U.S. patent application number 14/142592 was filed with the patent office on 2014-04-24 for non-aqueous inkjet ink and ink set.
This patent application is currently assigned to General Co., Ltd.. The applicant listed for this patent is General Co., Ltd.. Invention is credited to Kozo ISOBE, Kengo NAGAE.
Application Number | 20140113996 14/142592 |
Document ID | / |
Family ID | 43920971 |
Filed Date | 2014-04-24 |
United States Patent
Application |
20140113996 |
Kind Code |
A1 |
ISOBE; Kozo ; et
al. |
April 24, 2014 |
NON-AQUEOUS INKJET INK AND INK SET
Abstract
A non-aqueous inkjet ink includes a polyvinyl chloride resin
synthesized by a suspension polymerization method or an emulsion
polymerization method, an organic solvent that is a mixed solvent
including diethylene glycol ethyl methyl ether, diethylene glycol
diethyl ether, and diethylene glycol monoethyl ether in which the
polyvinyl chloride resin is dissolved. This inkjet ink also
includes a pigment, and a radical polymerization inhibitor. The
radical polymerization inhibitor prevents the polyvinyl chloride
resin from gelling in a short period and causing a discharge fault,
clogging, etc. An ink set of inkjet inks includes a combination of
the non-aqueous inkjet inks above having respective colors and
including at least a cyan ink, a magenta ink, a yellow ink, and a
black ink.
Inventors: |
ISOBE; Kozo; (Shiga, JP)
; NAGAE; Kengo; (Shiga, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
General Co., Ltd. |
Osaka |
|
JP |
|
|
Assignee: |
General Co., Ltd.
Osaka
JP
|
Family ID: |
43920971 |
Appl. No.: |
14/142592 |
Filed: |
December 27, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
12929557 |
Feb 1, 2011 |
8629198 |
|
|
14142592 |
|
|
|
|
Current U.S.
Class: |
524/88 ; 524/377;
524/90; 524/91; 524/99 |
Current CPC
Class: |
C09D 11/322 20130101;
C09D 11/36 20130101 |
Class at
Publication: |
524/88 ; 524/377;
524/99; 524/91; 524/90 |
International
Class: |
C09D 11/00 20060101
C09D011/00 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 2, 2010 |
JP |
2010-021433 |
Dec 22, 2010 |
JP |
2010-286398 |
Claims
1. A non-aqueous inkjet ink, comprising: a polyvinyl chloride resin
synthesized by a suspension polymerization method or an emulsion
polymerization method; an organic solvent that is a mixed solvent
comprising diethylene glycol ethyl methyl ether, diethylene glycol
diethyl ether, and diethylene glycol monoethyl ether in which the
polyvinyl chloride resin is dissolved; a pigment; and a radical
polymerization inhibitor.
2. The non-aqueous inkjet ink according to claim 1, wherein the
radical polymerization inhibitor is selected from the group
consisting of hydroquinones, catechols, hindered amines, phenols,
phenothiazines, condensed aromatic ring quinones, and combinations
thereof.
3. The non-aqueous inkjet ink according to claim 1, wherein the
polyvinyl chloride resin is a vinyl chloride-vinyl acetate
copolymer, and wherein the vinyl chloride-vinyl acetate copolymer
has a vinyl content that is no less than 1 mass % and no more than
36 mass %.
4. The non-aqueous inkjet ink according to claim 1, wherein the
non-aqueous inkjet ink further comprises a benzotriazole.
5. The non-aqueous inkjet ink according to claim 1, wherein the
pigment is a phthalocyanine pigment, and wherein the radical
polymerization inhibitor is a hindered amine present in an amount
based on total amount of the non-aqueous inkjet ink that is no less
than 0.2 mass % and no more than 2 mass %.
6. The non-aqueous inkjet ink according to claim 1, wherein the
pigment is a quinacridone pigment, and wherein the radical
polymerization inhibitor is a hindered phenol present in an amount
based on total amount of the non-aqueous inkjet ink that is no less
than 0.05 mass % and no more than 2 mass %.
7. The non-aqueous inkjet ink according to claim 1, wherein the
pigment is a chelate azo pigment, and wherein the radical
polymerization inhibitor is a hindered amine present in an amount
based on total amount of the non-aqueous inkjet ink that is no less
than 0.05 mass % and no more than 2 mass %.
8. The non-aqueous inkjet ink according to claim 1, wherein the
pigment is carbon black, and wherein the radical polymerization
inhibitor is a hindered amine present in an amount based on total
amount of the non-aqueous inkjet ink that is no less than 0.05 mass
% and no more than 2 mass %.
9. An ink set of inkjet inks, comprising: a combination of
non-aqueous inkjet inks according to claim 1 having respective
colors and including at least: a cyan ink having a cyan color; a
magenta ink having a magenta color; a yellow ink having a yellow
color; and a black ink having a black color.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a Continuation application of
co-pending U.S. application Ser. No. 12/929,557, filed on Feb. 1,
2011, which is herein incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates in particular to a non-aqueous
inkjet ink suitable for printing images, characters, etc., on a
surface of a polyvinyl chloride sheet, etc.
[0003] Conventionally, inkjet printing, with which images,
characters, etc., are printed by discharging an inkjet ink as
microscopic droplets from a nozzle of an inkjet printer, is
favorably used for printing mainly onto paper or other
water-absorbing surface. As the inkjet ink for this purpose, an
aqueous inkjet ink having a water-soluble dye or other colorant
added therein is widely used in general.
[0004] However, recently, inkjet printing is being used to perform
printing onto various surfaces, especially in business applications
and in various other fields. There is a demand for printing images
and characters, not only with good image quality but also with good
water resistance, light resistance, friction resistance, etc., on
the various surfaces.
[0005] For this purpose, non-aqueous inkjet inks that practically
do not contain water as a solvent and use only organic solvents,
and inkjet printers that use such inks are being put to practical
use and becoming popularly used in place of aqueous inkjet
inks.
[0006] For example, a large-size inkjet printer for printing images
and characters on a surface of a polyvinyl chloride sheet, etc.,
that is frequently used as a medium, for example, for outdoor
advertisements is becoming popularly used.
[0007] As the non-aqueous inkjet ink used in the inkjet printer, an
ink containing a pigment with excellent light resistance, a binder
resin for fixing the pigment onto a surface of a polyvinyl chloride
sheet, etc., and an organic solvent capable of dissolving the
binder resin is mainly used.
[0008] As the binder resin, any of various resins that are
excellent in fixing property with respect to the surface of a
polyvinyl chloride sheet, etc., such as an acrylic resin, polyester
resin, polyurethane resin, polyvinyl chloride resin, nitrocellulose
resin, etc., is used, and among these, a polyvinyl chloride resin,
which is best in fixing property, is used favorably.
[0009] Also, by copolymerizing vinyl acetate with vinyl chloride,
the solubility in the organic solvent can be improved, and images
and characters printed on the surface of the polyvinyl chloride
sheet can be increased in flexibility to improve scratch resistance
of a print. A vinyl chloride-vinyl acetate copolymer is thus used
especially favorably as the polyvinyl chloride resin.
[0010] A non-aqueous inkjet ink using a vinyl chloride-vinyl
acetate copolymer or other polyvinyl chloride resin is described,
for example, in JP 2004-231870A, JP 2005-23298A, JP 2005-200469A,
etc.
[0011] Also, a metal coordination compound or other additive is
added in a non-aqueous inkjet ink.
[0012] A surface of a nozzle plate, etc., making up a nozzle of an
inkjet printer must have a property of appropriately repelling a
non-aqueous inkjet ink in order to discharge the non-aqueous inkjet
ink satisfactorily through the nozzle.
[0013] A coating film having a property of repelling the
non-aqueous inkjet ink is thus formed on the surface of the nozzle
plate, etc. As the coating film, a eutectoid coating film of a
fluororesin and nickel, etc., is used.
[0014] The metal coordination compound coordinates to the nickel in
the eutectoid coating film and thereby functions to improve
resistance of the eutectoid coating film against the organic
solvent contained in the non-aqueous inkjet ink.
[0015] Nitrogen-containing compounds, such as imidazoles,
benzotriazoles, etc., can be cited as examples of the metal
coordination compound.
SUMMARY OF THE INVENTION
[0016] Conventionally, as the polyvinyl chloride resin, that
synthesized by a solution polymerization method is generally used.
However, with the solution polymerization method, a large amount of
an organic solvent must be used in synthesizing the polyvinyl
chloride resin and treatment thereof is a problem.
[0017] That is, an easiest method for taking out the synthesized
polyvinyl chloride resin from inside a reaction system is to remove
the organic solvent by performing a drying process, that is, by
letting the organic solvent evaporate into air. However, recently,
in consideration of lightening an environmental load, it is
becoming necessary to recover the organic solvent by an exhaust
treatment, waste liquid treatment, etc., and thereby avoid letting
the organic solvent evaporate into air as much as possible.
[0018] Equipment required for such treatments, energy required for
operation of such equipment, etc., lower productivity of polyvinyl
chloride resin and cause rise of production cost.
[0019] Use of a polyvinyl chloride resin synthesized by a
suspension polymerization method or emulsion polymerization method
that does not require the use of a large amount of an organic
solvent as in the solvent polymerization method is thus being
examined.
[0020] However, examination by the present inventor showed that a
non-aqueous inkjet ink prepared using a polyvinyl chloride resin
synthesized by either of these methods tends to gel within a short
period in comparison to a polyvinyl chloride resin synthesized by
the conventional solution polymerization method.
[0021] Gelling occurs especially readily in a case of storage upon
vacuum filling in a bag made of an aluminum laminate material,
etc., that is generally used as a means for supplying ink to a
large-size inkjet printer.
[0022] When the polyvinyl chloride resin gels, it becomes difficult
for a predetermined amount of the ink to be discharged
appropriately through the nozzle of the inkjet printer or the
nozzle becomes clogged so that the ink cannot be discharged at all.
A problem that images, characters, etc., of satisfactory image
quality cannot be printed thus occurs. Gelling of the polyvinyl
chloride resin must be suppressed as much as possible.
[0023] An object of the present invention is to provide a
non-aqueous inkjet ink, which contains a polyvinyl chloride resin
synthesized by a suspension polymerization method or an emulsion
polymerization method and yet with which there is no possibility of
the polyvinyl chloride resin gelling within a short period and
thereby causing a discharge fault, clogging, etc., and an ink set
that includes the non-aqueous inkjet ink.
