U.S. patent application number 15/069411 was filed with the patent office on 2016-09-15 for active-energy-ray-curable composition, active-energy-ray-curable ink, composition stored container, apparatus and method for forming two-dimensional or three-dimensional image, two-dimensional or three-dimensional image, structure, and processed product.
The applicant listed for this patent is Tsuyoshi ASAMI, Tomohiro Hirade. Invention is credited to Tsuyoshi ASAMI, Tomohiro Hirade.
Application Number | 20160264795 15/069411 |
Document ID | / |
Family ID | 56887403 |
Filed Date | 2016-09-15 |
United States Patent
Application |
20160264795 |
Kind Code |
A1 |
ASAMI; Tsuyoshi ; et
al. |
September 15, 2016 |
ACTIVE-ENERGY-RAY-CURABLE COMPOSITION, ACTIVE-ENERGY-RAY-CURABLE
INK, COMPOSITION STORED CONTAINER, APPARATUS AND METHOD FOR FORMING
TWO-DIMENSIONAL OR THREE-DIMENSIONAL IMAGE, TWO-DIMENSIONAL OR
THREE-DIMENSIONAL IMAGE, STRUCTURE, AND PROCESSED PRODUCT
Abstract
An active-energy-ray-curable composition, which satisfies the
following relationships of absorbance: a ratio of absorbance at a
wavelength of 400 nm to absorbance at a wavelength of 750 nm is 1.4
or more but 1.6 or less; and a ratio of absorbance at a wavelength
of 365 nm to absorbance at a wavelength of 500 nm is 1.2 or
less.
Inventors: |
ASAMI; Tsuyoshi; (Kanagawa,
JP) ; Hirade; Tomohiro; (Kanagawa, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ASAMI; Tsuyoshi
Hirade; Tomohiro |
Kanagawa
Kanagawa |
|
JP
JP |
|
|
Family ID: |
56887403 |
Appl. No.: |
15/069411 |
Filed: |
March 14, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09D 11/101 20130101;
C09D 11/324 20130101 |
International
Class: |
C09D 11/101 20060101
C09D011/101; C09D 11/324 20060101 C09D011/324; C09D 11/30 20060101
C09D011/30 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 13, 2015 |
JP |
2015-050603 |
Jan 21, 2016 |
JP |
2016-010070 |
Claims
1. An active-energy-ray-curable composition, which satisfies the
following relationships of absorbance. a ratio of absorbance at a
wavelength of 400 nm to absorbance at a wavelength of 750 nm is 1.4
or more but 1.6 or less; and a ratio of absorbance at a wavelength
of 365 nm to absorbance at a wavelength of 500 nm is 1.2 or
less.
2. The active-energy-ray-curable composition according to claim 1,
wherein: a volume average particle diameter of dispersoid particles
in the active-energy-ray-curable composition is 100 nm or more but
150 nm or less; an amount of the dispersoid particles having a
volume average particle diameter of 50 nm or less is 10% by mass or
less relative to a total amount of the dispersoid particles; and an
amount of the dispersoid particles having a volume average particle
diameter of 230 nm or more is 10% by mass or less relative to the
total amount of the dispersoid particles.
3. The active-energy-ray-curable composition according to claim 1,
wherein: the active-energy-ray-curable composition comprises a
carbon black subjected to oxidation treatment at pH 3.5 or less; a
number average particle diameter of the carbon black is 40 nm or
more but 60 nm or less; and a DBP oil absorption amount of the
carbon black is 35 g/100 g or more but 55 g /100 g or less.
4. The active-energy-ray-curable composition according to claim 1,
wherein the active-energy-ray-curable composition comprises an
acrylic block polymer having an acid value of 5 mg KOH/g or more
and an amine value of 15 mg KOH/g or more.
5. The active-energy-ray-curable composition according to claim 1,
wherein the active-energy-ray-curable composition is a material for
forming a three-dimensional object.
6. The active-energy-ray-curable composition according to claim 1,
wherein the active-energy-ray-curable composition has sensitivity
to light of a light-emitting diode having a luminescence peak in a
wavelength range of 360 nm or more but 400 nm or less.
7. An active-energy-ray-curable ink, which satisfies the following
relationships of absorbance: a ratio of absorbance at a wavelength
of 400 nm to absorbance at a wavelength of 750 nm is 1.4 or more
but 1.6 or less; and a ratio of absorbance at a wavelength of 365
nm to absorbance at a wavelength of 500 nm is 1.2 or less.
8. The active-energy-ray-curable ink according to claim 7, wherein
the active-energy-ray-curable ink is used for inkjet.
9. A composition stored container, comprising: a container; and the
active-energy-ray-curable composition according to claim 1.
10. An apparatus for forming a two-dimensional or three-dimensional
image, the apparatus comprising: the composition stored container
according to claim 9; and an irradiator configured to irradiate the
active-energy-ray-curable ink with active energy rays.
11. The apparatus for forming the two-dimensional or
three-dimensional image according to claim 10, further comprising:
an ejecting unit configured to eject the active-energy-ray-curable
ink.
12. A method for forming a two-dimensional or three-dimensional
image, the method comprising irradiating an
active-energy-ray-curable composition with active energy rays,
wherein the active-energy-ray-curable composition satisfies the
following relationships of absorbance: a ratio of absorbance at a
wavelength of 400 nm to absorbance at a wavelength of 750 nm is 1.4
or more but 1.6 or less; and a ratio of absorbance at a wavelength
of 365 nm to absorbance at a wavelength of 500 nm is 1.2 or
less.
13. The method for forming the two-dimensional or three-dimensional
image according to claim 12, comprising: ejecting an
active-energy-ray-curable ink comprising the
active-energy-ray-curable composition.
14. The method for forming the two-dimensional or three-dimensional
image according to claim 12, wherein the active energy rays
comprise light of a light-emitting diode.
15. A two-dimensional or three-dimensional image, which is obtained
through curing the active-energy-ray-curable composition according
to claim 1 by irradiating with active energy rays.
16. A structure comprising: a base; and the two-dimensional or
three-dimensional image according to claim 15 on the base.
17. A processed product, which is obtained by drawing the
two-dimensional or three-dimensional image according to claim 15.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority under 35 U.S.C.
.sctn.119 to Japanese Patent Application No. 2015-050603, filed on
Mar. 13, 2015 and Japanese Patent Application No. 2016-010070,
filed on Jan. 21, 2016. The contents of which are incorporated
herein by reference in their entirety.
BACKGROUND OF THE DISCLOSURE
[0002] 1. Field of the Invention
[0003] The present disclosure relates to active-energy-ray-curable
compositions, active-energy-ray-curable inks, composition stored
containers, apparatuses and methods for forming two-dimensional or
three-dimensional images, two-dimensional or three-dimensional
images, structures, and processed products.
[0004] 2. Description of the Related Art
[0005] Active-energy-ray-curable inks containing an
active-energy-ray-curable composition have little odor, are quickly
dried, and can be recorded on a recording medium that does not
absorb the ink.
[0006] Active-energy-ray-curable inks are cured using a light
source such as a mercury lamp and a metal halide lamp. Recently,
however, a need for using an UV-LED having a wavelength of 365 nm
or 385 nm is increasing due to a demand for saving of
electricity.
[0007] In general, the active-energy-ray-curable ink is cured by
binding the monomers in the ink using several kinds of
photopolymerizable initiator each having different absorption
wavelength, depending on the kinds of light source for curing.
However, a pigment in the ink absorbs the ultraviolet rays, and
thus the black pigment excellent in curing ability is particularly
difficult to obtain.
[0008] For example, Japanese Unexamined Patent Application
Publication No. 2009-57546 discloses that use of the pigment having
low absorbance at the ultraviolet region improves the yellow ink or
the magenta ink in curing ability.
[0009] Japanese Unexamined Patent Application Publication No.
2012-207117 discloses that use of the resin-coated carbon black
having low absorbance at the ultraviolet region improve the carbon
black-containing aqueous black ink in close adhesiveness and
rubfastness.
[0010] Japanese Unexamined Patent Application Publication No.
2012-031254 discloses that the ink obtained by optimizing
absorbance of an initiator, a sensitizer, and a fluorescent
brightening agent results in improvement in curing ability of the
ink.
[0011] Japanese Unexamined Patent Application Publication No.
03-258867 discloses that use of a magenta dye improves the ink in
curing ability, where the magenta dye has a ratio of absorbance at
a wavelength of 500 nm to absorbance at a wavelength of 360 nm is
0.8 or more.
SUMMARY OF THE INVENTION
[0012] An object of the present disclosure is to provide an
active-energy-ray-curable composition high in printing density, and
excellent in curing ability by active energy rays and close
adhesiveness to a base.
[0013] As means for solving the problems, an
active-energy-ray-curable composition of the present disclosure
satisfies the following relationships of absorbance: a ratio of
absorbance at a wavelength of 400 nm to absorbance at a wavelength
of 750 nm is 1.4 or more but 1.6 or less; and a ratio of absorbance
at a wavelength of 365 nm to absorbance at a wavelength of 500 nm
is 1.2 or less.
