U.S. patent application number 17/669711 was filed with the patent office on 2022-05-26 for photosensitive coloring composition, cured film, color filter, solid-state imaging element, and image display device.
This patent application is currently assigned to FUJIFILM Corporation. The applicant listed for this patent is FUJIFILM Corporation. Invention is credited to Shoichi NAKAMURA.
Application Number | 20220163885 17/669711 |
Document ID | / |
Family ID | 1000006135864 |
Filed Date | 2022-05-26 |
United States Patent
Application |
20220163885 |
Kind Code |
A1 |
NAKAMURA; Shoichi |
May 26, 2022 |
PHOTOSENSITIVE COLORING COMPOSITION, CURED FILM, COLOR FILTER,
SOLID-STATE IMAGING ELEMENT, AND IMAGE DISPLAY DEVICE
Abstract
A photosensitive coloring composition includes a magenta pigment
having an average primary particle diameter of 50 nm or less, a
polymerizable compound, a photopolymerization initiator, and an
ultraviolet absorber, in which the magenta pigment has a maximum
absorption wavelength in a range of 500 to 600 nm, the magenta
pigment is Color Index Pigment Violet 19, and in a case where an
absorbance of the maximum absorption wavelength is 1, a wavelength
at which an absorbance is 0.5 is 450 nm or more on a side where a
wavelength is shorter than the maximum absorption wavelength and is
650 nm or less on a side where a wavelength is longer than the
maximum absorption wavelength.
Inventors: |
NAKAMURA; Shoichi;
(Haibara-gun, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
FUJIFILM Corporation |
Tokyo |
|
JP |
|
|
Assignee: |
FUJIFILM Corporation
Tokyo
JP
|
Family ID: |
1000006135864 |
Appl. No.: |
17/669711 |
Filed: |
February 11, 2022 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16504745 |
Jul 8, 2019 |
11287739 |
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17669711 |
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PCT/JP2018/005367 |
Feb 16, 2018 |
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16504745 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09B 48/00 20130101;
C09B 19/00 20130101; C08F 2/44 20130101; G03F 7/0007 20130101; G03F
7/004 20130101; G02B 5/223 20130101 |
International
Class: |
G03F 7/00 20060101
G03F007/00; G03F 7/004 20060101 G03F007/004; C09B 48/00 20060101
C09B048/00; C09B 19/00 20060101 C09B019/00; G02B 5/22 20060101
G02B005/22 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 24, 2017 |
JP |
2017-059846 |
Feb 2, 2018 |
JP |
2018-017285 |
Claims
1. A photosensitive coloring composition comprising: a magenta
pigment having an average primary particle diameter of 50 nm or
less; a polymerizable compound; a photopolymerization initiator;
and an ultraviolet absorber, wherein the magenta pigment has a
maximum absorption wavelength in a range of 500 to 600 nm, the
magenta pigment is Color Index Pigment Violet 19, and in a case
where an absorbance of the maximum absorption wavelength is 1, a
wavelength at which an absorbance is 0.5 is 450 nm or more on a
side where a wavelength is shorter than the maximum absorption
wavelength, and is 650 nm or less on a side where a wavelength is
longer than the maximum absorption wavelength.
2. The photosensitive coloring composition according to claim 1,
wherein in the case where the absorbance of the maximum absorption
wavelength is 1, the magenta pigment has a difference of 130 nm or
less between the wavelengths at which the absorbance is 0.5 on the
side where a wavelength is longer than the maximum absorption
wavelength and on the side where a wavelength is shorter than the
maximum absorption wavelength.
3. The photosensitive coloring composition according to claim 1,
wherein a content of the ultraviolet absorber is 1% to 20% by mass
with respect to the total solid content of the photosensitive
coloring composition.
4. The photosensitive coloring composition according to claim 1,
wherein the photosensitive coloring composition contains 10 to 500
parts by mass of the ultraviolet absorber with respect to 100 parts
by mass of the photopolymerization initiator.
5. The photosensitive coloring composition according to claim 1,
wherein the photosensitive coloring composition contains 1 to 40
parts by mass of the ultraviolet absorber with respect to 100 parts
by mass of the magenta pigment.
6. The photosensitive coloring composition according to claim 1,
further comprising a resin having an amine value.
7. The photosensitive coloring composition according to claim 6,
wherein the resin having an amine value is a resin having a
nitrogen atom in a main chain.
8. The photosensitive coloring composition according to claim 6,
wherein the resin having an amine value is a resin having an acid
value and an amine value, and the acid value is 30 mgKOH/g or
more.