[0024] The inventor examined causes as to why a polyvinyl chloride
resin synthesized by the suspension polymerization method or the
emulsion polymerization method gels within a short period. As a
result, the inventor found that one cause of gelling readily is
that the polyvinyl chloride resin synthesized by the suspension
polymerization method or the emulsion polymerization method is high
in a residual amount of unreacted monomer in comparison to a resin
synthesized by the solution polymerization method.
[0025] That is, as is well known, the oxygen contained in air acts
as a polymerization inhibitor of a radical polymerization reaction.
However, when a non-aqueous inkjet ink is vacuum filled in the bag
and air is cut off, a state in which the unreacted monomer
undergoes the radical polymerization reaction readily is
entered.
[0026] A thermal history, etc., during storage after filling in the
bag then acts as a trigger that starts the radical polymerization
reaction, and gelling of the polyvinyl chloride resin and various
accompanying problems occur more readily the greater the residual
amount of the unreacted monomer.
[0027] Also, by examination by the inventor, it was found that
especially when the non-aqueous inkjet ink contains a basic
component with a pH in excess of 9, the basic component promotes
the radical polymerization reaction and the accompanying gelling of
the polyvinyl chloride resin.
[0028] By further examination, the inventor found that making a
radical polymerization inhibitor having a function of inhibiting
the radical polymerization reaction be contained in the non-aqueous
inkjet ink in advance is especially effective for preventing
gelling.
[0029] The present invention thus provides a non-aqueous inkjet ink
including a polyvinyl chloride resin synthesized by a suspension
polymerization method or an emulsion polymerization method, an
organic solvent for dissolving the polyvinyl chloride resin, a
pigment, and a radical polymerization inhibitor.
[0030] Although a radical polymerization inhibitor is a known
component, that the radical polymerization inhibitor
[0031] (a) is included in the non-aqueous inkjet ink containing the
polyvinyl chloride resin, with which the polymerization reaction is
completed and further polymerization reaction, crosslinking
reaction, etc., is not presumed, and
[0032] (b) thereby prevents a radical polymerization reaction of an
unreacted monomer that causes gelling of the polyvinyl chloride
resin, and
[0033] (c) further that the cause of gelling of the polyvinyl
chloride resin is the unreacted monomer contained at a large amount
especially in the polyvinyl chloride resin synthesized by the
suspension polymerization method or the emulsion polymerization
method, etc., are facts found for the first time and clarified for
the first time by the inventor in completing the present invention
and are by no means known facts.
[0034] As the radical polymerization inhibitor, at least one type
selected from the group consisting of hydroquinones, catechols,
hindered amines, phenols, phenothiazines, and condensed aromatic
ring quinones can be cited.
[0035] As is done conventionally, the non-aqueous inkjet ink may
contain a metal coordination compound or other additive.
Benzotriazoles are preferable as metal coordination compounds. In
addition to being excellent in function as metal coordination
compounds, the benzotriazoles do not exhibit basicity and thus do
not have a possibility of promoting a radical polymerization
reaction.
[0036] In a cyan non-aqueous inkjet ink that uses a phthalocyanine
pigment as the pigment, it is preferable to use a hindered amine as
the radical polymerization inhibitor. A content proportion of the
hindered amine is preferably no less than 0.2 mass % and no more
than 2 mass % of a total amount of the non-aqueous inkjet ink.
[0037] In a magenta non-aqueous inkjet ink that uses a quinacridone
pigment as the pigment, it is preferable to use a hindered phenol
as the radical polymerization inhibitor. The content proportion of
the hindered phenol is preferably no less than 0.05 mass % and no
more than 2 mass % of the total amount of the non-aqueous inkjet
ink.
[0038] In a yellow non-aqueous inkjet ink that uses a chelate azo
pigment as the pigment, it is preferable to use a hindered amine as
the radical polymerization inhibitor. The content proportion of the
hindered amine is preferably no less than 0.05 mass % and no more
than 2 mass % of the total amount of the non-aqueous inkjet
ink.
[0039] In a black non-aqueous inkjet ink that uses carbon black as
the pigment, it is preferable to use a hindered amine as the
radical polymerization inhibitor. The content proportion of the
hindered amine is preferably no less than 0.05 mass % and no more
than 2 mass % of the total amount of the non-aqueous inkjet
ink.
[0040] The organic solvent is preferably a mixed solvent of
diethylene glycol ethyl methyl ether and
[0041] at least one type of solvent selected from the group
consisting of diethylene glycol diethyl ether, tetraethylene glycol
dimethyl ether, and propylene glycol dimethyl ether.
[0042] Also, the mixed solvent may further contain at least one
type of solvent selected from the group consisting of ethylene
glycol monobutyl ether, diethylene glycol monoethyl ether,
triethylene glycol monomethyl ether, propylene glycol monobutyl
ether, dipropylene glycol monomethyl ether, dipropylene glycol
dimethyl ether, and tripropylene glycol dimethyl ether.
[0043] The present invention provides an ink set that includes at
least non-aqueous inkjet inks of respective colors of cyan,
magenta, yellow, and black and with which the non-aqueous inkjet
ink of at least one of the respective colors is the non-aqueous
inkjet ink according to the present invention.
[0044] By the present invention, a non-aqueous inkjet ink, which
contains a polyvinyl chloride resin synthesized by a suspension
polymerization method or an emulsion polymerization method and yet
with which there is no possibility of the polyvinyl chloride resin
gelling within a short period and thereby causing a discharge
fault, clogging, etc., and an ink set that includes the non-aqueous
inkjet ink can be provided.
DETAILED DESCRIPTION OF THE INVENTION
<<Non-Aqueous Inkjet Ink>>
[0045] A non-aqueous inkjet ink according to the present invention
is characterized in including a polyvinyl chloride resin
synthesized by a suspension polymerization method or an emulsion
polymerization method, an organic solvent for dissolving the
polyvinyl chloride resin, a pigment, and a radical polymerization
inhibitor.
<Polyvinyl Chloride Resin>
[0046] As the polyvinyl chloride resin, any of various polyvinyl
chloride resins synthesized by the suspension polymerization method
or the emulsion polymerization method may be used. In particular, a
vinyl chloride-vinyl acetate copolymer synthesized by the
suspension polymerization method or the emulsion polymerization
method is preferable as the polyvinyl chloride resin. When vinyl
chloride is copolymerized with vinyl acetate, solubility in the
organic solvent can be improved, and images and characters printed
on a surface of a polyvinyl chloride sheet, etc., can be increased
in flexibility to improve scratch resistance of a print.
[0047] A molecular weight, vinyl acetate content, etc., of the
vinyl chloride-vinyl acetate copolymer may be set as suited.
[0048] For example, a vinyl chloride-vinyl acetate copolymer
synthesized by the suspension polymerization method has a number
average molecular weight Mn of preferably no less than 5000 and
especially preferably no less than 10000, and preferably no more
than 100000 and especially preferably no more than 30000.
[0049] When the number average molecular weight Mn is less than the
above range, a fixing property of the vinyl chloride-vinyl acetate
copolymer with respect to the polyvinyl chloride sheet decreases
and the scratch resistance, etc., of the print may decrease.
[0050] On the other hand, when the above range is exceeded, the
non-aqueous inkjet ink becomes too high in viscosity and it may not
be possible to satisfactorily discharge the non-aqueous inkjet ink
as droplets through a nozzle of an inkjet printer.
[0051] Also, the vinyl acetate content of the vinyl chloride-vinyl
acetate copolymer is preferably no less than 1 mass %, more
preferably no less than 10 mass %, and especially preferably no
less than 13 mass %, and preferably no more than 36 mass %, more
preferably no more than 22 mass %, and especially preferably no
more than 15 mass %.
[0052] When the vinyl acetate content is less than the above range,
a solubility of the vinyl chloride-vinyl acetate copolymer
particularly in a first organic solvent to be described below
decreases so that precipitation occurs readily and the non-aqueous
inkjet ink may thereby decrease in stability.
[0053] On the other hand, when the above range is exceeded, the
fixing property of the vinyl chloride-vinyl acetate copolymer with
respect to the polyvinyl chloride sheet decreases and the scratch
resistance, etc., of the print may decrease.
[0054] Examples of the vinyl chloride-vinyl acetate copolymer
synthesized by the suspension polymerization method include one
type or two or more types among
[0055] SOLBIN CL (number average molecular weight Mn: 25000, vinyl
acetate content: 14 mass %),
[0056] SOLBIN CNL (number average molecular weight Mn: 12000, vinyl
acetate content: 10 mass %),
[0057] SOLBIN C5R (number average molecular weight Mn: 27000, vinyl
acetate content: 21 mass %),
[0058] SOLBIN AL (number average molecular weight Mn: 22000, vinyl
acetate content: 2 mass %),
[0059] SOLBIN TA5R (number average molecular weight Mn: 28000,
vinyl acetate content: 1 mass %),
[0060] SOLBIN TA0 (number average molecular weight Mn: 15000, vinyl
acetate content: 2 mass %),
[0061] SOLBIN TA3 (number average molecular weight Mn: 24000, vinyl
acetate content: 4 mass %), etc.,
[0062] which are vinyl chloride-vinyl acetate copolymers of the
SOLBIN (registered trademark) series manufactured by Nissin
Chemical Industry Co., Ltd.
[0063] A vinyl chloride-vinyl acetate copolymer synthesized by the
emulsion polymerization method has a weight average molecular
weight Mw of preferably no less than 5000, more preferably no less
than 30000, and especially preferably no less than 45000, and
preferably no more than 100000, more preferably no more than 60000,
and especially preferably no more than 55000.
[0064] When the weight average molecular weight Mw is less than the
above range, the fixing property of the vinyl chloride-vinyl
acetate copolymer with respect to the polyvinyl chloride sheet
decreases and the scratch resistance, etc., of the print may
decrease.
[0065] On the other hand, when the above range is exceeded, the
non-aqueous inkjet ink becomes too high in viscosity and it may not
be possible to satisfactorily discharge the non-aqueous inkjet ink
as droplets through a nozzle of an inkjet printer.
[0066] Also, the vinyl acetate content of the vinyl chloride-vinyl
acetate copolymer is preferably no less than 1 mass %, more
preferably no less than 10 mass %, and especially preferably no
less than 14 mass %, and preferably no more than 36 mass %, more
preferably no more than 20 mass %, and especially preferably no
more than 16 mass %.
[0067] When the vinyl acetate content is less than the above range,
the solubility of the vinyl chloride-vinyl acetate copolymer
particularly in the first organic solvent to be described below
decreases so that precipitation occurs readily and the non-aqueous
inkjet ink may thereby decrease in stability.