[0014] According to the present disclosure, an
active-energy-ray-curable composition high in printing density, and
excellent in curing ability by active energy rays and close
adhesiveness to a base can be provided.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 is a view of one example of an ultraviolet spectrum
of a mercury lamp;
[0016] FIG. 2 is a view of one example of an ultraviolet spectrum
of a metal halide lamp;
[0017] FIG. 3 is a view of one example of an ultraviolet spectrum
of an UV-LED;
[0018] FIG. 4 is a graph of absorbance of Examples and Comparative
Examples;
[0019] FIG. 5 is a schematic view of one example illustrating a
composition stored container;
[0020] FIG. 6 is a schematic view of an example of an image forming
apparatus of the present disclosure;
[0021] FIG. 7 is a schematic view of an example of another image
forming apparatus of the present disclosure;
[0022] FIG. 8A is a schematic view of an example of still another
image forming apparatus of the present disclosure;
[0023] FIG. 8B is a schematic view of an example of still another
image forming apparatus of the present disclosure;
[0024] FIG. 8C is a schematic view of an example of still another
image forming apparatus of the present disclosure; and
[0025] FIG. 8D is a schematic view of an example of still another
image forming apparatus of the present disclosure.
DETAILED DESCRIPTION OF THE INVENTION
[0026] (Active-Energy-Ray-Curable Composition)
[0027] An active-energy-ray-curable composition of the present
disclosure satisfies the following relationships of absorbance: a
ratio of absorbance at a wavelength of 400 nm to absorbance at a
wavelength of 750 nm is 1.4 or more but 1.6 or less; and a ratio of
absorbance at a wavelength of 365 nm to absorbance at a wavelength
of 500 nm is 1.2 or less.
[0028] The active-energy-ray-curable composition contains a
colorant, a polymerizable-unsaturated-monomer-compound, and a
polymerization initiator; and further contains other components, if
necessary.
[0029] The present disclosure is based on the findings that the
black inks disclosed in Japanese Unexamined Patent Application
Publication Nos. 2009-57546 and 03-258867 are not improved in
curing ability; that the active-energy-ray-curable compositions
disclosed in Japanese Unexamined Patent Application Publication No.
2012-207117 is used for aqueous inks, and not used for non-aqueous
inks as a target; and that the resultant inks disclosed in Japanese
Unexamined Patent Application Publication No. 2012-031254 is
deteriorated in printing density.
[0030] The active-energy-ray-curable composition of the present
disclosure can be used as an active-energy-ray-curable ink (may be
referred to as "ink"). An application field of the
active-energy-ray-curable ink is not particularly limited and may
be appropriately selected depending on the intended purpose, but
the active-energy-ray-curable ink is preferably used for
inkjet.
[0031] In general, "active energy rays" include electromagnetic
waves (e.g., radio waves, infrared rays, visible light, ultraviolet
rays, X-rays, and gamma-rays) and electron beams. Here, the active
energy rays of the present disclosure mean the electromagnetic
waves other than the radio waves and the gamma-rays. The electron
beams include electron beams generated through thermionic emission
and electron beams generated through photoelectric emission. The
electron beams of the present disclosure are electron beams having
a shorter wavelength than the visible light region. The active
energy rays are not particularly limited and may be appropriately
selected depending on the intended purpose, but it is preferably
light of a light-emitting diode.
[0032] A wavelength of the visible light is in a range of from
about 400 nm through 750 nm. The active-energy-ray-curable
composition and the ink preferably have higher absorbance in the
aforementioned range because an image having higher density can be
obtained.
[0033] In the present disclosure, a ratio of absorbance at a
wavelength of 400 nm to absorbance at a wavelength of 750 nm is 1.4
or more but 1.6 or less, which illustrates an approximation
gradient of absorbance at the visible light region. When the ratio
thereof is higher than the aforementioned range, the ink tends to
considerably absorb ultraviolet rays to lower curing ability. When
the ratio thereof is lower than the aforementioned range, the
thus-obtained image does not have high density.
[0034] Moreover, the active-energy-ray-curable composition and the
ink having the approximation gradient of the absorbance falling
within the aforementioned range have high absorption in the visible
light region, and have a potential for outputting an image having
high density.
[0035] Moreover, in the present disclosure, a ratio of absorbance
at a wavelength of 365 nm to absorbance at a wavelength of 500 nm
is 1.2 or less. In general, black pigment-containing
active-energy-ray-curable compositions and inks, which have high
absorbance at the visible light region, absorb an ultraviolet light
having a wave length of 400 nm or less to lower curing ability.
[0036] The active-energy-ray-curable composition of the present
disclosure has sensitivity to light of a light-emitting diode
having a luminescence peak in a wavelength range of 360 nm or more
but 400 nm or less. Particularly, a wavelength of 365 nm is a peak
wavelength of the UV-LED lamp. Therefore, in cases where the
active-energy-ray-curable composition and the ink are cured using a
UV-LED, it is important to have low absorbance at a wavelength of
365 nm. Therefore, when a ratio of absorbance at a wavelength of
365 nm to absorbance at a wavelength of 500 nm, which is a
representative wavelength in a lower side of the visible light
region, is less than 1.2, the resultant ink is excellent in curing
ability of absorbance.
[0037] In particular, when the active-energy-ray-curable
composition is diluted so as to have a pigment concentration of
0.0025% by mass for measurements of absorbance, it is preferable
that absorbance at a wavelength of 500 nm and absorbance at a
wavelength of 700 nm be 1.3 or more and 1.0 or more, respectively.
These two wavelengths are representative absorption wavelengths at
the visible light region for the black ink. Therefore, whether the
ink has a potential for outputting an image having high density can
be determined based on whether the black ink has high absorbance at
500 nm and 700 nm.
[0038] For example, a TG/DTA (differential heat/thermogravimetry
simultaneous measurement apparatus) can be used to quantify a
pigment concentration in the conventional ink so that a
concentration of the pigment is 0.0025% by mass through
dilution.
[0039] Measurements using a TG/DTA are described in "JIS K 0129".
However, a pigment concentration of the active-energy-ray-curable
composition and the ink can be confirmed using the TG/DTA as
follows.
[0040] A standard material (Al.sub.2O.sub.3) and the
active-energy-ray-curable composition are set in a sample holder,
followed by heating from 25.degree. C. to 500.degree. C. in a
nitrogen atmosphere at a heating rate of 10.degree. C/min. Then,
the atmosphere is purged with oxygen, followed by heating to
700.degree. C.
[0041] It can be confirmed that a weight of the sample is reduced
due to the thermal decomposition of water in
active-energy-ray-curable composition, and then is reduced due to
thermal decomposition of the resin at about 300.degree. C. as
measured by TG.
[0042] It can be confirmed that a weight of the sample is reduced
due to the thermal decomposition of the components such as water, a
surfactant, a dispersant, a polymerization initiator (which may be
referred to as "initiator"), and a polymerization inhibitor (which
may be referred to as "inhibitor") except for the pigment in the
active-energy-ray-curable composition until the heating temperature
rises to 500.degree. C. as measured by TG.
[0043] It is confirmed that, during heating from 500.degree. C.
through 600.degree. C., the pigment is decomposed, a large peak
appears by DTA, and a weight of the sample is reduced as measured
by TG.
[0044] The amount of the reduced weight measured at from
500.degree. C. through 600.degree. C. by TG can be used to quantify
of the pigment in the active-energy-ray-curable composition.
[0045] Based on the concentration of the pigment in the
active-energy-ray-curable composition as measured above can be
adjusted to 0.0025% by mass through dilution to measure absorbance
of the ink.
[0046] In order to obtain absorbance defined in the present
disclosure, it is preferable that a volume average particle
diameter of dispersoid particles in the active-energy-ray-curable
composition be 100 nm or more but 150 nm or less. When the volume
average particle diameter thereof is less than 100 nm, a ratio of
absorbance at a wavelength of 400 nm to absorbance at a wavelength
of 750 nm tends to be 1.6 or more, and a ratio of absorbance at a
wavelength of 365 nm to absorbance at a wavelength of 500 nm tends
to be more than 1.2. Here, dispersoid particles mean solid contents
in the active-energy-ray-curable composition.
[0047] Meanwhile, when the volume average particle diameter of
dispersoid particles is more than 150 nm, the ratio of absorbance
at a is wavelength of 365 nm to absorbance at a wavelength of 500
nm tends to be 1.2 or less, but the ratio of absorbance at a
wavelength of 400 nm to absorbance at a wavelength of 750 nm tends
to be less than 1.4.
[0048] An amount of the dispersoid particles having a volume
average particle diameter of 50 nm or less is preferably 10% by
mass or less relative to the total amount of the dispersoid
particles. When the amount of thereof is 10% by mass, the ratio of
absorbance at a wavelength of 365 nm or less to absorbance at a
wavelength of 500 nm tends to be 1.2 or less.