9. The photosensitive coloring composition according to claim 1,
further comprising a resin having an acid value of 50 mgKOH/g or
more.
10. The photosensitive coloring composition according to claim 1,
further comprising a resin having an acid value of 80 mgKOH/g or
more.
11. The photosensitive coloring composition according to claim 1,
further comprising an alkali-soluble resin having a polymerizable
group.
12. The photosensitive coloring composition according to claim 1,
wherein the ultraviolet absorber includes at least one compound
selected from the group consisting of a conjugated diene compound,
a methyldiebenzoyl compound, a coumarin compound, a salicylate
compound, a benzophenone compound, a benzotriazole compound, an
acrylonitrile compound, a triazine compound, and a benzodithiazole
compound.
13. The photosensitive coloring composition according to claim 1,
wherein the ultraviolet absorber includes at least one compound
selected from the group consisting of a benzophenone compound and a
benzotriazole compound.
14. The photosensitive coloring composition according to claim 1,
which is used for forming a magenta coloring pixel in a color
filter.
15. A cured film obtained from the photosensitive coloring
composition according to claim 1.
16. A color filter comprising the cured film according to claim
15.
17. A color filter comprising a magenta coloring pixel obtained
from the photosensitive coloring composition according to claim 1,
a cyan coloring pixel, and a yellow coloring pixel.
18. A solid-state imaging element comprising the color filter
according to claim 16.
19. An image display device comprising the color filter according
to claim 16.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of U.S. application Ser.
No. 16/504,745 filed on Jul. 8, 2019, which is a Continuation of
PCT International Application No. PCT/JP2018/005367, filed on Feb.
16, 2018, which claims priority under 35 U.S.C. .sctn. 119(a) to
Japanese Patent Application No. 2017-059846, filed on Mar. 24, 2017
and Japanese Patent Application No. 2018-017285, filed on Feb. 2,
2018. Each of the above application(s) is hereby expressly
incorporated by reference, in its entirety, into the present
application.
BACKGROUND OF THE INVENTION
1. Field of the Invention
[0002] The present invention relates to a photosensitive coloring
composition. The present invention further relates to a cured film,
a color filter, a solid-state imaging element, and an image display
device, each of which uses the photosensitive coloring
composition.
2. Description of the Related Art
[0003] In recent years, as a digital camera, a mobile phone with a
camera, and the like have been further spreading, there has been a
greatly increasing demand for a solid-state imaging element such as
a charge coupled device (CCD) image sensor. A color filter has been
used as a key device in a display or an optical element.
[0004] A color filter has been produced using a coloring
composition including a chromatic color pigment, a polymerizable
compound, and a photopolymerization initiator (for example, see
JP2015-106027A). In addition, a magenta color filter including
Color Index Pigment Red 122 as a magenta pigment is described in
JP2006-098684A.
[0005] In JP2013-254047A, it is described that a transparent pixel
for a color filter is formed by using a radiation sensitive
composition which includes a predetermined polymer, a polymerizable
compound including an acid group and a bi- or higher (meth)acrylate
compound, a polymerization initiator, an ultraviolet absorber, a
solvent, an adhesion enhancing agent, a polymerization inhibitor,
and a surfactant. In paragraph No. 0171 of JP2013-254047A, it is
described that the radiation sensitive composition described in
JP2013-254047A preferably does not contain a colorant.
SUMMARY OF THE INVENTION
[0006] In a color filter, refining of a pattern size is being
progressed. By reducing an average primary particle diameter of a
pigment to be used, linearity of the pattern is improved. However,
developability is reduced due to the refining of the pigment and
therefore a development residue between the patterns tends to
easily generate. In particular, since a magenta pigment has high
transparency to light used for exposure such as i-rays, in a case
where a photosensitive coloring composition including the magenta
pigment, a polymerizable compound, and a photopolymerization
initiator is exposed through a mask, an unexposed portion of the
mask circumference is easily exposed by reflected light or
scattered light from a support or the like and the development
residue tends to easily generate. As a result, in a photosensitive
coloring composition, further improvements in photolithographic
properties are desired.
[0007] In addition, according to the studies conducted by the
present inventors regarding the coloring photosensitive composition
including the magenta pigment, it was found that a mixed color
between adjacent pixels of other hues tends to easily occur in a
case of forming a pattern (pixel) by photolithography using the
photosensitive coloring composition.