[0068] On the other hand, when the above range is exceeded, the
fixing property of the vinyl chloride-vinyl acetate copolymer with
respect to the polyvinyl chloride sheet decreases and the scratch
resistance, etc., of the print may decrease.
[0069] Examples of the vinyl chloride-vinyl acetate copolymer
synthesized by the emulsion polymerization method include one type
or two or more types among
[0070] VINNOL E15/45 (weight average molecular weight Mw: 45000 to
55000, vinyl acetate content: 15.0.+-.1.0 mass %),
[0071] VINNOL H14/36 (weight average molecular weight Mw: 30000 to
40000, vinyl acetate content: 14.4.+-.1.0 mass %),
[0072] VINNOL H15/42 (weight average molecular weight Mw: 35000 to
50000, vinyl acetate content: 14.0.+-.1.0 mass %),
[0073] VINNOL H40/43 (weight average molecular weight Mw: 40000 to
50000, vinyl acetate content: 34.3.+-.1.0 mass %),
[0074] VINNOL E15/45M (weight average molecular weight Mw: 50000 to
60000, vinyl acetate content: 15.0.+-.1.0 mass %),
[0075] VINNOL E15/40M (weight average molecular weight Mw: 40000 to
50000, vinyl acetate content: 15.0.+-.1.0 mass %), etc.,
[0076] which are vinyl chloride-vinyl acetate copolymers of the
VINNOL (registered trademark) series manufactured by Wacker Chemie
AG.
[0077] The content proportion of the polyvinyl chloride resin with
respect to the total amount of the non-aqueous inkjet ink is
preferably no less than 1 mass % and especially preferably no less
than 3 mass %, and preferably no more than 10 mass % and especially
preferably no more than 7 mass %.
[0078] When the content proportion is less than the above range,
the effect due to containing of the polyvinyl chloride resin, that
is, the effect of fixing the pigment onto a surface of a polyvinyl
chloride sheet, etc., cannot be obtained adequately and the scratch
resistance of the print may decrease.
[0079] On the other hand, when the content proportion exceeds the
above range, the non-aqueous inkjet ink becomes too high in
viscosity and it may not be possible to satisfactorily discharge
the non-aqueous inkjet ink as droplets through a nozzle of an
inkjet printer.
<Organic Solvent>
[0080] As the organic solvent, any of various organic solvents that
can satisfactorily dissolve the polyvinyl chloride resin may be
used. Aprotic polar solvents, such as N-methyl-2-pyrrolidone and
other nitrogen-containing heterocyclic compounds and
.gamma.-butyrolactone and other oxygen-containing heterocyclic
compounds, etc., can be cited as examples of the organic solvent.
However, an aprotic polar solvent may degrade the above-described
eutectoid coating film of a fluororesin and nickel in a short
period. Also, an aprotic polar solvent has a possibility of readily
causing gelling of the polyvinyl chloride resin.
[0081] As the organic solvent, it is preferable to use an alkylene
glycol derivative that does not readily cause the gelling and with
which there is no possibility of degrading the eutectoid coating
film, etc., in a short period.
[0082] Also, as the organic solvent, it is further preferable to
use, from among the below-described three types of first to third
organic solvents that are all alkylene glycol derivatives, a mixed
solvent of the two types of the first and second organic solvents
or a mixed solvent of the three types of the first to third organic
solvents.
[0083] When any of the above mixed solvents is used, the polyvinyl
chloride resin and the pigment can be fixed firmly onto the surface
of the polyvinyl chloride sheet, etc., and images, characters,
etc., of excellent water resistance, light resistance, scratch
resistance, etc., can be printed. Also, gelling of the polyvinyl
chloride resin in a short period and aggregation and sedimentation
of the pigment in a short period can be prevented. Moreover with
these mixed solvents, there is no possibility of degrading the
eutectoid coating film in a short period.
[0084] As the first to third organic solvents that are mixed, it is
preferable to combine and use organic solvents that do not exhibit
basicity in particular, or more specifically, organic solvents with
a pH of approximately 2 to 9. This is because with such organic
solvents that do not exhibit basicity, there is no possibility of
promotion of a radical polymerization reaction of unreacted monomer
as described above or inhibition of the function of the radical
polymerization inhibitor.
(First Organic Solvent)
[0085] One type or two or more types among ethylene glycol dimethyl
ether, diethylene glycol dimethyl ether, diethylene glycol ethyl
methyl ether (pH=6.8), etc.
(Second Organic Solvent)
[0086] One type or two or more types among diethylene glycol
diethyl ether (pH=4.0), diethylene glycol isopropyl methyl ether,
diethylene glycol butyl methyl ether, tetraethylene glycol dimethyl
ether (pH=6.7), propylene glycol dimethyl ether (pH=2.6), etc.
(Third Organic Solvent)
[0087] One type or two or more types among ethylene glycol
monomethyl ether, ethylene glycol monobutyl ether (pH=4.9),
diethylene glycol monoethyl ether (pH=7.6), diethylene glycol
monobutyl ether, diethylene glycol dibutyl ether, triethylene
glycol monomethyl ether (pH=7.8), triethylene glycol monoethyl
ether, triethylene glycol monobutyl ether, triethylene glycol butyl
methyl ether, propylene glycol monomethyl ether, propylene glycol
monobutyl ether (pH=6.9), isopropylene glycol monomethyl ether,
dipropylene glycol monomethyl ether (pH=5.8), dipropylene glycol
monoethyl ether, dipropylene glycol monobutyl ether, dipropylene
glycol dimethyl ether (pH=3.5), tripropylene glycol monomethyl
ether, tripropylene glycol dimethyl ether (pH=7.2), etc.
[0088] The above classification of the first to third organic
solvents is based on a classification method described in
JP2009-74034A.
[0089] That is, the first organic solvent is an organic solvent
having both a dissolving ability as described in (1) below and a
swelling ability as described in (2), the second organic solvent is
an organic solvent not having the dissolving ability as described
in (1) but having the swelling ability as described in (2), and the
third organic solvent is an organic solvent having neither the
dissolving ability as described in (1) nor the swelling ability as
described in (2).
(1) Dissolving Ability Test
[0090] If after adding 0.2 g of a vinyl chloride-vinyl acetate
copolymer [VYHD, made by The Dow Chemical Company, number average
molecular weight Mn=22000, vinyl acetate content 14 mass %] to 20
ml of an organic solvent and performing stirring for 1 hour at
25.+-.1.degree. C., the entire amount of the copolymer could be
dissolved (the solution became transparent), the organic solvent
was evaluated as having a dissolving ability and if the entire
amount of the copolymer could not be dissolved (the solution became
turbid and solids precipitated) the organic solvent was evaluated
as not having the dissolving ability.
[0091] A detailed procedure of the dissolving ability test is as
follows.
[0092] 20 ml of the organic solvent to be evaluated is placed in a
beaker, a stirring element with a surface coated with Teflon
(registered trademark) is placed in the beaker, and a temperature
is stabilized by leaving the beaker to stand in a constant
temperature bath set at 25.+-.1.degree. C.
[0093] A magnetic stirrer is then operated to rotate the stirring
element and stirring is performed under a condition of a rotation
speed of no less than 500 rpm and no more than 1000 rpm.
[0094] While stirring, 0.2 g of the powder-form vinyl
chloride-vinyl acetate copolymer are added and after continuing to
stir further for 1 hour, the solution is observed visually.
[0095] Then, as described above, the organic solvent with which the
solution became transparent is evaluated as having the dissolving
ability and that with which the solution became turbid and solids
precipitated was evaluated as not having the dissolving
ability.
(2) Swelling Ability Test
[0096] An unplasticized vinyl chloride pipe (VP) (JIS K67427922,
Eslon pipe for water supply VP25 R00074261) defined in Japanese
Industrial Standards JIS K6742:2004 and having a standard outer
diameter dimension of 32.0 mm and a nominal inner diameter of 25 mm
is immersed in the organic solvent, and after leaving to stand for
3 days at 60.+-.1.degree. C., a rate of change of the inner
diameter is measured, and an organic solvent with which the rate of
change is no less than 1% is evaluated as having a swelling ability
and an organic solvent with which the rate of change is less than
1% is evaluated as not having the swelling ability.
[0097] A detailed procedure of the swelling ability test is as
follows.
[0098] 300 ml of the organic solvent to be evaluated are placed in
a beaker and the beaker is left to stand in a constant temperature
bath set at 60.degree. C..+-.1.degree. C. to stabilize the
temperature.
[0099] The unplasticized vinyl chloride pipe (VP), which has been
cut to a length of 80 mm in advance and the inner diameter of which
has been measured, is then immersed in the organic solvent, and
after leaving to stand for 3 days, the pipe is taken out of the
organic solvent and the inner diameter is measured immediately.
[0100] An organic solvent with which the rate of change of inner
diameter before and after immersion is no less than 1% is then
evaluated as having the swelling ability and that with which the
rate of change is less than 1% is evaluated as not having the
swelling ability.
[0101] When the two types of the first and second organic solvents
among the three types of the organic solvents are used in
combination, the polyvinyl chloride resin can be dissolved
satisfactorily without causing degradation of the eutectoid coating
film, etc., in a short period.
[0102] That is, the first organic solvent is a good solvent for the
polyvinyl chloride resin but is not as strong in dissolving ability
as an aprotic polar solvent. The second organic solvent is even
weaker in dissolving ability. Thus, with the mixed solvent of these
two types of organic solvent, there is no possibility of
degradation of the eutectoid coating film, etc., in a short
period.
[0103] Moreover with the mixed solvent, the polyvinyl chloride
resin dissolving ability of the first organic solvent can be
compensated by the swelling action by the second organic solvent,
and the polyvinyl chloride resin dissolving ability can thereby be
improved to a level approximately equivalent to that of an aprotic
polar solvent.
[0104] Thus, in combination with the molecular structures of the
first and second organic solvents being mutually similar, effects
of improving a storage stability of the non-aqueous inkjet ink and
preventing aggregation and sedimentation of the polyvinyl chloride
resin and the pigment in a short period can be provided.
[0105] Also, a permeability of the non-aqueous inkjet ink with
respect to the polyvinyl chloride sheet, etc., can be improved to
enable the polyvinyl chloride resin and pigment to be fixed firmly
to the surface of the polyvinyl chloride sheet, etc.
[0106] Further, the third organic solvent can be used in
combination to adjust a surface tension, viscosity, etc., of the
non-aqueous inkjet ink in a range suited for inkjet printing.