[0049] An amount of the dispersoid particles having a volume
average particle diameter of 230 nm or more is preferably 10% by
mass or less relative to the total amount of the dispersoid
particles. When the amount of thereof is 10% by mass or less, the
ratio of absorbance at a wavelength of 400 nm to absorbance at a
wavelength of 750 nm tends to be 1.4 or more.
[0050] A pigment serving as the colorant is preferably carbon
black, where the carbon black is subjected to oxidation treatment
at pH 3.5 or less, and has a number average particle diameter of 40
nm or more but 60 nm or less, and a DBP oil absorption amount is 35
g/100 g or more but 55 g/100 g or less.
[0051] When the number average particle diameter of the carbon
black is less than 40 nm, the ratio of absorbance at a wavelength
of 400 nm to absorbance at a wavelength of 750 nm tends to be more
than 1.7, and the ratio of absorbance at a wavelength of 365 nm to
absorbance at a wavelength of 500 nm tends to be 1.2 or more.
[0052] Moreover, when the black carbon does not satisfy the
aforementioned conditions, the active-energy-ray-curable
composition and the ink excellent in dispersibility may not be
obtained due to low dispersibility of the black carbon.
[0053] When the number average particle diameter of the carbon
black is more than 60 nm, the ratio of absorbance at a wavelength
of 365 nm to absorbance at a wavelength of 500 nm can easily be 1.2
or less, but the ratio of absorbance at a wavelength of 400 nm to
absorbance at a wavelength of 750 nm tends to be less than 1.4.
[0054] A DBP oil absorption amount is used for an indicator of
structure of carbon black. As the DBP oil absorption amount of the
carbon black is low, structure of carbon black of the carbon black
tends to be small. As the DBP oil absorption amount thereof is
high, structure of carbon black tends to be large. The DBP oil
absorption amount thereof is not particularly limited and may be
appropriately selected depending on the intended purpose, but it is
preferably 35 g/100 g or more but 55 g /100 g or less. When the DBP
oil absorption amount thereof is less than 35 g/100 g, particles of
the carbon have good dispersibility, but the resultant ink having
high density is difficult to obtain. When the DBP oil absorption
amount thereof is more than 55 g/100 g, the carbon black may
generate bound solvent that does not have liquidity between
particles to have high viscosity, and may be deteriorated in
dispersibility.
[0055] The carbon black is preferably subjected to oxidation
treatment at pH 3.5 or less. The acid-treated carbon black as
described in the following structural formula contains many
functional groups such as quinone, carboxyl, aldehyde, lactone, and
phenol, and has high adhesiveness to the dispersant. When the
carbon black is subjected to oxidation treatment at pH more than
3.5, the carbon black is deteriorated in adhesiveness to the
dispersant, has large particle diameter, and has high viscosity. As
a result, absorbance of the active-energy-ray-curable, which is
defined in the present disclosure, cannot be obtained.
##STR00001##
[0056] As an example of the carbon black suitable for the present
disclosure, Special Black 250 (product of Orion (Degussa)) and
MOGUL-L (product of CABOT) can be used.
[0057] These aforementioned carbon blacks were described as
examples of usable carbon black in Japanese Unexamined Patent
Application Publication No. 2012-144681, and were used in Examples
of Japanese Unexamined Patent Application Publication No.
2012-031254.
[0058] However, even if the similar blacks are used for the
conventional active-energy-ray-curable compositions and the inks,
the ink having absorbance defined in the present disclosure cannot
be obtained because a combinations with other materials, amounts of
materials, and preparation methods are each different. Therefore,
the ink defined in the present disclosure can be obtained by
adjusting and optimizing these materials, the amounts of materials,
and the preparation methods.
[0059] An amount of the colorant is preferably 2% by mass or more
but 5% by mass or less relative to the total amount of the
active-energy-ray-curable composition. When the amount thereof is
less than 2% by mass, the prescribed concentration of the colorant
cannot be obtained. When the amount thereof is more than 5% by
mass, viscosity of the active-energy-ray-curable composition and
viscosity of the active-energy-ray-curable ink rise to lower
ejecting ability.
[0060] The active-energy-ray-curable composition may contain a cyan
pigment or a derivative of a cyan pigment as a complementary color
in such a range that the absorbance defined in the present
disclosure can be maintained.
[0061] Examples of the cyan pigment include: a phthalocyanine
pigment such as C.I. Pigment Blue series (e.g., 15:1, 15:2, 15:3,
15:4, 15:5, and 15:6); and an alkaline blue pigment such as C.I.
Pigment Blue series (e.g., 18 and 56). Examples of the derivative
of a cyan pigment include an acid derivative of a cyan pigment and
a basic derivative of a cyan pigment, where examples of the acid
derivative thereof include a carboxyl group, a sulfonic group, or a
nitro group at a terminal group of the derivative, and examples of
the basic derivative thereof include an amino group or an acid
amide group at a terminal group of the derivative.
[0062] The dispersant is preferably a polymer dispersant. Specific
examples thereof include polyoxyalkylene polyalkylenepolyamine,
vinyl polymer, vinyl copolymer, acrylic polymer, acrylic copolymer,
polyester, polyamide, polyimide, polyurethane, and an amino
polymer.
[0063] Examples of commercially available products of the polymer
dispersant include AJISPER series (product of Ajinomoto Fine-Techno
Co., Inc.), SOLSPERSE series (e.g., SOLSPERSE 39000) (product of
The Lubrizol Corporation (Avecia and Noveon)), DISPERBYK series and
BYKJET series (both products are of BYK Japan KK), and DISPARLON
series (product of Kusumoto Chemicals, Ltd.).
[0064] The acrylic block polymer having an acid value of 5 mg KOH/g
or more and an amine value of 15 mg KOH/g or more is preferable
because it is excellent in adhesiveness to the acid-treated carbon
black. BYKJET-9151 (product of BYK Japan KK) having an acid value
of 8 mg KOH/g and an amine value of 18 mg KOH/g is particularly
preferable.
[0065] An amount of the dispersant added is preferably in a range
of from 1/10 through 1/2, particularly preferably in a range of
from 1/5 through 1/3 relative to the total amount of the pigment.
The amount of the dispersant is less than 1/10, the dispersant
cannot sufficiently cover the pigment particles, which causes
aggregation of the pigment particles. As a result, the pigment is
deteriorated in dispersibility, and thus absorbance at a wavelength
of 700 nm disadvantageously becomes less than 1.0.
[0066] When the amount of the dispersant added is more than 1/2,
the dispersant is excessively dissolved in a
polymerizable-unsaturated-monomer-compound (may be referred to as
"polymerizable-unsaturated-monomer" and "monomer"), and thus
viscosity of the active-energy-ray-curable composition and
viscosity of the ink rise to lower ejecting ability.
[0067] The polymerizable-unsaturated-monomer-compound used in the
present disclosure is not particularly limited and may be
appropriately selected depending on the intended purpose. Examples
thereof include a monofunctional
polymerizable-unsaturated-monomer-compound, a bifunctional
polymerizable-unsaturated-monomer-compound, a trifunctional
polymerizable-unsaturated-monomer-compound, and a tetrafunctional
or more polymerizable-unsaturated-monomer-compound.
[0068] Examples of the monofunctional
polymerizable-unsaturated-monomer-compound include 2-ethylhexyl
acrylate, 2-hydroxyl ethylacrylate, 2-hydroxy ethylacrylate,
2-hydroxypropyl acrylate, 2-vinyloxyethoxyethyl acrylate,
4-hydroxybutyl acrylate , 2-methyl-2-ethyl-1,3-dioxolan-4-ylmethyl
acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate,
phenoxyethyl acrylate, isobornyl acrylate, phenyl glycol
monoacrylate, cyclohexyl acrylate, and acryloyl morpholine.
[0069] Examples of bifunctional
polymerizable-unsaturated-monomer-compound include 1,4-butanediol
diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate,
tripropyleneglycol diacrylate, and tetraethyleneglycol
diacrylate.
[0070] Examples of the trifunctional
polymerizable-unsaturated-monomer-compound include
trimethylolpropane triacrylate, pentaerythritol triacrylate, and
tris(2-hydroxyethyDisocyanurate triacrylate.
[0071] Examples of the tetrafunctional or more
polymerizable-unsaturated-monomer-compound include pentaerythritol
tetraacrylate, dipentaerythritol pentaacrylate, ditrimethylol
propane tetraacrylate, dipentaerythritol hydroxyl pentaacrylate,
and dipentaerythritol hexaacrylate.
[0072] The polymerizable-unsaturated-monomer-compound may be used
alone or in combination thereof. Alternatively, different two
polymerizable-unsaturated-monomer-compounds may be used in
combination. The polymerizable-unsaturated-monomer-compound may be
a polymerizable oligomer compound.
[0073] The polymerizable oligomer compound may be appropriately
synthesized, or may be a commercially available product. Examples
of the commercially available product include EBECRYL 8402 (product
of DAICEL-ALLNEX LTD.).
