000.
Comparative Synthesis Example 1
Synthesis of Polymer 57
[0227] A flask equipped with a stirrer, a thermometer and a
nitrogen gas introduction pipe was charged with 500.0 parts of a
solvent (ethanol), 100.0 parts of
4-methacrylamide-1-hydroxybutane-1,1-diphosphonic acid having the
following formula (19) and 4.0 parts of a polymerization initiator
(azobisisobutylonitrile), and the mixture was heated to have a
temperature of 70.degree. C.
##STR00016##
[0228] Next, after the mixture was polymerized for 5 hrs under a
nitrogen stream, about a half of the solvent in the reactant was
removed. The resultant reactant was injected in acetone to extract
a polymer, and the polymer is further dried to prepare a polymer.
Potassium hydroxide was added to the polymer while diluted with
water so as to include a solid content of 10% by weight. Thus, a
polymer 57 was synthesized, in which the phosphonic acid groups
were neutralized by 100%. The polymer 57 had a weight-average
molecular weight of 4,100.
Comparative Synthesis Example 2
Preparation of Aqueous Solution of Hydroxy Ethylidene Diphosphonic
Acid Potassium
[0229] Potassium hydroxide was added to hydroxy ethylidene
diphosphonic acid (HEDP) represented by the following formula (20)
to be neutralized by 100% while diluted with water so as to include
a solid content of 10% by weight.
##STR00017##
[0230] Thus, an aqueous solution of hydroxy ethylidene diphosphonic
acid potassium (including a solid content of 10% by weight) was
prepared.
[0231] Properties of these polymers and the aqueous solution of
hydroxy ethylidene diphosphonic acid potassium are shown in Table
2.
TABLE-US-00002 TABLE 2 Polymer Constituents Polymer Synthesis
Monomer 1 Monomer 2 Weight- Example Polymer Parts by Parts by
Average M No. No. Weight Weight M/W in (1) 31 31 1-M 30 OM 70 30000
K 32 32 1-A 30 OM 70 27000 K 33 33 1-M 30 OA 70 32000 K 34 34 1-A
30 OA 70 33000 K 35 35 1-M 30 OM 70 30000 K, H 36 36 1-M 30 OM 70
31000 EA 37 37 1-M 30 OM 70 3100 K 38 38 1-M 30 OM 70 4100 K 39 39
1-M 30 OM 70 50000 K 40 40 1-M 30 OM 70 69000 K 41 41 1-M 5 OM 95
3200 K 42 42 1-M 5 OM 95 4000 K 43 43 1-M 5 OM 95 49000 K 44 44 1-M
5 OM 95 70000 K 45 45 1-M 10 OM 90 3100 K 46 46 1-M 10 OM 90 4200 K
47 47 1-M 10 OM 90 50000 K 48 48 1-M 10 OM 90 69000 K 49 49 1-M 60
OM 40 3200 K 50 50 1-M 60 OM 40 4100 K 51 51 1-M 60 OM 40 48000 K
52 52 1-M 60 OM 40 70000 K 53 53 1-M 80 OM 20 3100 K 54 54 1-M 80
OM 20 4100 K 55 55 1-M 80 OM 20 49000 K 56 56 1-M 80 OM 20 71000 K
Compara- 57 4-M 100 -- 0 4100 K tive Synthesis Example 1 Compara-
-- HEDP 100 -- 0 206 K tive Synthesis Example 2 *1-M:
1-methacrloxyethane-1, 1-diphosphonic acid 1-A: 1-acrloxyethane-1,
1-diphosphonic acid OM: oleyl methacrylate OA: oleyl acrylate 4-M:
4-methacrylamide-1-hydroxybutane-1, 1-diphosphonic acid EA: ethanol
amine
Example 1
Preparation of Pigment Dispersion 1
[0232] The following materials were premixed, subjected to a
circulation dispersion by a disc type beads mill (KDL type from
Shinmaru Enterprises Corp., using zirconia beads having a diameter
of 0.1 mm) at a peripheral speed of 10 m/s for 10 min, and filtered
with a membrane filter having an aperture of 1.2 .mu.m to prepare a
pigment dispersion 1.
TABLE-US-00003 Carbon black (NIPEX150 from Degussa AG) 20.0
Naphthalene sulfonic acid Na formalin condensate 13.0 (including a
solid content of 10% by weight) (Pionine A-45PN manufactured by
Takemoto Oil & Fat Co., Ltd.) Pure water 67.0
--Preparation of Ink--
[0233] The following materials were mixed, stirred for 1.5 hrs and
filtered with a membrane filter having an aperture of 1.2 .mu.m to
prepare an ink of Example 1.