[0107] In the mixed solvent combining the two types of the first
and second organic solvents, the content proportion of the first
organic solvent with respect to the total amount of the mixed
solvent is preferably no less than 5 mass % and especially
preferably no less than 8 mass %, and preferably no more than 50
mass % and especially preferably no more than 40 mass %.
[0108] When the content proportion is less than the above range,
the effect due to the first organic solvent of improving the
polyvinyl chloride resin dissolving ability and improving the
storage stability of the non-aqueous inkjet ink may not be obtained
adequately. Also, the effect of increasing the permeability to fix
the polyvinyl chloride resin and the pigment firmly onto the
surface of the polyvinyl chloride sheet, etc., may not be obtained
adequately.
[0109] On the other hand, when the content proportion exceeds the
above range, the dissolving ability of the mixed solvent may become
too strong so that especially when solid printing is performed on
the surface of the polyvinyl chloride sheet, etc., the surface may
become roughened and luster, smoothness, etc., of the print may
decrease.
[0110] In the mixed solvent combining the three types of the first
to third organic solvents, the content proportion of the first
organic solvent with respect to the total amount of the mixed
solvent is preferably no less than 5 mass % and especially
preferably no less than 8 mass %, and preferably no more than 50
mass % and especially preferably no more than 40 mass %. The
reasons for this are the same as those in the case of the mixed
solvent combining the two types of the first and second organic
solvents.
[0111] Also, the content proportion of the third organic solvent
with respect to the total amount of the mixed solvent is preferably
no less than 1 mass % and especially preferably no less than 2 mass
%, and preferably no more than 50 mass % and especially preferably
no more than 40 mass %.
[0112] When the content proportion is less than the above range,
the action due to containing of the third solvent of adjusting the
surface tension, viscosity, etc., may not be obtained
adequately.
[0113] Also, depending on the types and content proportions of the
first and second organic solvents, the dissolving ability of the
mixed solvent may be too strong so that especially when solid
printing is performed on the surface of the polyvinyl chloride
sheet, etc., the surface may become roughened and the luster,
smoothness, etc., of the print may decrease.
[0114] On the other hand, when the content proportion exceeds the
above range, the content proportions of the first and second
organic solvents become too low relatively. Thus, the effect due to
the first organic solvent of improving the polyvinyl chloride resin
dissolving ability and the effect due to the second organic solvent
of assisting the action of the first organic solvent may be
inadequate.
[0115] As a result, the effect of improving the storage stability
of the non-aqueous inkjet ink and the effect of increasing the
permeability to fix the polyvinyl chloride resin and the pigment
firmly onto the surface of the polyvinyl chloride sheet, etc., may
not be obtained adequately.
[0116] Of the various components making up the non-aqueous inkjet
ink, the pH of the components that are liquids in themselves, such
as the organic solvent, etc., shall be expressed as a value
measured by a glass electrode method.
[0117] That is, the pH is determined from a potential difference
arising across a glass electrode and a reference electrode when
both electrodes are immersed in a liquid to be measured under an
environment of 25.+-.1.degree. C. temperature. A 3 mol/1 aqueous
KCl solution is used as an internal liquid inside the glass
electrode.
[0118] The pH of a solid component in a case where the component is
water-soluble shall be expressed as the value measured by the glass
electrode method under an environment of 25.+-.1.degree. C.
temperature with the component being put in a state of a 5% aqueous
solution by dissolving in pure water. The 3 mol/1 aqueous KCl
solution is used as the internal liquid inside the glass
electrode.
[0119] As an example of an apparatus (pH meter) for pH measurement
by the glass electrode method, HM-40V made by DKK-Toa Corporation,
etc., can be cited.
[0120] As a specific measurement method, the glass electrode and
the reference electrode are immersed in the liquid to be measured
and the pH value is read after an elapse of 1 minute. Particularly
in a case of an organic solvent system, the pH value may not
stabilize, and in this case a central value of fluctuation of the
pH value is determined as the pH value.
[0121] As a preferable example of the mixed solvent, a mixed
solvent of diethylene glycol ethyl methyl ether as the first
organic solvent and at least one type of the following preferable
second organic solvents can be cited.
(Preferable Second Solvents)
[0122] Diethylene glycol diethyl ether, tetraethylene glycol
dimethyl ether, and propylene glycol dimethyl ether.
[0123] Also, a mixed solvent with which at least one type of the
following preferable third organic solvent is added to diethylene
glycol ethyl methyl ether and at least one type of the preferable
second organic solvents can be cited as a preferable example.
(Preferable Third Solvents)
[0124] Ethylene glycol monobutyl ether, diethylene glycol monoethyl
ether, triethylene glycol monomethyl ether, propylene glycol
monobutyl ether, dipropylene glycol monomethyl ether, dipropylene
glycol dimethyl ether, and tripropylene glycol dimethyl ether.
<Pigment>
[0125] As the pigment, any inorganic pigment and/or organic pigment
can be cited.
[0126] Titanium oxide, iron oxide, and other metal compounds, and
neutral, acidic, basic, and other various carbon blacks
manufactured by such known methods as a contact method, furnace
method, thermal method, etc., can be cited as examples of the
inorganic pigment among the above.
[0127] Azo pigments, polycyclic pigments, dye chelates, nitro
pigments, nitroso pigments, aniline black, etc., can be cited as
examples of organic pigments.
[0128] Azo lakes, insoluble azo pigments, condensed azo pigments,
chelate azo pigments, etc., can be cited as examples of azo
pigments.
[0129] Phthalocyanine pigments, perylene pigments, perinone
pigments, anthraquinone pigments, quinacridone pigments, dioxazine
pigments, thioindigo pigments, isoindolinone pigments,
quinophthalone pigments, etc., can be cited as examples of
polycyclic pigments.
[0130] Further, basic dye chelates, acidic dye chelates, etc., can
be cited as examples of dye chelates.
[0131] One type or two or more types of pigments may be used
according to a color type of the non-aqueous inkjet ink. Also, the
pigment may be surface-treated to improve dispersion stability in
the non-aqueous inkjet ink.
[0132] The following various pigments can be cited as specific
examples of the pigment.
(Cyan Pigment)
[0133] C. I. Pigment Blue 1, 2, 3, 15, 15:1, 15:3, 15:4, 15:6,
15:34, 16, 22, and 60.
(Magenta Pigment)
[0134] C. I. Pigment Red 5, 7, 9, 12, 48 (Ca), 48 (Mn), 49, 52, 53,
57 (Ca), 57:1, 97, 112, 122, 123, 149, 168, 177, 178, 179, 184,
202, 206, 207, 209, 242, 254, and 255.
(Yellow Pigment)
[0135] C. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 14C, 16, 17, 20,
24, 73, 74, 75, 83, 86, 93, 94, 95, 97, 98, 109, 110, 114, 117,
120, 125, 128, 129, 130, 137, 138, 139, 147, 148, 150, 151, 154,
155, 166, 168, 180, 185, 213, and 214.
(Black Pigment)
[0136] C. I. Pigment Black 7.
(Orange Pigment)
[0137] C. I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, and 74.
(Green Pigment)
[0138] C. I. Pigment Green 7 and 36.
(Violet Pigment)
[0139] C. I. Pigment Violet 19, 23, 29, 30, 37, 40, and 50.
[0140] The content proportion of the pigment with respect to the
total amount of the non-aqueous inkjet ink is preferably no less
than 0.1 mass % and especially preferably no less than 0.4 mass %,
and preferably no more than 10 mass % and especially preferably no
more than 8 mass %.
[0141] The pigment is preferably used as a manufacturing raw
material of the non-aqueous inkjet ink in a state of a pigment
dispersion prepared by dispersing in a suitable solvent.
[0142] As the solvent making up the pigment dispersion, any of
various solvents that are soluble in the organic solvent making up
the non-aqueous inkjet ink and are yet capable of satisfactorily
dispersing the pigment may be used. For example, when the organic
solvent is a combined system of two or more types among the three
types of the first to third organic solvents, one type or two or
more types of the three types of organic solvents is or are
favorably used as the solvent making up the pigment dispersion.
[0143] Also, the pigment dispersion may contain various additives
such as a dispersing agent for satisfactorily dispersing the
pigment.
[0144] The pH of the pigment dispersion is preferably approximately
2 to 9 to prevent promotion of the radical polymerization reaction
of the unreacted monomer or inhibition of the function of the
radical polymerization inhibitor. For adjustment of the pH of the
pigment dispersion within the above range, the type, amount,
combination, etc., of the solvent, pigment, dispersing agent, etc.,
are selected as suited.
<Radical Polymerization Inhibitor>
[0145] As the radical polymerization inhibitor, any of various
compounds having a function of trapping radicals and thereby
inhibiting the radical polymerization reaction of the unreacted
monomer contained in the polyvinyl chloride resin may be used.
[0146] However, a radical polymerization inhibitor that does not
inhibit a dischargeability of the non-aqueous inkjet ink and yet is
excellent in efficiency of polymerization inhibition effect is
preferable.
[0147] The efficiency of polymerization inhibition effect refers to
the content proportion of the radical polymerization inhibitor
required to express the effect of inhibiting the radical
polymerization reaction of the unreacted monomer at a fixed level.
It can be said that the lower this content proportion, the higher
the efficiency of polymerization inhibition effect.
[0148] A radical polymerization inhibitor that can efficiently
inhibit the radical polymerization reaction of the monomer and
suppress gelling of the polyvinyl chloride resin by being contained
at as low an amount as possible is preferable.
[0149] Especially in a case of using the mixed solvent of the two
types of the first and second organic solvents or the mixed solvent
of the three types of the first to third organic solvents that is
not as strong in dissolving ability as an aprotic polar organic
solvent as described above, it is preferable to select and use a
radical polymerization inhibitor of excellent efficiency of
polymerization inhibition effect that provides a high
polymerization inhibition effect at as low an addition amount as
possible.
[0150] Satisfactory dissolution of the polyvinyl chloride resin can
thereby be maintained while minimizing decrease of the content
proportion of the mixed solvent due to the containing of the
radical polymerization inhibitor.
[0151] As the radical polymerization inhibitor that meets these
conditions, one type or two or more types among hydroquinones,
catechols, hindered amines, phenols, phenothiazines, and condensed
aromatic ring quinones can be cited as examples.
[0152] As examples of hydroquinones, one type or two or more types
among hydroquinone, hydroquinone monomethyl ether,
1-o-2,3,5-trimethylolhydroquinone, 2-tert-butylhydroquinone, etc.,
can be cited.
[0153] As examples of catechols, one type or two or more types
among catechol, 4-methylcatechol, and 4-tert-butylcatechol, etc.,
can be cited.