[0074] The multifunctional
polymerizable-unsaturated-monomer-compound is more excellent in
curing speed than the monofunctional
polymerizable-unsaturated-monomer-compound. As a result, however,
viscosity of the resultant ink may be high, and considerable
volumetric shrinkage may occur. Therefore, it is preferable that
the polymerizable-unsaturated-monomer-compound have low viscosity,
and desirably have a low degree of volumetric shrinkage.
[0075] The degree of volumetric shrinkage of the
polymerizable-unsaturated-monomer-compound is preferably 15% or
less.
[0076] P. I. I. (skin irritation) of the
polymerizable-unsaturated-monomer-compound and the polymerizable
oligomer compound is not particularly limited and may be
appropriately selected depending on the intended purpose, but it is
preferably 1.0 or less. When the P. I. I. is 5.0 or more, skin is
subjected to intense stimulation, which may be problematic for
safety reasons.
[0077] Hue of the polymerizable-unsaturated-monomer-compound and
the polymerizable oligomer is preferably close to colorless and
transparent as far as possible, but is preferably 2 or less
according to the Gardner gray scale. When the hue thereof is more
than 2 according to the Gardner gray scale, color of image may
change.
[0078] The active-energy-ray-curable black ink of the present
disclosure necessarily contains a polymerization initiator.
[0079] The polymerization initiator is not particularly limited and
may be appropriately selected depending on the intended purpose.
Examples thereof include benzophenone, benzoin ethyl ether, benzoin
isopropyl ether, benzyl, benzyl dimethyl ketal,
.alpha.-hydroxyalkylphenone, .alpha.-aminoalkylphenone,
acylphosphine oxide, oxime ester, .alpha.-dicarbonyl, thioxanthone,
diethyl thioxanthone, isopropyl thioxanthone, and
chlorothioxanthone. Examples of a commercially available product of
the polymerization initiator include IRGACURE 819, IRGACURE 369,
IRGACURE 907, DAROCURE TPO, Darocur ITX, and Lucirin TPO (all
products are of BASF); and Vicure series 10 and 30 (product of
Stauffer Chemical).
[0080] The polymerization initiator is desirably selected depending
on wavelength characteristics of exposure lamps for curing such as
a mercury lamp, a metal halide lamp, and an UV-LED lamp. In
particular, it is preferable that a thioxanthone polymerization
initiator be valid during forming a thin film that easily undergoes
inhibition by oxygen.
[0081] Examples of a commercially available product of the
thioxanthone polymerization initiator include Speedcure DETX
(2,4-diethyl thioxanthone) and Speedcure ITX (2-isopropyl
thioxanthone) (both products are of Lambson); and KAYACURE DETX-S
(2,4-diethyl thioxanthone) (product of Nippon Kayaku Co.,
Ltd.).
[0082] Moreover, it is preferable that the polymerization initiator
satisfy the following properties: (i) high absorption efficiency of
active energy rays; (ii) being highly dissolved in the
polymerizable-unsaturated-compound; (iii) low odor, low property of
yellowing, and low toxicity; and (iv) non-occurrence of dark
reaction.
[0083] An amount of the polymerization initiator is preferably 1.0%
by mass or more but 20.0% by mass or less, more preferably 5.0% by
mass or more but 15.0% by mass or less, relative to the total
amount of the active-energy-ray-curable composition of the present
disclosure.
[0084] It is problematic that the amount of the polymerization
initiator falling within a range of less than 1.0% by mass results
in reduction in curing ability of the ink, and that the amount of
the polymerization inhibitor falling within a range of more than
20.0% by mass results in deterioration in film properties such as
rubfastness and problematic is coloring due to the color of the
polymerization initiator itself.
[0085] When a mixture of the
polymerizable-unsaturated-monomer-compound and the polymerization
initiator is irradiated with active energy rays, the polymerization
initiator generates radicals as described in formulas (I) and (II)
below. The radicals allow the polymerizable double bond of the
polymerizable oligomer or the
polymerizable-unsaturated-monomer-compound to cause additional
reaction. The radicals are further generated through the
aforementioned additional reaction. The polymerization reaction
proceeds as described in formula (III) below by repeating the
additional reaction in the polymerizable double bond in another
polymerizable oligomer or another
polymerizable-unsaturated-monomer-compound.
##STR00002##
[0086] When a benzophenone polymerization initiator of
hydrogen-abstraction type described in the formula (I) is used,
polymerization reaction may be slow using the polymerization
initiator alone. Thus, the benzophenone polymerization initiator of
hydrogen-abstraction type is preferably used in combination with an
amine sensitizer to enhance reactivity. The amine sensitizer
prevents the polymerization initiator from providing hydrogen
through the hydrogen-abstraction effect, and prevents
polymerization reaction from reaction inhibition caused by oxygen
in the air.
[0087] The amine sensitizer is not particularly limited and may be
appropriately selected depending on the intended purpose. Examples
of the amine sensitizer include triethanol amine,
triisopropanolamine, 4,4-diethylamino benzophenone,
2-dimethylaminoethyl benzoic acid, 4-dimethylamino benzoic acid
ethyl, and 4-dimethylamino benzoic acid isoacyl.
[0088] An amount of the sensitizer in the active-energy-ray-curable
composition and the active-energy-ray-curable ink is not
particularly limited and may be appropriately selected depending on
the intended purpose, but it is preferably 1% by mass or more but
15% by mass or less, more preferably 3% by mass or more but 8% by
mass or less.
[0089] The active-energy-ray-curable composition and the
active-energy-ray-curable ink preferably contain the polymerization
inhibitor in order to enhance storage stability.
[0090] The polymerization inhibitor is not particularly limited and
may be appropriately selected depending on the intended purpose.
Examples of the polymerization inhibitor include
2,6-di-tert-butyl-p-cresol (BHT), 2,3-dimethyl-6-tert-butylphenol
(IA), anthraquinone, hydroquinone (HQ), hydroquinone monomethyl
ether (MEHQ), and p-methoxyphenol.
[0091] An amount of the polymerization inhibitor in the
active-energy-ray-curable composition and the
active-energy-ray-curable ink is not particularly limited and may
be appropriately selected depending on the intended purpose, but it
is preferably 0.0025% by mass or more but 3% by mass or less.
[0092] When the amount of the polymerization inhibitor is less than
0.0025% by mass, the resultant ink is deteriorated in storage
stability and raises viscosity under high temperature environment.
When the amount thereof is more than 3% by mass, the resultant ink
is deteriorated in ultraviolet curing ability.
[0093] When the active-energy-ray-curable composition and the
active-energy-ray-curable ink contain a surfactant, the surfactant
imparts interface adsorptivity to the active-energy-ray-curable
composition and the ink, and a surface tension of the active energy
ray curable black ink is reduced, which results in improvement of
wettability and leveling ability.
[0094] The surfactant is not particularly limited and may be
appropriately selected depending on the intended purpose. Examples
of the surfactant include an anionic surfactant, a nonionic
surfactant, a silicone surfactant, and a fluoro surfactant.
[0095] Examples of the anionic surfactant include sulfosuccinate,
disulfonate, phosphate ester, sulfate, sulfonate, and a mixture
thereof.
[0096] Examples of the nonionic surfactant include polyvinyl
alcohol, polyacrylic acid, isopropyl alcohol, acetylene diol,
ethoxylated octyl phenol, ethoxylated branched secondary alcohol,
perfluorobutane sulfonic acid, and alkoxylated alcohol.
[0097] Examples of the silicone surfactant include
polyether-modified polydimethylsiloxane, polyester-denatured
silicone, polyether-denatured silicone, polyether-denatured
polydimethylsiloxane, and polyester-denatured
polydimethylsiloxane.
[0098] These silicone surfactants are preferably used for the
present disclosure.
[0099] BYK-347, BYK-348, BYK-UV 3500, and BYK-UV series (3510,
3530, 3570, and 3576) (all products are of BYK Japan KK) are
particularly preferable.
[0100] Examples of the fluoro surfactant include ethoxylated
nonylphenol.
[0101] An amount of the surfactant in the active-energy-ray-curable
composition and the active-energy-ray-curable ink is not
particularly limited and may be appropriately selected depending on
the intended purpose, but it is preferably 0.1% by mass or more but
3% by mass or less, more preferably 0.2% by mass or more but 1% by
mass or less relative to the total amount of the
active-energy-ray-curable composition. When the amount thereof is
less than 0.1% by mass, wettability of the resultant ink may not be
obtained. When the amount thereof is more than 3% by mass, the
resultant ink is prevented from curing ability. It is advantageous
in that the amount thereof falling within the preferable range
results in improvement of wettability and leveling ability.
[0102] Viscosity of the active-energy-ray-curable composition and
the ink s during ejection from a head is preferably 3 mPas or more
but 10 mPas or less. Viscosity during ejection of the ink can be
adjusted by heating a head until a temperature of the ink is up to
about 50.degree. C. When the viscosity thereof is less than 3 mPas,
the resultant ink contains dust particles. When the viscosity
thereof is more than 10 mPas, the resultant ink is deteriorated in
ejecting stability.