TABLE-US-00004 Pigment Dispersion 1 40.0 (including a solid content
of pigment in an amount of 20% by weight) 1,3-butanediol
(hydrosoluble solvent) 20.0 Glycerin (hydrosoluble solvent) 10.0
2-ethyl-1,3-hexanediol (hydrosoluble solvent) 1.0
2,2,4-trimethyl-1,3-pentadiol (hydrosoluble solvent) 1.0 Fluorine
surfactant 2.0 (Zonyl FS-300 from DuPont including a solid content
in an amount of 40% by weight) Aqueous Solution of Polymer 1 20.0
(including a solid content in an amount of 10% by weight) Distilled
water 6.0
Example 2
[0234] The procedure for preparation of the ink in Example 1 was
repeated except for replacing the aqueous solution of polymer 1
with the aqueous solution of polymer 2 (including a solid content
in an amount of 10% by weight) to prepare an ink of Example 2.
Example 3
[0235] The procedure for preparation of the ink in Example 1 was
repeated except for replacing the aqueous solution of polymer 1
with the aqueous solution of polymer 3 (including a solid content
in an amount of 10% by weight) to prepare an ink of Example 3.
Example 4
[0236] The procedure for preparation of the ink in Example 1 was
repeated except for replacing the aqueous solution of polymer 1
with the aqueous solution of polymer 4 (including a solid content
in an amount of 10% by weight) to prepare an ink of Example 4.
Example 5
[0237] The procedure for preparation of the ink in Example 1 was
repeated except for replacing the aqueous solution of polymer 1
with the aqueous solution of polymer 5 (including a solid content
in an amount of 10% by weight) to prepare an ink of Example 5.
Example 6
[0238] The procedure for preparation of the ink in Example 1 was
repeated except for replacing the aqueous solution of polymer 1
with the aqueous solution of polymer 6 (including a solid content
in an amount of 10% by weight) to prepare an ink of Example 6.
Example 7
Preparation of Pigment Dispersion 7
[0239] The following materials were premixed, subjected to a
circulation dispersion by a disc type beads mill (KDL type from
Shinmaru Enterprises Corp., using zirconia beads having a diameter
of 0.1 mm) at a peripheral speed of 10 m/s for 10 min, and filtered
with a membrane filter having an aperture of 1.2 .mu.m to prepare a
pigment dispersion 7.
TABLE-US-00005 Carbon black (NIPEX150 from Degussa AG) 20.0 Aqueous
Solution of Polymer 1 50.0 (including a solid content of 10% by
weight) Pure water 30.0
--Preparation of Ink--
[0240] The following materials were mixed, stirred for 1.5 hrs and
filtered with a membrane filter having an aperture of 1.2 .mu.m to
prepare an ink of Example 7.
TABLE-US-00006 Pigment Dispersion 7 40.0 (including a solid content
of pigment in an amount of 20% by weight) 1,3-butanediol
(hydrosoluble solvent) 20.0 Glycerin (hydrosoluble solvent) 10.0
2-ethyl-1,3-hexanediol (hydrosoluble solvent) 1.0
2,2,4-trimethyl-1,3-pentadiol (hydrosoluble solvent) 1.0 Fluorine
surfactant 2.0 (Zonyl FS-300 from DuPont including a solid content
in an amount of 40% by weight) Distilled water 26.0
Example 8
[0241] The procedure for preparation of the pigment dispersion 7 in
Example 7 was repeated except for replacing the carbon black with
Pigment Blue 15:3 (Cyan Pigment CHROMOFINE BLUE from Dainichiseika
Color & Chemicals Mfg. Co., Ltd.) to prepare a pigment
dispersion 8.
[0242] Next, the procedure for preparation of the ink in Example 7
was repeated except for replacing the pigment dispersion 7 with the
pigment dispersion 8 to prepare an ink of Example 8.
Example 9
[0243] The procedure for preparation of the pigment dispersion 7 in
Example 7 was repeated except for replacing the carbon black with
Pigment Red 122 (Magenta Pigment Toner Magenta EO02 from Clariant)
to prepare a pigment dispersion 9.
[0244] Next, the procedure for preparation of the ink in Example 7
was repeated except for replacing the pigment dispersion 7 with the
pigment dispersion 9 to prepare an ink of Example 9.
Example 10
[0245] The procedure for preparation of the pigment dispersion 7 in
Example 7 was repeated except for replacing the carbon black with
Pigment Yellow (Yellow Pigment Fast Yellow 531 from Dainichiseika
Color & Chemicals Mfg. Co., Ltd.) to prepare a pigment
dispersion 10.