[0154] As examples of hindered amines, any of hindered amines
having a polymerization inhibition effect can be cited, and among
these, one type or two or more types of hindered amine having a
tetramethylpiperidinyl group in the molecule is or are
preferable.
[0155] As examples of phenols, one type or two or more types among
phenol, butylhydroxytoluene, butylhydroxyanisole, pyrogallol, alkyl
esters of gallic acid, hindered phenols, etc., can be cited.
[0156] As examples of phenothiazines, phenothiazine, etc., can be
cited.
[0157] Further as examples of condensed aromatic ring quinones,
naphthoquinone, etc., can be cited.
[0158] Among the above, hindered amines and/or hindered phenols,
which are especially excellent in the efficiency of polymerization
inhibition effect, are used favorably as radical polymerization
inhibitors.
[0159] As the hindered amines,
4,4'-[(1,10-dioxo-1,10-decanediyl)bis(oxy)]bis[2,2,6,6-tetramethyl]-1-pip-
eridinyloxy [alternative name:
bis(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl) sebacate, Irgastab
(registered trademark) UV10 made by Ciba Specialty Chemicals Corp.
or equivalent product], etc., are especially preferable.
[0160] As examples of the hindered phenols, a mixture in which
.alpha.,.alpha.',.alpha.''-1,2,3-propanetriyltris[.omega.[(1-oxo-2-propen-
e-1-yl)ox y]]-poly[oxy(methyl-1,2-ethanediyl)] has
2,6-bis(1,1-dimethylethyl)-4-(phenylmethylene)-2,5-cyclohexadine-1-one
mixed therein as an effective component [Irgastab UV22 made by Ciba
Specialty Chemicals Corp. (mixture with the proportion of the
former being 76 to 90 mass % and the proportion of the latter being
24 to 10 mass %)], etc., are preferable.
[0161] The efficiency of polymerization inhibition effect varies
greatly not only according to the type of the radical
polymerization inhibitor but also according to the types of other
components combined with the radical polymerization inhibitor,
especially the pigment. Although the reason for this is not clear,
it is considered that a structure of a chromogenic group, etc.,
contained in the pigment has an effect.
[0162] That is, a mechanism by which the radical polymerization
reaction is inhibited differs according to the type of the radical
polymerization inhibitor, and it is considered that whether a
favorable effect or unfavorable effect is applied to the different
mechanisms differs according to the type of the pigment, that is,
according to the structure of the chromogenic group, etc.
[0163] It is thus preferable that, in accordance with the type of
the pigment used, a radical polymerization inhibitor, with which
the efficiency of polymerization inhibition effect is maximized
when combined with the pigment, is contained at an optimal
range.
[0164] For example, the following pigment and radical
polymerization inhibitor combinations may be considered for inks of
the respective colors of cyan, magenta, yellow, and black that are
used in combination to form a full-color image on the surface of
the polyvinyl chloride sheet, etc.
<Cyan Ink>
[0165] In a cyan non-aqueous inkjet ink using a phthalocyanine
pigment, such as C. I. Pigment Blue 15, 15:1, 15:3, 15:4, 15:6,
15:34, etc., a hindered amine is preferably used as the radical
polymerization inhibitor.
[0166] Also, as the hindered amine, Irgastab UV10 or an equivalent
product is preferably used.
[0167] The content proportion of the hindered amine with respect to
the total amount of the non-aqueous inkjet ink is preferably no
less than 0.2 mass % and especially preferably no less than 0.5
mass %, and preferably no more than 2 mass % and especially
preferably no more than 1.5 mass %.
[0168] When the content proportion is below the above range, the
effect due to the hindered amine of inhibiting the radical
polymerization reaction and preventing the gelling of the polyvinyl
chloride resin may not be obtained adequately.
[0169] On the other hand, when the above range is exceeded, a
further effect is not obtained and in addition, the excess hindered
amine may inhibit color expression by the pigment and change a hue
of an image or character printed on the surface of the polyvinyl
chloride sheet, etc.
[0170] Also, many of the hindered amines take a form of a brown
powder at room temperature.
[0171] Thus, when a large amount of the hindered amine is contained
in excess of the above range, the viscosity of the non-aqueous
inkjet ink becomes too high and it may not be possible to
satisfactorily discharge the non-aqueous inkjet ink as droplets
through the nozzle of the inkjet printer.
[0172] Further, the excess hindered amine may precipitate and
decrease the fixing property of the print and decrease the image
quality.
<Magenta Ink>
[0173] In a magenta non-aqueous inkjet ink using a quinacridone
pigment, such as C. I. Pigment Red 122, etc., a hindered phenol is
preferably used as the radical polymerization inhibitor.
[0174] Also, as the hindered phenol, Irgastab UV22 is preferably
used.
[0175] The content proportion of the hindered phenol with respect
to the total amount of the non-aqueous inkjet ink is preferably no
less than 0.05 mass % and especially preferably no less than 0.1
mass %, and preferably no more than 2 mass % and especially
preferably no more than 1 mass %.
[0176] When the content proportion is below the above range, the
effect due to the hindered phenol of inhibiting the radical
polymerization reaction and preventing the gelling of the polyvinyl
chloride resin may not be obtained adequately.
[0177] On the other hand, when the above range is exceeded, a
further effect is not obtained and in addition, the excess hindered
phenol may inhibit color expression by the pigment and change the
hue of an image or character printed on the surface of the
polyvinyl chloride sheet, etc.
[0178] Also, many of the hindered phenols take a form of a viscous
yellow liquid at room temperature.
[0179] Thus, when a large amount of the hindered phenol is
contained in excess of the above range, the viscosity of the inkjet
ink becomes too high and it may not be possible to satisfactorily
discharge the non-aqueous inkjet ink as droplets through the nozzle
of the inkjet printer.
[0180] Further, the excess hindered phenol may precipitate and
decrease the fixing property of the print and decrease the image
quality.
<Yellow Ink>
[0181] In a yellow non-aqueous inkjet ink using a chelate azo
pigment, such as C. I. Pigment Yellow 150, etc., a hindered amine
is preferably used as the radical polymerization inhibitor.
[0182] Also, as the hindered amine, Irgastab UV10 or an equivalent
product is preferably used.
[0183] The content proportion of the hindered amine with respect to
the total amount of the non-aqueous inkjet ink is preferably no
less than 0.05 mass % and especially preferably no less than 0.1
mass %, and preferably no more than 2 mass % and especially
preferably no more than 0.5 mass %.
[0184] The reasons why the above range is preferable for the
content proportion of the hindered amine are the same as those in
the case of the cyan non-aqueous inkjet ink.
<Black Ink>
[0185] In a black non-aqueous inkjet ink using carbon black as the
pigment, a hindered amine is preferably used as the radical
polymerization inhibitor.
[0186] Also, as the hindered amine, Irgastab UV10 or an equivalent
product is preferably used.
[0187] The content proportion of the hindered amine with respect to
the total amount of the non-aqueous inkjet ink is preferably no
less than 0.05 mass % and especially preferably no less than 0.1
mass %, and preferably no more than 2 mass % and especially
preferably no more than 0.5 mass %.
[0188] The reasons why the above range is preferable for the
content proportion of the hindered amine are the same as those in
the case of the cyan non-aqueous inkjet ink.
<Metal Coordination Compound>
[0189] The non-aqueous inkjet ink according to the present
invention may contain a metal coordination compound.
[0190] As described above, the metal coordination compound
coordinates to the nickel in the eutectoid coating film and thereby
functions to improve resistance of the eutectoid coating film
against the organic solvent.
[0191] Nitrogen-containing compounds, such as imidazoles,
benzotriazoles, etc., can be cited as examples of the metal
coordination compound.
[0192] Benzotriazoles are especially preferable as metal
coordination compounds. In addition to being excellent in function
as metal coordination compounds, the benzotriazoles do not exhibit
basicity and thus do not have a possibility of promoting a radical
polymerization reaction.
[0193] As specific examples of the benzotriazoles,
1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, etc., can be
cited. This compound is a water-soluble solid and the pH measured
with a 5% aqueous solution prepared by dissolving in pure water is
7.5.
[0194] The content proportion of the metal coordination compound
with respect to the total amount of the non-aqueous inkjet ink is
preferably no less than 0.1 mass % and especially preferably no
less than 0.3 mass %, and preferably no more than 5 mass % and
especially preferably no more than 3 mass %.
[0195] When the content proportion is below the above range, the
effect due to containing of the metal coordination compound of
improving the resistance of the eutectoid film against the organic
solvent may not be obtained adequately.
[0196] On the other hand, when the content proportion exceeds the
above range, the non-aqueous inkjet ink becomes too high in
viscosity and it may not be possible to satisfactorily discharge
the non-aqueous inkjet ink as droplets through the nozzle of the
inkjet printer.
[0197] Also, the excess metal coordination compound may precipitate
to decrease the fixing property of the print and decrease the image
quality.
<Others>
[0198] In addition to the above components, an epoxidized substance
for trapping chlorine produced by dehydrochlorination of the
polyvinyl chloride resin or any of other various additives, such as
a polymer dispersing agent, surfactant, plasticizer, antistatic
agent, viscosity modifier, surface tension modifier, leveling
agent, antifoaming agent, antioxidant, pH adjuster, ultraviolet
absorber, photostabilizer, fungicide, biocidal agent, etc., may be
contained as necessary at suitable proportions in the non-aqueous
inkjet ink.
<<Ink Set>>
[0199] The present invention provides an ink set that is used in an
inkjet printer, is used to form, for example, a full-color image on
a surface of a polyvinyl chloride sheet, etc., includes non-aqueous
inkjet inks at least of respective colors of cyan, magenta, yellow,
and black, and is characterized in that the non-aqueous inkjet ink
of at least one of the respective colors is the non-aqueous inkjet
ink according to the present invention.
[0200] The polyvinyl chloride resin that is synthesized by the
suspension polymerization method or the emulsion polymerization
method and is contained in the non-aqueous inkjet ink is thereby
prevented from gelling in a short period and causing a discharge
fault, clogging, etc., upon being vacuum filled and stored in a bag
made, for example, of an aluminum laminate material, etc.
[0201] In particular, the gelling occurs most readily in a cyan
non-aqueous inkjet ink that contains a phthalocyanine pigment and
is least likely to occur in a yellow non-aqueous inkjet ink that
contains a chelate azo pigment. Although the reason for this is not
clear, it is considered that the structure of the pigment has an
effect.