[0103] The viscosity can be measured using an E-type viscometer,
for example.
[0104] The aforementioned materials can be used to prepare the
active-energy-ray-curable composition and the ink of the present
disclosure. A pigment, a dispersant, and a
polymerizable-unsaturated-monomer are charged into a dispersion
device such as a ball-mill, a disc-mill, a pin-mill, and a
Dino-mill, and are dispersed and kneaded to prepare a pigment
dispersion liquid. Then, the pigment dispersion liquid is mixed
with a polymerizable-unsaturated-monomer, an initiator, an
inhibitor, and a surfactant, and then the resultant mixture is
formed into an ink to obtain the active-energy-ray-curable ink.
[0105] A characteristic of absorbance of the ink is different
depending on materials, amounts of materials, and dispersion
methods. Therefore, in order to obtain the
active-energy-ray-curable composition and the ink having the
characteristic of absorbance defined in the present disclosure, it
is necessary to select appropriate materials, optimize amounts of
the materials, a dispersion method, and a method for preparing the
ink.
[0106] The active-energy-ray-curable composition and the ink of the
present disclosure can be cured by the active energy rays. Examples
of the light source emitting the active energy rays include a
mercury lamp, a metal halide lamp, and a UV-LED lamp.
[0107] The mercury lamp is a lamp obtained by encapsulating mercury
(Hg) having high purity and a small amount of noble gas in an arc
tube made of quartz glass. The mercury lamp has a dominant
wavelength of 365 nm, effectively emits ultraviolet rays having a
wavelength of 254 nm, 303 nm, and 313 nm, and has high output power
of ultraviolet rays having a short wavelength.
[0108] The metal halide lamp is a lamp obtained by encapsulating
mercury and a halogenated metal in an arc tube, emits an active
energy ray spectrum falling within a broad range of 200 nm or more
but 450 nm or less, and has higher output power of ultraviolet rays
having a long wavelength of 300 nm or more but 450 nm or less,
compared to the mercury lamp.
[0109] The UV-LED lamp can reduce the environmental load due to a
LED system (long lifetime and low electricity consumption), does
not generate ozone, and can be compact. Therefore, the UV-LED lamp
is the most suitable for curing the active-energy-ray-curable
composition of the present disclosure.
[0110] One example of wavelength of the light source is given in
FIGS. 1, 2, and 3.
<Application Field>
[0111] The application field of the active-energy-ray-curable
composition of the present disclosure is not particularly limited.
It can be applied to any field where active-energy-ray-curable
compositions are used. For example, the curable composition is
selected to a particular application and used for a resin for
processing, a paint, an adhesive, an insulant, a releasing agent, a
coating material, a sealing material, various resists, and various
optical materials.
[0112] Furthermore, the active-energy-ray-curable composition of
the present disclosure can be used as an ink to form
two-dimensional texts, images, and designed coating film on various
substrates and in addition as a solid object forming material to
form a three-dimensional object. This three dimensional object
forming material may also be used as a binder for powder particles
used in a powder layer laminating method of forming a
three-dimensional object by repeating curing and layer-forming of
powder layers, and as a three-dimensional object constituent
material (a model material) and a supporting member used in an
additive manufacturing method (a stereolithography method) as
illustrated in FIG. 7, FIG. 8A, FIG. 8B, FIG. 8C, and FIG. 8D. FIG.
7 is a diagram illustrating a method of additive manufacturing to
sequentially form layers of the active-energy-ray-curable
composition of the present disclosure one on top of the other by
repeating discharging the curable composition to particular areas
followed by curing upon irradiation of an active energy ray
(details will be described hereinafter). FIGS. 8A to 8D are each a
diagram illustrating a method of additive manufacturing to
sequentially form cured layers 6 having respective predetermined
forms one on top of the other on a movable stage 3 by irradiating a
storing pool (storing part) 1 of the active energy ray curable
composition 5 of the present disclosure with the active energy ray
4.
[0113] An apparatus for fabricating a three-dimensional object by
the active-energy-ray-curable composition of the present disclosure
is not particularly limited and can be a known apparatus. For
example, the apparatus includes a containing device, a supplying
device, and a discharging device of the curable composition, and an
active energy ray irradiator.
<Composition Stored Container>
[0114] The composition stored container of the present disclosure
contains a container and the active-energy-ray-curable composition
or the active-energy-ray-curable composition. For example, if the
active-energy-ray-curable composition of the present disclosure is
used for ink, a container that stores the ink can be used as an ink
cartridge or an s ink bottle. Therefore, users can avoid direct
contact with the ink during operations such as transfer or
replacement of the ink, so that fingers and clothes are prevented
from contamination. Furthermore, inclusion of foreign matters such
as dust in the ink can be prevented. In addition, the container can
be of any size, any form, and any material. For example, the
container can be designed to a particular application. It is
preferable to use a light blocking material to block the light or
cover a container with a light blocking sheet, etc.
[0115] FIG. 5 illustrates one example of an ink cartridge serving
as the composition stored container that contains a container, and
the is active-energy-ray-curable composition or the
active-energy-ray-curable ink in the container. An ink bag 11
contains an ink inlet 12 and an ink outlet 13. The ink bag 11 is
filled with the ink by injecting the ink from the ink inlet 12.
After removing the air present inside the ink bag 11, the ink inlet
12 is sealed by fusion bonding.
[0116] When the ink bag 11 is used, a needle attached to the main
body of an ink ejecting device such as an inkjet recording device
is inserted into the ink outlet 13 to supply the ink to the device.
The ink outlet 13 is formed of a rubber member, for example. The
ink bag 11 is stored in a plastic cartridge case 14, which is used
as an ink cartridge 10. The ink cartridge 10 is detachably mounted
in the inkjet recording device. The ink cartridge configured to be
detachably mounted makes it possible to improve the ink in work
efficiency of replenishment and replacement.
<Image Forming Method and Image Forming Apparatus>
[0117] An apparatus for forming the two-dimensional or
three-dimensional image of the present disclosure includes the
composition stored container, and an irradiator unit configured to
irradiate the active-energy-ray-curable composition or the
active-energy-ray-curable ink with active energy rays; and further
preferably includes an ejecting unit configured to eject the
active-energy-ray-curable ink stored in the composition stored
container.
[0118] A method for forming the two-dimensional or
three-dimensional image of the present disclosure includes a step
of irradiating the active-energy-ray-curable composition or the
ejected active-energy-ray-curable ink ejected with active energy
rays, and further preferably includes a step of ejecting the
active-energy-ray-curable composition or the
active-energy-ray-curable ink. Moreover, in the method for forming
the two-dimensional or three-dimensional image, the active energy
rays with which the active-energy-ray-curable composition is
irradiated is preferably light of a light-emitting diode.
[0119] The method of discharging the curable composition is not
particularly limited, and examples thereof include a continuous
jetting method and an on-demand method. The on-demand method
includes a piezo method, a thermal method, an electrostatic method,
etc.
[0120] FIG. 6 is a diagram illustrating a two-dimensional image
forming apparatus equipped with an inkjet discharging device.
Printing units 23a, 23b, 23c, and 23d respectively having ink
cartridges and discharging heads for yellow, magenta, cyan, and
black active-energy-ray-curable inks discharge the inks onto a
recording medium 22 fed from a supplying roller 21. Thereafter,
light sources 24a, 24b, 24c, and 24d configured to cure the inks
emit active energy rays to the inks, thereby curing the inks to
form a color image. Thereafter, the recording medium 22 is conveyed
to a processing unit 25 and a printed matter reeling roll 26. Each
of the printing unit 23a, 23b, 23c and 23d may have a heating
mechanism to liquidize the ink at the ink discharging portion.
Moreover, in another embodiment of the present disclosure, a
mechanism may optionally be included to cool down the recording
medium to around room temperature in a contact or non-contact
manner. In addition, the inkjet recording method may be either of
serial methods or line methods. The serial methods include
discharging an ink onto a recording medium by moving the head while
the recording medium intermittently moves according to the width of
a discharging head. The line methods include discharging an ink
onto a recording medium from a discharging head held at a fixed
position while the recording medium continuously moves.
[0121] The recording medium 22 is not particularly limited.
Specific examples thereof include, but are not limited to, paper,
film, metal, or complex materials thereof. The recording medium 22
takes a sheet-like form but is not limited thereto. The image
forming apparatus may have a one-side printing configuration and/or
a two-side printing configuration.
[0122] Optionally, multiple colors can be printed with no or weak
active energy ray from the light sources 24a, 24b, and 24c followed
by irradiation of the active energy ray from the light source 24d.
As a result, energy and cost can be saved.