[0246] Next, the procedure for preparation of the ink in Example 7
was repeated except for replacing the pigment dispersion 7 with the
pigment dispersion 10 to prepare an ink of Example 10.
Examples 11 to 39
[0247] The procedure for preparation of the pigment dispersion 7 in
Example 7 was repeated except for replacing the aqueous solution of
polymer 7 with aqueous solutions of polymer 2 to 30 (each including
a solid content of 10% by weight) as shown in Table 3 to prepare
pigment dispersions 11 to 39.
[0248] Next, the procedure for preparation of the ink in Example 7
was repeated except for replacing the pigment dispersion 7 with the
pigment dispersions 11 to 39 to prepare inks of Examples 11 to
39.
Example 40
Preparation of Pigment Dispersion 40
[0249] The following materials were premixed, subjected to a
circulation dispersion by a disc type beads mill (KDL type from
Shinmaru Enterprises Corp., using zirconia beads having a diameter
of 0.1 mm) at a peripheral speed of 10 m/s for 10 min, and filtered
with a membrane filter having an aperture of 1.2 .mu.m to prepare a
pigment dispersion 40.
TABLE-US-00007 Carbon black (NIPEX150 from Degussa AG) 20.0
Naphthalene sulfonic acid Na formalin condensate 13.0 (including a
solid content of 10% by weight) Pure water 67.0
--Preparation of Ink--
[0250] The following materials were mixed, stirred for 1.5 hrs and
filtered with a membrane filter having an aperture of 1.2 .mu.m to
prepare an ink of Example 40.
TABLE-US-00008 Pigment Dispersion 40 40.0 (including a solid
content of pigment in an amount of 20% by weight) 1,3-butanediol
(hydrosoluble solvent) 20.0 Glycerin (hydrosoluble solvent) 10.0
2-ethyl-1,3-hexanediol (hydrosoluble solvent) 1.0
2,2,4-trimethyl-1,3-pentadiol (hydrosoluble solvent) 1.0 Fluorine
surfactant 2.0 (Zonyl FS-300 from DuPont including a solid content
in an amount of 40% by weight) Aqueous Solution of Polymer 31 20.0
(including a solid content in an amount of 10% by weight) Distilled
water 6.0
Example 41
[0251] The procedure for preparation of the ink in Example 40 was
repeated except for replacing the aqueous solution of polymer 31
with the aqueous solution of polymer 32 to prepare an ink of
Example 41.
Example 42
[0252] The procedure for preparation of the ink in Example 40 was
repeated except for replacing the aqueous solution of polymer 31
with the aqueous solution of polymer 33 to prepare an ink of
Example 42.
Example 43
[0253] The procedure for preparation of the ink in Example 40 was
repeated except for replacing the aqueous solution of polymer 31
with the aqueous solution of polymer 34 to prepare an ink of
Example 43.
Example 44
Preparation of Pigment Dispersion 41
[0254] The following materials were premixed, subjected to a
circulation dispersion by a disc type beads mill (KDL type from
Shinmaru Enterprises Corp., using zirconia beads having a diameter
of 0.1 mm) at a peripheral speed of 10 m/s for 10 min, and filtered
with a membrane filter having an aperture of 1.2 .mu.m to prepare a
pigment dispersion 41.
TABLE-US-00009 Carbon black (NIPEX150 from Degussa AG) 20.0 Aqueous
Solution of Polymer 31 50.0 (including a solid content of 10% by
weight) Pure water 30.0
--Preparation of Ink--
[0255] The following materials were mixed, stirred for 1.5 hrs and
filtered with a membrane filter having an aperture of 1.2 .mu.m to
prepare an ink of Example 7.
TABLE-US-00010 Pigment Dispersion 41 40.0 (including a solid
content of pigment in an amount of 20% by weight) 1,3-butanediol
(hydrosoluble solvent) 20.0 Glycerin (hydrosoluble solvent) 10.0
2-ethyl-1,3-hexanediol (hydrosoluble solvent) 1.0
2,2,4-trimethyl-1,3-pentadiol (hydrosoluble solvent) 1.0 Fluorine
surfactant 2.0 (Zonyl FS-300 from DuPont including a solid content
in an amount of 40% by weight) Distilled water 26.0
Example 45
[0256] The procedure for preparation of the pigment dispersion 41
in Example 44 was repeated except for replacing the carbon black
with Pigment Blue 15:3 (Cyan Pigment CHROMOFINE BLUE from
Dainichiseika Color & Chemicals Mfg. Co., Ltd.) to prepare a
pigment dispersion 42.