[0202] Thus, with the ink set, at least the cyan ink should be the
non-aqueous inkjet ink according to the present invention. That is,
a radical polymerization inhibitor should be contained in the cyan
non-aqueous inkjet ink.
[0203] However, in consideration of reliably preventing gelling in
the non-aqueous inkjet inks of the other colors to form an image,
especially a full-color image of excellent image quality and color
reproducibility on the surface of the polyvinyl chloride sheet, it
is preferable for the inks of all four colors to contain radical
polymerization inhibitors and be the non-aqueous inkjet ink
according to the present invention.
[0204] In addition to the above four colors, light-color
non-aqueous inkjet inks of light cyan, light magenta, light yellow,
gray, etc., may be combined in the ink set.
[0205] In this case, all of the light-color non-aqueous inkjet inks
are low in the amounts of pigment and polyvinyl chloride resin and
are thus less likely to gel even in comparison to yellow and thus
do not have to contain radical polymerization inhibitors. However
in consideration of reliably preventing gelling, radical
polymerization inhibitors may be contained in the light-color
non-aqueous inkjet inks.
EXAMPLES
[0206] Preparation, measurement, and testing of non-aqueous inkjet
inks of the following examples and comparative examples were
carried out under an environment of 25.+-.1.degree. C. temperature
and 55.+-.1% relative humidity unless noted otherwise.
Cyan Ink
Example 1
[0207] While stirring 18 mass parts of diethylene glycol monoethyl
ether (2EG-1E, pH=7.6), 4 mass parts of a vinyl chloride-vinyl
acetate copolymer synthesized by the emulsion polymerization method
[VINNOL (registered trademark) E15/45 made by Wacker Chemie AG,
weight average molecular weight Mw: 45000 to 55000, vinyl acetate
content: 15.0.+-.1.0 mass %] were added and dispersed as a binder
resin, and thereafter 25.3 mass parts of diethylene glycol diethyl
ether (2EG-2E, pH=4.0) were added to swell the copolymer.
[0208] Then, while continuing to stir, 22 mass parts of diethylene
glycol ethyl methyl ether (2EG-EM, pH=6.8) were added to dissolve
the copolymer and thereafter, 0.2 mass parts of
4,4-[(1,10-dioxo-1,10-decanediyl)bis(oxy)]bis[2,2,6,6-tetramethyl]-1-pipe-
ridinyloxy [product equivalent to Irgastab (registered trademark)
UV10 made by Ciba Specialty Chemicals Corp.] as a hindered amine
(radical polymerization inhibitor) and 0.5 mass parts of
1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole (pH measured in
the state of 5% aqueous solution=7.5) as a metal coordination
compound were added to prepare a resin solution.
[0209] Also, a pigment dispersion was prepared in which C. I.
Pigment Blue 15:3 was dispersed as a phthalocyanine pigment in
diethylene glycol diethyl ether (pigment concentration 15 mass %,
pH=8.6), and 30 mass parts of the pigment dispersion were added to
70 mass parts of the resin solution prepared in advance and further
stirring was performed to form a uniform phase and thereby
manufacture a non-aqueous inkjet ink.
Example 2
[0210] Besides setting the amount of the hindered amine in the
resin solution to 0.5 mass parts and the amount of diethylene
glycol diethyl ether to 25 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 1.
Example 3
[0211] Besides setting the amount of the hindered amine in the
resin solution to 1 mass part and the amount of diethylene glycol
diethyl ether to 24.5 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 1.
Example 4
[0212] Besides setting the amount of the hindered amine in the
resin solution to 1.5 mass parts and the amount of diethylene
glycol diethyl ether to 24 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 1.
Example 5
[0213] Besides setting the amount of the hindered amine in the
resin solution to 2 mass parts and the amount of diethylene glycol
diethyl ether to 23.5 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 1.
Comparative Example 1
[0214] Besides not adding the hindered amine to the resin solution
and setting the amount of diethylene glycol diethyl ether to 25.5
mass parts, a non-aqueous inkjet ink was manufactured in the same
manner as in Example 1.
<Storage Property Test>
[0215] Approximately 50 g of each of the non-aqueous inkjet inks
manufactured in Examples 1 to 5 and Comparative Example 1 were
injected into a bag (approximately 8 cm long.times.approx. 9 cm
wide) made of an aluminum laminate material and vacuum filling was
performed, that is, an interior of the bag was degassed and then
heat sealing was performed.
[0216] The bag was then left to stand under an environment of
90.+-.1.degree. C. to reproduce a thermal history during storage,
which is considered to be one of triggers that start the radical
polymerization reaction, and then opened four days later to
determine, from a change of viscosity of the non-aqueous inkjet
ink, whether or not the radical polymerization reaction occurred.
That is, the viscosity of each non-aqueous inkjet ink was measured
under conditions of 25.+-.1.degree. C. and 20 rpm before filling
into the bag and after taking out from the bag and the difference
in viscosity was determined to evaluate whether or not the radical
polymerization reaction occurred according to the following
standards.
[0217] Excellent: The difference in viscosity was less than 1.0
mPas and it was judged that the radical polymerization reaction did
not proceed at all.
[0218] Good: The difference in viscosity was no less than 1.0 mPas
and no more than 1.5 mPas and it was judged that the radical
polymerization reaction hardly proceeded.
[0219] Normal: The difference in viscosity was no less than 1.5
mPas and no more than 2.0 mPas and it was judged that although the
radical polymerization reaction proceeded, there are no problems in
terms of practical use.
[0220] Poor: The difference in viscosity was no less than 2.0 mPas
or gelling of the polyvinyl chloride resin occurred and it was
judged that the radical polymerization reaction proceeded.
<Hue Difference Evaluation>
[0221] Approximately 0.5 ml of each of the non-aqueous inkjet inks
manufactured in Examples and Comparative Example were dropped onto
a surface of a polyvinyl chloride sheet and after coating the ink
onto the surface of the polyvinyl chloride sheet using a wire bar
(0.1 mm diameter), hot air was blown on for approximately 20
seconds using a hairdryer, and thereafter the sheet was left to
stand for 10 minutes at 25.+-.1.degree. C. to thereby prepare a
drawdown sample.
[0222] A hue of the drawdown sample was measured using a handy type
spectrophotometric color difference meter [NF999 made by Nippon
Denshoku Industries Co., Ltd.]. With each drawdown sample,
measurements were made at three locations and an average value was
determined. A hue difference .DELTA.E with respect to the drawdown
sample formed using the non-aqueous inkjet ink of Comparative
Example 1 that does not contain the polymerization inhibitor was
determined, and whether a deviation of the hue was large or small
was evaluated according to the following standards.
[0223] Good: The .DELTA.E was less than 1.0 and it was judged that
there was no deviation of hue.
[0224] Normal: The .DELTA.E was no less than 1.0 and less than 1.5
and it was judged that although the hue deviated slightly, there
are no problems in terms of practical use.
[0225] Poor: The .DELTA.E was no less than 1.5 and it was judged
that deviation of hue occurred.
[0226] The results of the above are shown in Table 1.
TABLE-US-00001 TABLE 1 Comparative Example 1 Example 2 Example 3
Example 4 Example 5 Example 1 Mass parts Cyan pigment dispersion
(pH = 8.6) 30 30 30 30 30 30 Organic 2EG-EM (pH = 6.8) 22 22 22 22
22 22 solvent 2EG-2E (pH = 4.0) 25.3 25 24.5 24 23.5 25.5 2EG-1E
(pH = 7.6) 18 18 18 18 18 18 N-methyl-2-pyrrolidone -- -- -- -- --
-- (pH = 11.7) Radical UV10 0.2 0.5 1 1.5 2 -- Polymerization
(hindered amine compound) inhibitor UV22 -- -- -- -- -- --
(hindered phenol compound) Binder resin VINNOL E15/45 4 4 4 4 4 4
(emulsion polymerization) SOLBIN CL -- -- -- -- -- -- (suspension
polymerization) Metal 2-methylimidazole -- -- -- -- -- --
Coordination (pH = 11.0) compound 1-[N,N-bis(2-ethylhexyl) 0.5 0.5
0.5 0.5 0.5 0.5 aminomethyl]benzotriazole (pH = 7.5) Evaluation
Storage property Normal Excellent Excellent Excellent Excellent
Poor Hue difference .DELTA.E Good Good Good Good Normal
Reference
[0227] From the results for Examples 1 to 5 and Comparative Example
1 shown in Table 1, it was found that by making the cyan
non-aqueous inkjet ink that uses the phthalocyanine pigment as the
pigment contain a hindered amine as the radical polymerization
inhibitor, the radical polymerization reaction of the unreacted
monomer and the accompanying gelling of the polyvinyl chloride
resin can be prevented.
[0228] Also, from the results for Examples 1 to 5, it was found
that in the cyan non-aqueous inkjet ink, the content proportion of
the hindered amine with respect to the total amount of the
non-aqueous inkjet ink is preferably no less than 0.2 mass % and
especially preferably no less than 0.5 mass %, and preferably no
more than 2 mass % and especially preferably no more than 1.5 mass
%.
Example 6
[0229] As the binder resin, a vinyl chloride-vinyl acetate
copolymer synthesized by the suspension polymerization method
[SOLBIN (registered trademark) CL manufactured by Nissin Chemical
Industry Co., Ltd., number average molecular weight Mn: 25000,
vinyl acetate content: 14 mass] was used in place of the vinyl
chloride-vinyl acetate copolymer synthesized by the emulsion
polymerization method.
[0230] Also, besides adding 4 mass parts of the vinyl
chloride-vinyl acetate copolymer to the resin solution and setting
the amount of the hindered amine to 1 mass part and the amount of
diethylene glycol diethyl ether to 24.5 mass parts, a non-aqueous
inkjet ink was manufactured in the same manner as in Example 1.
Comparative Example 2
[0231] Besides not adding the hindered amine to the resin solution
and setting the amount of diethylene glycol diethyl ether to 25.5
mass parts, a non-aqueous inkjet ink was manufactured in the same
manner as in Example 6.
Example 7
[0232] As the metal coordination compound, 2-methylimidazole
(pH=11.0) was used in place of
1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole.
[0233] Also, besides adding 0.5 mass parts of the 2-methylimidazole
to the resin solution and setting the amount of the hindered amine
to 1 mass part and the amount of diethylene glycol diethyl ether to
24.5 mass parts, a non-aqueous inkjet ink was manufactured in the
same manner as in Example 1.
Example 8
[0234] N-methyl-2-pyrrolidone (pH=11.7) was used in place of
diethylene glycol ethyl methyl ether.