[0008] Therefore, an object of the present invention is to provide
a photosensitive coloring composition which has excellent
photolithographic properties and is capable of suppressing an
occurrence of mixed color between adjacent pixels of other hues.
The object of the present invention is also to provide a cured
film, a color filter, a solid-state imaging element, and an image
display device, each of which uses the photosensitive coloring
composition.
[0009] According to the studies conducted by the present inventors,
it was found that the above object can be achieved by using a
photosensitive coloring composition as described later, thereby
leading to completion of the present invention. The present
invention provides the following aspects.
[0010] <1> A photosensitive coloring composition
comprising:
[0011] a magenta pigment having an average primary particle
diameter of 50 nm or less;
[0012] a polymerizable compound;
[0013] a photopolymerization initiator; and
[0014] an ultraviolet absorber,
[0015] in which the magenta pigment has a maximum absorption
wavelength in a range of 500 to 600 nm, and
[0016] in a case where an absorbance of the maximum absorption
wavelength is 1, a wavelength at which an absorbance is 0.5 is 450
nm or more on a side where a wavelength is shorter than the maximum
absorption wavelength, and is 650 nm or less on a side where the
wavelength is longer than the maximum absorption wavelength.
[0017] <2> The photosensitive coloring composition according
to <1>,
[0018] in which the magenta pigment is a compound having a coloring
agent skeleton selected from a quinacridone skeleton and a
dioxazine skeleton.
[0019] <3> The photosensitive coloring composition according
to <1> or <2>,
[0020] in which, in the case where the absorbance of the maximum
absorption wavelength is 1, the magenta pigment has a difference of
130 nm or less between the wavelengths at which the absorbance is
0.5 on the side where the wavelength is longer than the maximum
absorption wavelength and on the side where the wavelength is
shorter than the maximum absorption wavelength.
[0021] <4> The photosensitive coloring composition according
to any one of <1> to <3>,
[0022] in which a content of the ultraviolet absorber is 1% to 20%
by mass with respect to the total solid content of the
photosensitive coloring composition.
[0023] <5> The photosensitive coloring composition according
to any one of <1> to <4>,
[0024] in which the photosensitive coloring composition contains 10
to 500 parts by mass of the ultraviolet absorber with respect to
100 parts by mass of the photopolymerization initiator.
[0025] <6> The photosensitive coloring composition according
to any one of <1> to <5>,
[0026] in which the photosensitive coloring composition contains 1
to 40 parts by mass of the ultraviolet absorber with respect to 100
parts by mass of the magenta pigment.
[0027] <7> The photosensitive coloring composition according
to any one of <1> to <6>, further comprising a resin
having an amine value.
[0028] <8> The photosensitive coloring composition according
to <7>,
[0029] in which the resin having an amine value is a resin having a
nitrogen atom in a main chain.
[0030] <9> The photosensitive coloring composition according
to <7> or <8>,
[0031] in which the resin having an amine value is a resin having
an acid value and an amine value, and
[0032] the acid value is 30 mgKOH/g or more.
[0033] <10> The photosensitive coloring composition according
to any one of <1> to <7>, further comprising a resin
having an acid value of 50 mgKOH/g or more.
[0034] <11> The photosensitive coloring composition according
to any one of <1> to <7>, further comprising a resin
having an acid value of 80 mgKOH/g or more.
[0035] <12> The photosensitive coloring composition according
to any one of <1> to <11>, further comprising an
alkali-soluble resin having a polymerizable group.
[0036] <13> The photosensitive coloring composition according
to any one of <1> to <12>,
[0037] in which the magenta pigment is at least one pigment
selected from Color Index Pigment Red 122, Color Index Pigment Red
202, Color Index Pigment Red 209, Color Index Pigment Red 269,
Color Index Pigment Violet 19, or Color Index Pigment Violet
23.
[0038] <14> The photosensitive coloring composition according
to any one of <1> to <13>, which is used for forming a
magenta coloring pixel in a color filter.
[0039] <15> A cured film obtained from the photosensitive
coloring composition as described in any one of <1> to
<14>.
[0040] <16> A color filter comprising the cured film as
described in <15>.
[0041] <17> A color filter comprising a magenta coloring
pixel obtained from the photosensitive coloring composition
according to any one of <1> to <14>, a cyan coloring
pixel, and a yellow coloring pixel.
[0042] <18> A solid-state imaging element comprising the
color filter as described in <16> or <17>.
[0043] <19> An image display device comprising the color
filter as described in <16> or <17>.