[0123] The recorded matter having images printed with the ink of
the present disclosure includes articles having printed images or
texts on a plain surface of conventional paper, resin film, etc., a
rough surface, or a surface made of various materials such as metal
or ceramic. In addition, by laminating layers of images in part or
the entire of a recording medium, a partially stereoscopic image
(formed of two dimensional part and three-dimensional part) and a
three dimensional objects can be fabricated.
[0124] FIG. 7 is a schematic diagram illustrating another example
of the image forming apparatus (apparatus to fabricate a 3D object)
of the present disclosure. An image forming apparatus 39
illustrated in FIG. 7 sequentially forms thin layers one on top of
the other using a head unit having inkjet heads arranged movable in
the directions indicated by the arrows A and B. In the image
forming apparatus 39, an ejection head unit 30 for additive
manufacturing ejects a first active-energy-ray-curable composition,
and ejection head units 31 and 32 for support and curing these
compositions ejects a second active-energy-ray-curable composition
having a different composition from the first
active-energy-ray-curable composition, while ultraviolet
irradiators 33 and 34 adjacent to the ejection head units 31 and 32
cure the compositions. To be more specific, for example, after the
ejection head units 31 and 32 for support eject the second
active-energy-ray-curable composition onto a substrate 37 for
additive manufacturing and the second active-energy-ray-curable
composition is solidified by irradiation of an active energy ray to
form a first substrate layer having a space for composition, the
ejection head unit 30 for additive manufacturing ejects the first
active-energy-ray-curable composition onto the pool followed by
irradiation of an active energy ray for solidification, thereby
forming a first additive manufacturing layer. This step is repeated
multiple times lowering the stage 38 movable in the vertical
direction to laminate the supporting layer (or support layer) and
the additive manufacturing layer to fabricate a solid object 35.
Thereafter, an additive manufacturing support 36 is removed, if
desired. Although only a single ejection head unit 30 for additive
manufacturing is provided to the image forming apparatus
illustrated 39 in FIG. 7, it can have two or more units 30.
(Two-Dimensional or Three-Dimensional Image)
[0125] The two-dimensional or three-dimensional image can be
obtained through curing by irradiating the
active-energy-ray-curable composition or the
active-energy-ray-curable ink with the active energy rays. Examples
of the two-dimensional image include a printed matter.
[0126] Examples of the printed matter include a printed matter
recorded on a smooth surface of conventional plain paper or resin
film, a printed matter recorded on a concave-convex surface of the
recording medium, and a printed matter on a surface of the
recording medium formed of various materials such as metal and
ceramic. The photopolymerizable compound or the photosetting
composition of the present disclosure is suitable for a material of
the ink, but is applicable to a resin for processing, a paint, an
adhesive agent, an insulant, a release agent, a coating material, a
sealing material, various resists, and various optical
materials.
(Structure)
[0127] The structure contains a base and the two-dimensional or
three-dimensional image on the base.
[0128] The base is not particularly limited and may be
appropriately selected depending on the intended purpose. Examples
thereof include paper, thread, fiber, fabrics, leather, metal,
plastic, glass, wood, ceramic, and composite materials thereof. A
plastic substrate is preferable in terms of processability.
(Processed Product)
[0129] Examples of the processed product include meters or
operation panels of vehicles, office machines, electric and
electronic machines, and cameras. Among them, a processed product
obtained by drawing the two-dimensional or three-dimensional image,
or the structure is preferable.
EXAMPLES
[0130] The present disclosure will be described with reference to
the following Examples. However, it should be noted that the
present disclosure is not limited to these Examples.
Example 1
[0131] The following materials were charged in the following
respective amounts into a 100 ml-ball-mill loaded with zirconia
beads having a diameter of 2 mm, and were dispersed at 70
revolutions/minute for 48 hours. Then, the resultant materials were
charged into a sand-mill loaded with zirconia beads having a
diameter of 0.1 mm for 3 hours at a circumferential velocity of 8
m/s, to obtain a pigment dispersing element. [0132] Carbon black
(Special Black 250: product of Orion): 45 parts by mass [0133]
Dispersant (BYKJET-9151: product of BYK Japan KK): 18 parts by mass
[0134] Monomer (phenoxyethyl acrylate: product of Osaka Organic
Chemical Industry Ltd.): 162 parts by mass
[0135] The following materials were mixed in the following
respective amounts with the aforementioned pigment dispersing
element (15 parts by mass) to obtain an ink. [0136] Monomer (benzyl
acrylate: product of Osaka Organic Chemical Industry Ltd.): 60
parts by mass [0137] Monomer (tripropylene glycol diacrylate:
product of Shin Nakamura Chemical Co., Ltd.): 5 parts by mass
[0138] Monomer (pentaerythritol triacrylate: product of Shin
Nakamura Chemical Co., Ltd.): 5 parts by mass [0139] Surfactant
(BYK-UV 3510: product of BYK Japan KK): 0.3 parts by mass [0140]
Initiator (IRGACURE 819: product of BASF): 6 parts by mass [0141]
Initiator (DAROCURE TPO: product of BASF): 5 parts by mass [0142]
Initiator (Speedcure DETX: product of Lambson): 3.5 parts by mass
[0143] Polymerization inhibitor (p-methoxyphenol: product of Nippon
Kayaku Co., Ltd.): 0.2 parts by mass
[0144] The obtained ink was printed and cured with an UV-LED lamp
to obtain a printed sample.
Example 2
[0145] The following materials were dispersed in the following
respective amounts using a homogenizer at 5,000 revolutions for 20
minutes. Then, the resultant mixture was charged into a sand-mill
loaded with zirconia beads having a diameter of 0.3 mm, and was
dispersed at a circumferential velocity of 8 m/s for 1 hour to
obtain a pigment dispersing element. [0146] Carbon black (Special
Black 250: product of Orion): 45 parts by mass [0147] Dispersant
(BYKJET-9151: product of BYK Japan KK): 18 parts by mass [0148]
Monomer (phenoxyethyl acrylate: product of Osaka Organic Chemical
Industry Ltd.): 162 parts by mass
[0149] The following materials were mixed in the following
respective amounts with the aforementioned pigment dispersing
element (15 parts by mass) to obtain an ink. [0150] Monomer (benzyl
acrylate: product of Osaka Organic Chemical Industry Ltd.): 55
parts by mass [0151] Monomer (tripropylene glycol diacrylate:
product of Shin Nakamura Chemical Co., Ltd.): 15 parts by mass
[0152] Monomer (pentaerythritol triacrylate: product of Shin
Nakamura Chemical Co., Ltd.): 7 parts by mass [0153] Surfactant
(BYK-UV 3510: product of BYK Japan KK): 0.3 parts by mass [0154]
Initiator (IRGACURE 819: product of BASF): 5 parts by mass [0155]
Initiator (DAROCURE TPO: product of BASF): 3 parts by mass [0156]
Initiator (Speedcure DETX: product of Lambson): 3.5 parts by mass
[0157] Polymerization inhibitor (p-methoxyphenol: product of Nippon
Kayaku Co., Ltd.): 0.2 parts by mass
[0158] The obtained ink was printed and cured with an UV-LED lamp
to obtain a printed sample.
Example 3
[0159] The following materials were charged in the following
respective amounts into a 100 ml-ball-mill loaded with zirconia
beads having a diameter of 2 mm at 70 revolutions/minute for 150
hours to obtain a pigment dispersing element. [0160] Carbon black
(MOGUL-L: product of CABOT): 45 parts by mass [0161] Dispersant
(SOLSPERSE 39000: product of The Lubrizol Corporation): 15 parts by
mass [0162] Monomer (acryloyl morpholine: product of Kohjin Co.,
Ltd.): 165 parts by mass
[0163] The following materials were mixed in the following
respective amounts with the aforementioned pigment dispersing
element (15 parts by mass) to obtain an ink. [0164] Monomer
(acryloyl morpholine: product of Kohjin Co., Ltd.): 35 parts by
mass [0165] Monomer (isobornyl acrylate: product of Osaka Organic
Chemical Industry Ltd.): 20 parts by mass [0166] Monomer
(dipentaerythritol pentaacrylate: product of Sartomer): 15 parts by
mass [0167] Surfactant (BYK-UV 3575: product of BYK Japan KK): 0.3
parts by mass [0168] Initiator (IRGACURE 819: product of BASF): 5
parts by mass [0169] Initiator (DAROCURE TPO: product of BASF): 5
parts by mass [0170] Initiator (Speedcure ITX: product of Lambson):
4.5 parts by mass [0171] Polymerization inhibitor
(2,6-di-tert-butyl-p-cresol: product of Nippon Kayaku Co., Ltd.):
0.2 parts by mass
[0172] The obtained ink was printed and cured with an UV-LED lamp
to obtain a printed sample.