[0235] Also, besides adding 22 mass parts of the
N-methyl-2-pyrrolidone to the resin solution and setting the amount
of the hindered amine to 1 mass part and the amount of diethylene
glycol diethyl ether to 24.5 mass parts, a non-aqueous inkjet ink
was manufactured in the same manner as in Example 1.
[0236] The storage property test and the hue difference evaluation
were carried out on the non-aqueous inkjet inks manufactured in
Examples 6 to 8. The results are shown in Table 2.
TABLE-US-00002 TABLE 2 Comparative Example 6 Example 7 Example 8
Example 2 Mass parts Cyan pigment dispersion (pH = 8.6) 30 30 30 30
Organic 2EG-EM (pH = 6.8) 22 22 -- 22 Solvent 2EG-2E (pH = 4.0)
24.5 24.5 24.5 25.5 2EG-1E (pH = 7.6) 18 18 18 18
N-methyl-2-pyrrolidone -- -- 22 -- (pH = 11.7) Radical UV10 1 1 1
-- Polymerization (hindered amine compound) inhibitor UV22 -- -- --
-- (hindered phenol compound) Binder resin VINNOL E15/45 -- 4 4 --
(emulsion polymerization) SOLBIN CL 4 -- -- 4 (suspension
polymerization) Metal 2-methylimidazole -- 0.5 -- -- Coordination
(pH = 11.0) compound 1-[N,N-bis(2-ethylhexyl) 0.5 -- 0.5 0.5
aminomethyl]benzotriazole (pH = 7.5) Evaluation Storage property
Excellent Good Good Poor Hue difference .DELTA.E Good Good Good
Good
[0237] From the results for Examples 1 to 5 and Comparative Example
1 in the previous Table 1 and the results for Example 6 and
Comparative Example 2 in Table 2, it was found that equivalent
results are obtained using either of the resin synthesized by the
suspension polymerization method and the resin synthesized by the
emulsion polymerization method as the polyvinyl chloride resin.
[0238] Also, from the results of Examples 1 to 5 and Example 7, it
was found that a benzotriazole is preferable as the metal
coordination compound.
[0239] Further, from the results of Examples 1 to 5 and Example 8,
it was found that it is preferable to use a combination of alkylene
glycol derivatives all having a pH of 2 to 9 as the organic
solvent, and that combined use of diethylene glycol ethyl methyl
ether, diethylene glycol diethyl ether, which is the preferable
second solvent, and diethylene glycol monoethyl ether, which is the
preferable third solvent, is especially preferable.
Example 9
[0240] A mixture in which
.alpha.,.alpha.',.alpha.''-1,2,3-propanetriyltris[.omega.-[(1-oxo-2-prope-
ne-1-yl) ox y]]-poly[oxy(methyl-1,2-ethanediyl)] has
2,6-bis(1,1-dimethylethyl)-4-(phenylmethylene)-2,5-cyclohexadine-1-one
mixed therein as an effective component [Irgastab UV22 made by Ciba
Specialty Chemicals Corp. (mixture of 76 to 90 mass % of the former
and 24 to 10 mass % of the latter)] was used as a hindered phenol
radical polymerization inhibitor in place of the hindered
amine.
[0241] Also, besides adding 1 mass part of the hindered phenol to
the resin solution and setting the amount of diethylene glycol
diethyl ether to 24.5 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 1.
Example 10
[0242] Besides setting the amount of the hindered phenol in the
resin solution to 1.5 mass parts and the amount of diethylene
glycol diethyl ether to 24 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 9.
Example 11
[0243] Besides setting the amount of the hindered phenol in the
resin solution to 2 mass parts and the amount of diethylene glycol
diethyl ether to 23.5 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 9.
Example 12
[0244] N-methyl-2-pyrrolidone (pH=11.7) was used in place of
diethylene glycol ethyl methyl ether.
[0245] Also, besides adding 22 mass parts of the
N-methyl-2-pyrrolidone to the resin solution and setting the amount
of the hindered phenol to 1.5 mass parts and the amount of
diethylene glycol diethyl ether to 24 mass parts, a non-aqueous
inkjet ink was manufactured in the same manner as in Example 9.
[0246] The storage property test and the hue difference evaluation
were carried out on the non-aqueous inkjet inks manufactured in
Examples 9 to 12. The results are shown in Table 3.
TABLE-US-00003 TABLE 3 Example 9 Example 10 Example 11 Example 12
Mass parts Cyan pigment dispersion (pH = 8.6) 30 30 30 30 Organic
2EG-EM (pH = 6.8) 22 22 22 -- Solvent 2EG-2E (pH = 4.0) 24.5 24
23.5 24 2EG-1E (pH = 7.6) 18 18 18 18 N-methyl-2-pyrrolidone -- --
-- 22 (pH = 11.7) Radical UV10 -- -- -- -- Polymerization (hindered
amine compound) inhibitor UV22 1 1.5 2 1.5 (hindered phenol
compound) Binder resin VINNOL E15/45 4 4 4 4 (emulsion
polymerization) SOLBIN CL -- -- -- -- (suspension polymerization)
Metal 2-methylimidazole -- -- -- -- Coordination (pH = 11.0)
compound 1-[N,N-bis(2-ethylhexyl) 0.5 0.5 0.5 0.5
aminomethyl]benzotriazole (pH = 7.5) Evaluation Storage property
Normal Good Good Normal Hue difference .DELTA.E Good Good Normal
Good
[0247] From the results for Examples 1 to 5 in the previous Table 1
and the results for Examples 9 to 12 in Table 3, it was found that
with the cyan non-aqueous inkjet ink, although a hindered phenol
can be used as the radical polymerization inhibitor, a hindered
amine is more effective in terms of the effect of inhibiting the
radical polymerization reaction of the unreacted monomer and
preventing the gelling of the polyvinyl chloride resin.
[0248] Also, from the results of Examples 9 to 11 and Example 12,
it was found that even in the non-aqueous inkjet ink using a
hindered phenol, it is preferable to use a combination of alkylene
glycol derivatives all having a pH of 2 to 9 as the organic solvent
and that combined use of diethylene glycol ethyl methyl ether,
diethylene glycol diethyl ether, which is the preferable second
solvent, and diethylene glycol monoethyl ether, which is the
preferable third solvent, is especially preferable.
Magenta Ink
Example 13
[0249] While stirring 18 mass parts of diethylene glycol monoethyl
ether (2EG-1E, pH=7.6), 4 mass parts of a vinyl chloride-vinyl
acetate copolymer synthesized by the emulsion polymerization method
[VINNOL (registered trademark) E15/45 made by Wacker Chemie AG,
weight average molecular weight Mw: 45000 to 55000, vinyl acetate
content: 15.0.+-.1.0 mass %] were added and dispersed as a binder
resin, and thereafter 25.45 mass parts of diethylene glycol diethyl
ether (2EG-2E, pH=4.0) were added to swell the copolymer.
[0250] Then, while continuing to stir, 22 mass parts of diethylene
glycol ethyl methyl ether (2EG-EM, pH=6.8) were added to dissolve
the copolymer, and thereafter, 0.05 mass parts of the mixture in
which
.alpha.,.alpha.',.alpha.''-1,2,3-propanetriyltris[.omega.-[(1-oxo-2-prope-
ne-1-yl)ox y]]-poly[oxy(methyl-1,2-ethanediyl)] has
2,6-bis(1,1-dimethylethyl)-4-(phenylmethylene)-2,5-cyclohexadine-1-one
mixed therein as the effective component [Irgastab UV22 made by
Ciba Specialty Chemicals Corp. (mixture of 76 to 90 mass % of the
former and 24 to 10 mass % of the latter)] as a hindered phenol
(radical polymerization inhibitor) and 0.5 mass parts of
1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole (pH measured in
the state of 5% aqueous solution=7.5) as a metal coordination
compound were added to prepare a resin solution.
[0251] A pigment dispersion was prepared in which C. I. Pigment Red
122 was dispersed as a quinacridone pigment in diethylene glycol
diethyl ether (pigment concentration 15 mass %, pH=7.6), and 30
mass parts of the pigment dispersion were added to 70 mass parts of
the resin solution prepared in advance and further stirring was
performed to form a uniform phase and thereby manufacture a
non-aqueous inkjet ink.
Example 14
[0252] Besides setting the amount of the hindered phenol in the
resin solution to 0.1 mass parts and the amount of diethylene
glycol diethyl ether to 25.4 mass parts, a non-aqueous inkjet ink
was manufactured in the same manner as in Example 13.
Example 15
[0253] Besides setting the amount of the hindered phenol in the
resin solution to 0.5 mass parts and the amount of diethylene
glycol diethyl ether to 25 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 13.
Example 16
[0254] Besides setting the amount of the hindered phenol in the
resin solution to 1 mass part and the amount of diethylene glycol
diethyl ether to 24.5 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 13.
Example 17
[0255] Besides setting the amount of the hindered phenol in the
resin solution to 2 mass parts and the amount of diethylene glycol
diethyl ether to 23.5 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 13.
Example 18
[0256] 4,4'-[(1,10-dioxo-1,10-decanediyl)bis(oxy)]bis[2,2,6,
6-tetramethyl]-1-piperidinyloxy [product equivalent to Irgastab
(registered trademark) UV10 made by Ciba Specialty Chemicals Corp.]
was used as a hindered amine radical polymerization inhibitor in
place of the hindered phenol.
[0257] Also, besides adding 1 mass part of the hindered amine to
the resin solution and setting the amount of diethylene glycol
diethyl ether to 24.5 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 13.
[0258] The storage property test and the hue difference evaluation
were carried out on the non-aqueous inkjet inks manufactured in
Examples 13 to 18. For the hue difference evaluation, a drawdown
sample formed using a separately-prepared magenta non-aqueous
inkjet ink that does not contain a polymerization inhibitor was
used as a reference. The results are shown in Table 4.