[0257] Next, the procedure for preparation of the ink in Example 44
was repeated except for replacing the pigment dispersion 41 with
the pigment dispersion 42 to prepare an ink of Example 45.
Example 46
[0258] The procedure for preparation of the pigment dispersion 41
in Example 44 was repeated except for replacing the carbon black
with Pigment Red 122 (Magenta Pigment Toner Magenta EO02 from
Clariant) to prepare a pigment dispersion 43.
[0259] Next, the procedure for preparation of the ink in Example 44
was repeated except for replacing the pigment dispersion 41 with
the pigment dispersion 43 to prepare an ink of Example 46.
Examples 47 to 72
[0260] The procedure for preparation of the pigment dispersion 41
in Example 44 was repeated except for replacing the aqueous
solution of polymer 41 with aqueous solutions of polymer 32 to 56
(each including a solid content of 10% by weight) as shown in Table
4 to prepare pigment dispersions 44 to 69.
[0261] Next, the procedure for preparation of the ink in Example 44
was repeated except for replacing the pigment dispersion 41 with
the pigment dispersions 44 to 69 to prepare inks of Examples 47 to
72.
Comparative Example 1
[0262] The procedure for preparation of the ink in Example 40 was
repeated except for replacing the aqueous solution of polymer 31
with the aqueous solution of polymer 57 to prepare an ink of
Comparative Example 1.
Comparative Example 2
[0263] The procedure for preparation of the ink in Example 40 was
repeated except for replacing the aqueous solution of polymer 31
with hydroxy ethylidenediphosphonic acid to prepare an ink of
Comparative Example 2.
[0264] The inks prepared in Examples 1 to 72 and Comparative
Examples 1 to 2 were evaluated as follows. The results are shown in
Tables 3 and 4.
<Image Density>
[0265] In an environment of 23.degree. C. and 50 RH, the ink was
filled in an inkjet printer IPSiO GX5000 from Ricoh Company, Ltd.
After a chart on which general marks of JIS X 0208 (1997), 2223
having 64 points are described by Microsoft Word 2003 was printed
on a plain paper 1 (XEROX 4200 from XEROX, Inc.) and a plain paper
2 (My Paper from Ricoh Company, Ltd.), the image density of the
general marks was measured using X-Rite938 from X-Rite, Inc. Then,
the printing mode was "plain paper-fast" mode by a driver of the
printer "without color calibration".
[0266] Image density was evaluated under the following
standard.
[0267] A: not less than 1.25
[0268] B: not less than 1.20 and less than 1.25
[0269] C: not less than 1.10 and less than 1.20
[0270] D: less than 1.10
[0271] E: Unprintable as pigment was gelated and undispersible
<Storage Stability of Pigment Dispersion>
[0272] Each of the pigment dispersions was placed in a polyethylene
container and sealed. The viscosity after stored at 60.degree. C.
for 1 week was measured to evaluate under the following standard,
compared with the initial viscosity. The viscosity was measured by
a viscometer RE500L from TOKI SANGYO CO., LTD. at 25.degree. C.
Viscosity Variation (%)=[(Y-X)/X].times.100
wherein X represents a viscosity of the pigment dispersion before
stored and Y represents a viscosity thereof after stored.
[0273] A: Viscosity variation was not greater than .+-.5%
[0274] B: Viscosity variation was greater than .+-.5% and not
greater than .+-.8%
[0275] C: Viscosity variation was greater than .+-.8% and not
greater than .+-.10%
[0276] D: Viscosity variation was greater than .+-.10% and not
greater than .+-.30%
[0277] E: Viscosity variation was greater than .+-.30% (Unevaluable
as pigment was gelated)
<Storage Stability of Ink>
[0278] Each of the inks was filled in an ink cartridge. The
viscosity after stored at 60.degree. C. for 1 week was measured to
evaluate under the following standard, compared with the initial
viscosity. The viscosity was measured by a viscometer RE500L from
TOKI SANGYO CO., LTD. at 25.degree. C.