Example 4
[0173] The following materials were charged in the following
respective amounts into a 100 ml-ball-mill loaded with zirconia
beads having a diameter of 2 mm at 70 revolutions/minute for 180
hours to obtain a pigment dispersing element. [0174] Carbon black
(Special Black 250: product of Orion): 45 parts by mass [0175]
Dispersant (BYKJET-9151: product of BYK Japan KK): 10 parts by mass
[0176] Monomer (2-vinyloxyethoxyethyl acrylate: product of NIPPON
SHOKUBAI CO., LTD.): 170 parts by mass
[0177] The following materials were mixed in the following
respective amounts with the aforementioned pigment dispersing
element (15 parts by mass) to obtain an ink. [0178] Monomer
(tetrahydrofurfuryl acrylate: product of Hitachi Chemical Company,
Ltd.): 72 parts by mass [0179] Surfactant (BYK-UV 3510: product of
BYK Japan KK): 0.5 parts by mass [0180] Initiator (IRGACURE 819:
product of BASF): 8 parts by mass [0181] Initiator (KAYACURE
DETX-S: product of Nippon Kayaku Co., Ltd.): 4.5 parts by mass
[0182] The obtained ink was printed and cured with an UV-LED lamp
to obtain a printed sample.
Example 5
[0183] The following materials were dispersed in the following
respective amounts using a homogenizer at 8,000 revolutions for 15
minutes. Then, the resultant mixture was charged into a sand-mill
loaded with zirconia beads having a diameter of 0.3 mm, and was
dispersed at a circumferential velocity of 8 m/s for 1 hour to
obtain a pigment dispersing element. [0184] Carbon black (Special
Black 250: product of Orion): 45 parts by mass.cndot.Dispersant
(SOLSPERSE 39000: product of The Lubrizol Corporation): 14 parts by
mass [0185] Monomer (4-hydroxybutyl acrylate: product of Osaka
Organic Chemical Industry Ltd.): 166 parts by mass
[0186] The following materials were mixed in the following
respective amounts with the aforementioned pigment dispersing
element (15 parts by mass) to obtain an ink. [0187] Monomer
(4-hydroxybutyl acrylate: product of Osaka Organic Chemical
Industry Ltd.): 40 parts by mass [0188] Monomer (tripropylene
glycol diacrylate: product of Shin Nakamura Chemical Co., Ltd.): 5
parts by mass [0189] Monomer (pentaerythritol triacrylate: product
of Shin Nakamura Chemical Co., Ltd.): 5 parts by mass [0190]
Surfactant (BYK-UV 3510: product of BYK Japan KK): 0.3 parts by
mass [0191] Initiator (IRGACURE 819: product of BASF): 6 parts by
mass [0192] Initiator (DAROCURE TPO: product of BASF): 5 parts by
mass [0193] Initiator (Speedcure DETX: product of Lambson): 3.5
parts by mass [0194] Polymerization inhibitor (p-methoxyphenol:
product of Nippon Kayaku Co., Ltd.): 0.2 parts by mass
[0195] The obtained ink was printed and cured with an UV-LED lamp
to obtain a printed sample.
Example 6
[0196] The following materials were mixed in the following
respective amounts with the pigment dispersing element of Example 1
(15 parts by mass) to obtain an ink. [0197] Monomer (acryloyl
morpholine: product of Kohjin Co., Ltd.): 45 parts by mass [0198]
Monomer (tripropylene glycol diacrylate: product of Osaka Organic
Chemical Industry Ltd.): 30 parts by mass [0199] Oligomer (urethane
acrylate oligomer EBECRYL 8402: product of Daicel-Cytec): 6 parts
by mass [0200] Surfactant (BYK-UV 3576: product of BYK Japan KK):
0.3 parts by mass [0201] Initiator (IRGACURE 369: product of BASF):
3.5 parts by mass [0202] Polymerization inhibitor (p-methoxyphenol:
product of Nippon Kayaku Co., Ltd.): 0.2 parts by mass
[0203] The obtained ink was printed and cured with a mercury lamp
to obtain a printed sample.
Example 7
[0204] The following materials were mixed in the following
respective amounts with the pigment dispersing element of Example 2
(15 parts by mass) to obtain an ink. [0205] Monomer
(2-methyl-2-ethyl-1,3-dioxolan-4-ylmethyl acrylate: product of
Osaka Organic Chemical Industry Ltd.): 30 parts by mass [0206]
Monomer (isobornyl acrylate: product of Osaka Organic Chemical
Industry Ltd.): 30 parts by mass [0207] Monomer (dimethylol
tricyclodecane diacrylate: product of Nippon Kayaku Co., Ltd.): 20
parts by mass [0208] Surfactant (BYK-UV 3535: product of BYK Japan
KK): 0.3 parts by mass [0209] Initiator (IRGACURE 907: product of
BASF): 4.5 parts by mass [0210] Polymerization inhibitor
(p-methoxyphenol: product of Nippon Kayaku CO., Ltd.): 0.2 parts by
mass
[0211] The obtained ink was printed and cured with a metal halide
lamp to obtain a printed sample.
Comparative Example 1
[0212] Printing was performed in the same manner as in Example 1
except that the pigment of Example 1 was changed to MA11 (product
of Mitsubishi Chemical Corporation).
Comparative Example 2
[0213] Printing was performed in the same manner as in Example 2
except that the pigment of Example 2 was changed to SBX45 (product
of Asahi Carbon Co., Ltd.).
Comparative Example 3
[0214] Printing was performed in the same manner as in Example 3
except that the pigment of Example 3 was changed to MA220 (product
of Mitsubishi Chemical Corporation).
Comparative Example 4
[0215] Printing was performed in the same manner as in Example 4
except that the dispersant of Example 4 was changed to
DISPERBYK-168 having an amine value of 11 mg KOH/g.
Comparative Example 5
[0216] Printing was performed in the same manner as in Example 2
except that the pigment of Example 2 was changed to SB350 (product
of Orion).
Comparative Example 6
[0217] Printing was performed in the same manner as in Example 2
except that the pigment of Example 2 was changed to #5 (product of
Mitsubishi Chemical Corporation).
Comparative Example 7
[0218] Printing was performed in the same manner as in Example 2
except that the materials of Example 2 were not dispersed using a
homogenizer but were dispersed by a dyno-mill loaded with beads
having a diameter of 1.0 mm.
Comparative Example 8
[0219] Printing was performed in the same manner as in Example 2
except that the pigment of Example 2 was changed to SB550 (product
of Orion).
<Evaluation>
--Absorbance--
[0220] The prepared ink was 1,200-fold diluted with precise in
phenoxyethyl acrylate so that a concentration of the pigment was
0.0025% by mass to measure absorbance of the ink using a
spectrophotometer U-3900H (product of Hitachi High-Technologies
Corporation).
[0221] A graph of results of Examples and Comparative Examples was
given in FIG. 4.
--Particle Diameter--
[0222] The prepared ink was about 100-fold diluted to measure a
rate of the volume average particle diameter having a diameter of
50 nm or less and a rate of the volume average particle diameter
having a diameter of 230 nm or more using a particle size analyzer
UPA150 (product of NIKKISO CO., LTD.).
--Preparation of Printed Matter--
[0223] A solid image of the prepared ink (10 cm.times.10 cm) was
output on a recording medium (product name: COSMOSHINE A4300 coat
PET film (100 .mu.m), product of TOYOBO CO., LTD.) using a printer
for evaluation obtained by modifying a printer (device name:
SG7100, product of Ricoh Company, Ltd.) to obtain a printed
sample.
--UV Curing Treatment--
[0224] A UV-LED device for inkjet printer or an UV curing device of
metal halide lamp (both products are of USHIO INC.) was
appropriately selected depending on the Examples. The selected
device was used to cure the ink at an irradiation dose of 300
mJ/cm.sup.2.
[0225] Here, an ultraviolet intensity meter (device name: UM-10)
and a receiver (device name: UM-400) (both products are of Konica
Minolta Sensing) were used to measure an irradiation dose.
--Printing Density--
[0226] A density of the sample subjected to curing treatment was
measured using X-Rite 939, and was evaluated based on the following
criteria. Results are given in Tables 1-1 and 1-2.
[Evaluation Criteria]
[0227] A: 1.80 or more
[0228] B: 1.60 or more but less than 1.80, which is not problematic
for practical use.
[0229] C: 1.40 or more but less than 1.60
[0230] D: Less than 1.40
--Evaluation of Curing Ability--
[0231] A white cotton attached to a crock meter was rubbed ten
times in a reciprocating manner with a load of 50 g/cm.sup.2, and
then a density on the white cotton was measured based on the
following criteria. Results are given in Tables 1-1 and 1-2.
[0232] Curing ability was evaluated by the following formula:
[0233] Density of ink on white cotton after measurement--density of
ink on white cotton before measurement.
[Evaluation Criteria]
[0234] A: Less than 0.001
[0235] B: 0.001 or more but less than 0.006
[0236] C: 0.006 or more but less than 0.010
[0237] D: 0.010 or more
--Close Adhesiveness--
[0238] A part of a solid image of the printed sample after curing
was cut with a cutter knife at 1 mm-intervals to have 100 squares
in the solid image according to JIS K5400. Then, the solid image
was peeled with a piece of an adhesive cellophane tape. Squares
that were not peeled were observed and counted with a loupe to
evaluate "close adhesiveness" based on the following criteria.