TABLE-US-00004 TABLE 4 Example 13 Example 14 Example 15 Example 16
Example 17 Example 18 Mass parts Magenta pigment dispersion (pH =
7.6) 30 30 30 30 30 30 Organic 2EG-EM (pH = 6.8) 22 22 22 22 22 22
solvent 2EG-2E (pH = 4.0) 25.45 25.4 25 24.5 23.5 24.5 2EG-1E (pH =
7.6) 18 18 18 18 18 18 N-methyl-2-pyrrolidone -- -- -- -- -- -- (pH
= 11.7) Radical UV10 -- -- -- -- -- 1 Polymerization (hindered
amine compound) inhibitor UV22 0.05 0.1 0.5 1 2 -- (hindered phenol
compound) Binder resin VINNOL E15/45 4 4 4 4 4 4 (emulsion
polymerization) SOLBIN CL -- -- -- -- -- -- (suspension
polymerization) Metal 2-methylimidazole -- -- -- -- -- --
Coordination (pH = 11.0) compound 1-[N,N-bis(2-ethylhexyl) 0.5 0.5
0.5 0.5 0.5 0.5 aminomethyl]benzotriazole (pH = 7.5) Evaluation
Storage property Normal Excellent Excellent Excellent Excellent
Normal Hue difference .DELTA.E Good Good Good Good Normal Good
[0259] From the results for Examples 13 to 17 and Example 18 in
Table 4, it was found that with the magenta non-aqueous inkjet ink
using the quinacridone pigment as the pigment, although a hindered
amine can be used as the radical polymerization inhibitor, a
hindered phenol is more effective in terms of the effect of
inhibiting the radical polymerization reaction of the unreacted
monomer and preventing the gelling of the polyvinyl chloride
resin.
[0260] Also, from the results of Examples 13 to 17, it was found
that in the magenta non-aqueous inkjet ink, the content proportion
of the hindered phenol with respect to the total amount of the
non-aqueous inkjet ink is preferably no less than 0.05 mass % and
especially preferably no less than 0.1 mass %, and preferably no
more than 2 mass % and especially preferably no more than 1 mass
%.
Yellow Ink
Example 19
[0261] While stirring 18 mass parts of diethylene glycol monoethyl
ether (2EG-1E, pH=7.6), 4 mass parts of a vinyl chloride-vinyl
acetate copolymer synthesized by the emulsion polymerization method
[VINNOL (registered trademark) E15/45 made by Wacker Chemie AG,
weight average molecular weight Mw: 45000 to 55000, vinyl acetate
content: 15.0.+-.1.0 mass %] were added and dispersed as a binder
resin, and thereafter 25.45 mass parts of diethylene glycol diethyl
ether (2EG-2E, pH=4.0) were added to swell the copolymer.
[0262] Then, while continuing to stir, 22 mass parts of diethylene
glycol ethyl methyl ether (2EG-EM, pH=6.8) were added to dissolve
the copolymer, and thereafter, 0.05 mass parts of
4,4'-[(1,10-dioxo-1,10-decanediyl)bis(oxy)]bis[2,2,6,6-tetramethyl]-1-pip-
eridinyloxy [product equivalent to Irgastab (registered trademark)
UV10 made by Ciba Specialty Chemicals Corp.] as a hindered amine
(radical polymerization inhibitor) and 0.5 mass parts of
1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole (pH measured in
the state of 5% aqueous solution=7.5) as a metal coordination
compound were added to prepare a resin solution.
[0263] A pigment dispersion was prepared in which C. I. Pigment
Yellow 150 was dispersed as a chelate azo pigment in diethylene
glycol diethyl ether (pigment concentration 15 mass %, pH=6.5), and
30 mass parts of the pigment dispersion were added to 70 mass parts
of the resin solution prepared in advance and further stirring was
performed to form a uniform phase and thereby manufacture a
non-aqueous inkjet ink.
Example 20
[0264] Besides setting the amount of the hindered amine in the
resin solution to 0.1 mass parts and the amount of diethylene
glycol diethyl ether to 25.4 mass parts, a non-aqueous inkjet ink
was manufactured in the same manner as in Example 19.
Example 21
[0265] Besides setting the amount of the hindered amine in the
resin solution to 0.3 mass parts and the amount of diethylene
glycol diethyl ether to 25.2 mass parts, a non-aqueous inkjet ink
was manufactured in the same manner as in Example 19.
Example 22
[0266] Besides setting the amount of the hindered amine in the
resin solution to 0.5 mass parts and the amount of diethylene
glycol diethyl ether to 25 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 19.
Example 23
[0267] Besides setting the amount of the hindered amine in the
resin solution to 2 mass parts and the amount of diethylene glycol
diethyl ether to 23.5 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 19.
[0268] The storage property test and the hue difference evaluation
were carried out on the non-aqueous inkjet inks manufactured in
Examples 19 to 23. For the hue difference evaluation, a drawdown
sample formed using a separately-prepared yellow non-aqueous inkjet
ink that does not contain a polymerization inhibitor was used as a
reference. The results are shown in Table 5.
TABLE-US-00005 TABLE 5 Example 19 Example 20 Example 21 Example 22
Example 23 Mass parts Yellow pigment dispersion (pH = 6.5) 30 30 30
30 30 Organic 2EG-EM (pH = 6.8) 22 22 22 22 22 Solvent 2EG-2E (pH =
4.0) 25.45 25.4 25.2 25 23.5 2EG-1E (pH = 7.6) 18 18 18 18 18
N-methyl-2-pyrrolidone -- -- -- -- -- (pH = 11.7) Radical UV10 0.05
0.1 0.3 0.5 2 Polymerization (hindered amine compound) inhibitor
UV22 -- -- -- -- -- (hindered phenol compound) Binder resin VINNOL
E15/45 4 4 4 4 4 (emulsion polymerization) SOLBIN CL -- -- -- -- --
(suspension polymerization) Metal 2-methylimidazole -- -- -- -- --
Coordination (pH = 11.0) compound 1-[N,N-bis(2-ethylhexyl) 0.5 0.5
0.5 0.5 0.5 aminomethyl]benzotriazole (pH = 7.5) Evaluation Storage
property Normal Excellent Excellent Excellent Excellent Hue
difference .DELTA.E Good Good Good Good Normal
[0269] From the results for Examples 19 to 23 in Table 5, it was
found that with the yellow non-aqueous inkjet ink using a chelate
azo pigment as the pigment, the content proportion with respect to
the total amount of the non-aqueous inkjet ink of the hindered
amine as the radical polymerization inhibitor is preferably no less
than 0.05 mass % and especially preferably no less than 0.1 mass %,
and preferably no more than 2 mass % and especially preferably no
more than 0.5 mass %.
Black Ink
Example 24
[0270] While stirring 18 mass parts of diethylene glycol monoethyl
ether (2EG-1E, pH=7.6), 4 mass parts of a vinyl chloride-vinyl
acetate copolymer synthesized by the emulsion polymerization method
[VINNOL (registered trademark) E15/45 made by Wacker Chemie AG,
weight average molecular weight Mw: 45000 to 55000, vinyl acetate
content: 15.0.+-.1.0 mass %] were added and dispersed as a binder
resin, and thereafter 25.45 mass parts of diethylene glycol diethyl
ether (2EG-2E, pH=4.0) were added to swell the copolymer.
[0271] Then, while continuing to stir, 22 mass parts of diethylene
glycol ethyl methyl ether (2EG-EM, pH=6.8) were added to dissolve
the copolymer, and thereafter, 0.05 mass parts of
4,4'-[(1,10-dioxo-1,10-decanediyl)bis(oxy)]bis[2,2,6,6-tetramethyl]-1-pip-
eridinyloxy [product equivalent to Irgastab (registered trademark)
UV10 made by Ciba Specialty Chemicals Corp.] as a hindered amine
(radical polymerization inhibitor) and 0.5 mass parts of
1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole (pH measured in
the state of 5% aqueous solution=7.5) as a metal coordination
compound were added to prepare a resin solution.
[0272] A pigment dispersion was prepared in which carbon black was
dispersed in diethylene glycol diethyl ether (pigment concentration
15 mass %, pH=5.8), and 30 mass parts of the pigment dispersion
were added to 70 mass parts of the resin solution prepared in
advance and further stirring was performed to form a uniform phase
and thereby manufacture a non-aqueous inkjet ink.
Example 25
[0273] Besides setting the amount of the hindered amine in the
resin solution to 0.1 mass parts and the amount of diethylene
glycol diethyl ether to 25.4 mass parts, a non-aqueous inkjet ink
was manufactured in the same manner as in Example 24.
Example 26
[0274] Besides setting the amount of the hindered amine in the
resin solution to 0.3 mass parts and the amount of diethylene
glycol diethyl ether to 25.2 mass parts, a non-aqueous inkjet ink
was manufactured in the same manner as in Example 24.
Example 27
[0275] Besides setting the amount of the hindered amine in the
resin solution to 0.5 mass parts and the amount of diethylene
glycol diethyl ether to 25 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 24.
Example 28
[0276] Besides setting the amount of the hindered amine in the
resin solution to 2 mass parts and the amount of diethylene glycol
diethyl ether to 23.5 mass parts, a non-aqueous inkjet ink was
manufactured in the same manner as in Example 24.
[0277] The storage property test and the hue difference evaluation
were carried out on the non-aqueous inkjet inks manufactured in
Examples 24 to 28. For the hue difference evaluation, a drawdown
sample formed using a separately-prepared black non-aqueous inkjet
ink that does not contain a polymerization inhibitor was used as a
reference. The results are shown in Table 6.
TABLE-US-00006 TABLE 6 Example 24 Example 25 Example 26 Example 27
Example 28 Mass parts Black pigment dispersion (pH = 5.8) 30 30 30
30 30 Organic 2EG-EM (pH = 6.8) 22 22 22 22 22 solvent 2EG-2E (pH =
4.0) 25.45 25.4 25.2 25 23.5 2EG-1E (pH = 7.6) 18 18 18 18 18
N-methyl-2-pyrrolidone -- -- -- -- -- (pH = 11.7) Radical UV10 0.05
0.1 0.3 0.5 2 Polymerization (hindered amine compound) inhibitor
UV22 -- -- -- -- -- (hindered phenol compound) Binder resin VINNOL
E15/45 4 4 4 4 4 (emulsion polymerization) SOLBIN CL -- -- -- -- --
(suspension polymerization) Metal 2-methylimidazole -- -- -- -- --
Coordination (pH = 11.0) compound 1-[N,N-bis(2-ethylhexyl) 0.5 0.5
0.5 0.5 0.5 aminomethyl]benzotriazole (pH = 7.5) Evaluation Storage
property Normal Excellent Excellent Excellent Excellent Hue
difference .DELTA.E Good Good Good Good Normal
[0278] From the results for Examples 24 to 28 in Table 6, it was
found that with the black non-aqueous inkjet ink using carbon black
as the pigment, the content proportion with respect to the total
amount of the non-aqueous inkjet ink of the hindered amine as the
radical polymerization inhibitor is preferably no less than 0.05
mass % and especially preferably no less than 0.1 mass %, and
preferably no more than 2 mass % and especially preferably no more
than 0.5 mass %.
* * * * *