Viscosity Variation (%)=[(Q-P)/P].times.100
wherein Q represents a viscosity of the ink before stored and Y
represents a viscosity thereof after stored
[0279] A: Viscosity variation was not greater than .+-.5%
[0280] B: Viscosity variation was greater than .+-.5% and not
greater than .+-.8%
[0281] C: Viscosity variation was greater than .+-.8% and not
greater than .+-.10%
[0282] D: Viscosity variation was greater than .+-.10% and not
greater than .+-.30%
[0283] E: Viscosity variation was greater than .+-.30% (Unevaluable
as pigment was gelated)
TABLE-US-00011 TABLE 3 Effect Pigment Dispersion Plain Plain
Pigment Other Paper 1 Paper 2 Dispersion Ink Polymer Dispersible
Image Image Storage Storage Example No. Material Pigment Density
Density Stability Stability Example 1 1 *1 CB A B B B Example 2 2
*1 CB B B B B Example 3 3 *1 CB A B B C Example 4 4 *1 CB B B C C
Example 5 5 *1 CB A B C C Example 6 6 *1 CB A B C C Example 7 1 --
CB A A A A Example 8 1 -- CP A A A A Example 9 1 -- MP A A A A
Example 10 1 -- YP A A A A Example 11 2 -- CB A A B A Example 12 3
-- CB A A B A Example 13 4 -- CB A A B B Example 14 5 -- CB A A B B
Example 15 6 -- CB A A A A Example 16 7 -- CB A B A A Example 17 8
-- CB B B A A Example 18 9 -- CB B B A A Example 19 10 -- CB A B A
A Example 20 11 -- CB A B A A Example 21 12 -- CB A B B B Example
22 13 -- CB B C B B Example 23 14 -- CB B B B B Example 24 15 -- CB
B B B B Example 25 16 -- CB B B C C Example 26 17 -- CB B B A A
Example 27 18 -- CB A B A A Example 28 19 -- CB A B A A Example 29
20 -- CB A B B B Example 30 21 -- CB B B A A Example 31 22 -- CB A
B A A Example 32 23 -- CB A B A A Example 33 24 -- CB A B B B
Example 34 25 -- CB A B C C Example 35 26 -- CB A B B B Example 36
27 -- CB A B B B Example 37 28 -- CB A B C C Example 38 29 -- CB A
B A A Example 39 30 -- CB A B A A CB: Carbon Black CP: Cyan Pigment
MP: Magenta Pigment YP: Yellow Pigment *1: Naphthalene sulfonic
acid Na formalin condensate *2: Aqueous solution of hydroxy
ethylidene diphosphonic acid potassium
TABLE-US-00012 TABLE 4 Effect Pigment Dispersion Plain Plain
Pigment Other Paper 1 Paper 2 Dispersion Ink Polymer Dispersible
Image Image Storage Storage Example No. Material Pigment Density
Density Stability Stability Example 40 31 *1 CB A B B B Example 41
32 *1 CB B B B B Example 42 33 *1 CB A B B B Example 43 34 *1 CB B
B C A Example 44 31 *1 CB A A A A Example 45 31 -- CP A A A A
Example 46 31 -- MP A A A A Example 47 31 -- YP A A A A Example 48
32 -- CB A A B A Example 49 33 -- CB A A B A Example 50 34 -- CB A
A A A Example 51 35 -- CB A B A B Example 52 36 -- CB A B B A
Example 53 37 -- CB B B A A Example 54 38 -- CB A B A A Example 55
39 -- CB A B A A Example 56 40 -- CB A B B B Example 57 41 -- CB B
C B B Example 58 42 -- CB B B B B Example 59 43 -- CB B B B B
Example 60 44 -- CB B B C C Example 61 45 -- CB B B A A Example 62
46 -- CB A B B B Example 63 47 -- CB A B B B Example 64 48 -- CB A
B B B Example 65 49 -- CB B B A A Example 66 50 -- CB A B A A
Example 67 51 -- CB A B A A Example 68 52 -- CB A B B B Example 69
53 -- CB A B C C Example 70 54 -- CB A B B B Example 71 55 -- CB A
B B B Example 72 56 -- CB A B C C Comparative 57 -- CB B C D D
Example 1 Comparative *2 -- CB E E E E Example 2 CB: Carbon Black
CP: Cyan Pigment MP: Magenta Pigment YP: Yellow Pigment *1:
Naphthalene sulfonic acid Na formalin condensate *2: Aqueous
solution of hydroxy ethylidene diphosphonic acid potassium
[0284] Tables 3 and 4 prove the inks of Examples produce images
having higher image density than those produced by the inks of
Comparative Examples even on plain papers, and have good storage
stability even when including the hydrosoluble organic solvent in
an amount greater than 20% by weight.
[0285] Having now fully described the invention, it will be
apparent to one of ordinary skill in the art that many changes and
modifications can be made thereto without departing from the spirit
and scope of the invention as set forth therein.
* * * * *