Results are given in Tables 1-1 and 1-2.
[Evaluation Criteria]
[0239] A: 100/100
[0240] B: 80/100 or more but 99/100 or less
[0241] C: 40/100 or more but 79/100 or less
[0242] D: 0/100 or more but 39/100 or less
TABLE-US-00001 TABLE 1-1 Example Example Example Example Example
Example Example 1 2 3 4 5 6 7 Carbon Product name SB250 SB250 MOGUL
L SB250 SB250 SB250 SB250 black Number average 56 56 55 55 55 55 55
particle diameter (nm) DBP oil 46 46 45 45 45 45 45 absorption
amount (g/100 g) pH 3.1 3.1 3.0 3.0 3.0 3.0 3.0 Absorbance 500 nm
1.364 1.333 1.326 1.341 1.330 1.364 1.333 750 nm 1.081 1.032 1.027
1.031 1.021 1.081 1.032 400 nm/750 nm 1.48 1.55 1.54 1.56 1.57 1.48
1.55 365 nm/500 nm 1.15 1.17 1.16 1.17 1.17 1.15 1.17 Particle
Volume average 122 133 140 141 135 122 133 diameter particle
diameter of dispersoid (nm) particles Rate of particles 5.5 6.1 6.7
7.0 6.5 5.5 6.1 having 50 nm or less (% by mass) Rate of particles
2.8 7.5 9.1 9.2 7.8 2.8 7.5 having 230 nm or more (% by mass)
Evaluation Printing 1.88 1.85 1.83 1.82 1.84 1.88 1.85 results
density A A A A A A A Curing ability A A A A A A A Close A A A A A
A A adhesiveness
TABLE-US-00002 TABLE 1-2 Comparative Comparative Comparative
Comparative Comparative Comparative Comparative Comparative Example
Example Example Example Example Example Example Example 1 2 3 4 5 6
7 8 Carbon Product name MA11 SBX45 MA220 SB250 SB250 SB250 SB250
SB250 black Number average 29 22 55 55 31 76 55 25 particle
diameter (nm) DBP oil 64 55 93 45 4.5 71 45 47 absorption amount
(g/100 g) pH 3.5 3.0 3.0 3.0 3.5 7.5 3.0 2.8 Absorbance 500 nm
1.418 1.401 1.109 1.212 1.425 0.982 1.198 1.366 750 nm 1.026 0.952
0.978 0.981 1.041 0.875 0.986 0.968 400 nm/750 nm 1.78 2.04 1.23
1.42 1.73 1.20 1.39 1.87 365 nm/500 nm 1.27 1.40 1.05 1.21 1.24
1.04 1.11 1.33 Particle Volume average 135 106 229 155 127 251 131
199 diameter particle diameter of dispersoid (nm) particles Rate of
particles 15.8 20.5 0.8 11.8 16.2 0.5 15.1 2.5 having 50 nm or less
(% by mass) Rate of particles 10.4 1.8 43.2 11.5 8.4 73.5 10.5 23.5
having 230 nm or more (% by mass) Evaluation Printing 1.83 1.90
1.33 1.58 1.84 1.24 1.83 1.45 results density A A D C A D A C
Curing ability C D A A C A C A Close C D A B D B C A
adhesiveness
[0243] As is clear from the results in Table 1, the black inks of
Examples 1 to 7 having absorbance defined in the present disclosure
can be excellent in printing density, curing ability, and close
adhesiveness. Meanwhile, in black inks of Comparative Examples 1 to
8, the black inks having high printing density were deteriorated in
curing ability and close adhesiveness, and the black inks excellent
in curing ability and close adhesiveness (Comparative Examples 3
and 8) were deteriorated in printing density.
[0244] Moreover, even if the same material is used, the ink having
absorbance defined in the present disclosure may or may not be
obtained.
[0245] Therefore, the ink defined in the present disclosure can be
obtained by optimizing the materials, the formulations, and the
preparation methods.
[0246] Embodiments of the present disclosure are as follows, for
example. [0247] <1> An active-energy-ray-curable composition,
which satisfies the following relationships of absorbance:
[0248] a ratio of absorbance at a wavelength of 400 nm to
absorbance at a wavelength of 750 nm is 1.4 or more but 1.6 or
less; and
[0249] a ratio of absorbance at a wavelength of 365 nm to
absorbance at a wavelength of 500 nm is 1.2 or less. [0250]
<2> The active-energy-ray-curable composition according to
<1>, wherein a volume average particle diameter of dispersoid
particles in the active-energy-ray-curable composition is 100 nm or
more but 150 nm or less, [0251] wherein an amount of the dispersoid
particles having a volume average particle diameter of 50 nm or
less is 10% by mass or less relative to a total amount of the
dispersoid particles, and [0252] wherein an amount of the
dispersoid particles having a volume average particle diameter of
230 nm or more is 10% by mass or less relative to the total amount
of the dispersoid particles. [0253] <3> The
active-energy-ray-curable composition according to <1> or
<2>, [0254] wherein the active-energy-ray-curable composition
includes a carbon black subjected to oxidation treatment at pH 3.5
or less, [0255] wherein a number average particle diameter of the
carbon black is 40 nm or more but 60 nm or less, and [0256] wherein
a DBP oil absorption amount of the carbon black is 35 g/100 g or
more but 55 g/100 g or less. [0257] <4> The
active-energy-ray-curable composition according to any one of
<1> to <3>, [0258] wherein the
active-energy-ray-curable composition includes an acrylic block
polymer having an acid value of 5 mg KOH/g or more and an amine
value of 15 mg KOH/g or more. [0259] <5> The
active-energy-ray-curable composition according to any one of
<1> to <4>, [0260] wherein the
active-energy-ray-curable composition is a material for forming a
three-dimensional object. [0261] <6> The
active-energy-ray-curable composition according to any one of
<1> to <5>, [0262] wherein the
active-energy-ray-curable composition has sensitivity to light of a
light-emitting diode having a luminescence peak in a wavelength
range of 360 nm or more but 400 nm or less. [0263] <7> An
active-energy-ray-curable ink, which satisfies the following
relationships of absorbance:
[0264] a ratio of absorbance at a wavelength of 400 nm to
absorbance at a wavelength of 750 nm is 1.4 or more but 1.6 or
less; and
[0265] a ratio of absorbance at a wavelength of 365 nm to
absorbance at a wavelength of 500 nm is 1.2 or less. [0266]
<8> The active-energy-ray-curable ink according to <7>,
wherein the active-energy-ray-curable ink is used for inkjet.
[0267] <9> A composition stored container including: [0268] a
container; and [0269] the active-energy-ray-curable composition
according to any one of <1> to <6> or the
active-energy-ray-curable ink according to <7> or <8>
in the container. [0270] <10> An apparatus for forming a
two-dimensional or three-dimensional image, the apparatus
including: [0271] the composition stored container according to
<9>; [0272] an irradiator configured to irradiate the
active-energy-ray-curable composition or the
active-energy-ray-curable ink with active energy rays. [0273]
<11> The apparatus for forming the two-dimensional or
three-dimensional image according to <10>, the apparatus
further including: [0274] an ejecting unit configured to eject the
active-energy-ray-curable composition or the
active-energy-ray-curable ink. [0275] <12> A method for
forming a two-dimensional or three-dimensional image, the method
including [0276] irradiating the active-energy-ray-curable
composition according to any one of <1> to <6> or the
active-energy-ray-curable ink according to <7> or <8>
with active energy rays. [0277] <13> The method for forming
the two-dimensional or three-dimensional image according to
<12>, the method further including; [0278] ejecting the
active-energy-ray-curable composition or the
active-energy-ray-curable ink. [0279] <14> The method for
forming the two-dimensional or three-dimensional image according to
<12> or <13>, [0280] wherein the active energy rays
include light of a light-emitting diode. [0281] <15> A
two-dimensional or three-dimensional image, which is obtained
through curing by irradiating the active-energy-ray-curable
composition according to any one of <1> to <6> or the
active-energy-ray-curable ink according to <7> or <8>
with active energy rays. [0282] <16> A structure including:
[0283] a base; and [0284] the two-dimensional or three-dimensional
image according to <15> on the base. [0285] <17> A
processed product, which is obtained by drawing the two-dimensional
or three-dimensional image according to <15>, or the
structure according to <16>.
[0286] The active-energy-ray-curable composition according to any
one of <1> to <6>, the active-energy-ray-curable ink
according to <7> or <8>, the composition stored
container according to <9>, the apparatus for forming the
dimensional or three-dimensional image according to <10> or
<11>, the method for forming the dimensional or
three-dimensional image is according to any one of <12> to
<14>, the two-dimensional or three-dimensional image
according to <15>, the structure according to <16>, and
the processed product according to <17> can solve the
existing problems and can achieve the object of the present
disclosure.
* * * * *