[0044] According to the present invention, it is possible to
provide a photosensitive coloring composition which has excellent
photolithographic properties and is capable of suppressing the
occurrence of mixed color between adjacent pixels of other hues. It
is also possible to provide a cured film, a color filter, a
solid-state imaging element, and an image display device, each of
which uses the photosensitive coloring composition.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0045] Hereinafter, the contents of the present invention will be
described in detail.
[0046] In citations for a group (atomic group) in the present
specification, in a case where the group is denoted without
specifying whether it is substituted or unsubstituted, the group
includes both a group having no substituent and a group having a
substituent. For example, an "alkyl group" includes not only an
alkyl group having no substituent (unsubstituted alkyl group), but
also an alkyl group having a substituent (substituted alkyl
group).
[0047] In the present specification, "exposure" includes, unless
otherwise specified, not only exposure using light but also
lithography using particle rays such as electron beams and ion
beams. In addition, examples of light used for the exposure
generally include actinic rays or radiation such as a bright line
spectrum of a mercury lamp, far ultraviolet rays typified by an
excimer laser, extreme ultraviolet rays (EUV light), X-rays,
electron beams, or the like.
[0048] In the present specification, a numerical range expressed
using "to" means a range that includes the preceding and succeeding
numerical values of "to" as the lower limit value and the upper
limit value, respectively.
[0049] In the present specification, the total solid content refers
to a total amount of the components other than a solvent from all
the components of a composition.
[0050] In the present specification, "(meth)acrylate" represents
either or both of acrylate and methacrylate, "(meth)acryl"
represents either or both of acryl and methacryl, "(meth)allyl"
represents either or both of allyl and methallyl, and
"(meth)acryloyl" represents either or both of acryloyl and
methacryloyl.
[0051] In the present specification, a term "step" not only means
an independent step, but also includes a step which is not clearly
distinguished from other steps in a case where an intended action
of the step is obtained.
[0052] In the present specification, a weight-average molecular
weight (Mw) and a number-average molecular weight (Mn) are each
defined as a value in terms of polystyrene through measurement by
means of gel permeation chromatography (GPC).
[0053] <Photosensitive Coloring Composition>
[0054] A photosensitive coloring composition of an embodiment of
the present invention (hereinafter also referred to as a coloring
composition) includes a magenta pigment having an average primary
particle diameter of 50 nm or less, a polymerizable compound, a
photopolymerization initiator, and an ultraviolet absorber, in
which the magenta pigment has a maximum absorption wavelength in a
range of 500 to 600 nm, and in a case where an absorbance of the
maximum absorption wavelength is 1, a wavelength at which an
absorbance is 0.5 is 450 nm or more on a side where the wavelength
is shorter than the maximum absorption wavelength, and is 650 nm or
less on a side where the wavelength is longer than the maximum
absorption wavelength.
[0055] The magenta pigment included in the coloring composition of
an embodiment of the present invention has the average primary
particle diameter of 50 nm or less. Therefore the magenta pigment
can form a pattern excellent in linearity. In addition, as
described above, since the magenta pigment has high transparency to
light used for exposure such as i-rays, in the related art, in a
case where a coloring composition including the magenta pigment, a
polymerizable compound, and a photopolymerization initiator is
exposed through a mask, an unexposed portion of the mask
circumference is easily exposed by reflected light or scattered
light from a support or the like and the development residue
between patterns tends to easily generate. However, since the
coloring composition of the embodiment of the present invention
further includes the ultraviolet absorber, the reflected light or
the scattered light in the unexposed portion of the mask
circumference can be absorbed, and as a result, the generation of
the development residue can be effectively suppressed. Accordingly,
the coloring composition of the embodiment of the present invention
has excellent photolithographic properties.
[0056] In addition, since the coloring composition of the
embodiment of the present invention can suppress the generation of
the development residue between the patterns as described above, in
a case where a pixel of other hues is formed next to a pixel
(pattern) formed by using the coloring composition of the
embodiment of the present invention, mixed color between the pixel
formed by using the coloring composition of the embodiment of the
present invention and the pixel of other hues can be suppressed. In
addition, since a pixel formed by using the coloring composition
including the magenta pigment has high transparency to the light
used for the exposure such as i-rays, in the related art, a
development residue of other coloring pixels occurs on the pixel
(hereinafter also referred to as magenta coloring pixel) formed by
using the coloring composition including the magenta pigment and
the magenta coloring pixel is mixed with the development residue of
the other coloring pixels. However, since the coloring composition
of the embodiment of the present invention includes the ultraviolet
absorber, the pixel itself formed by using the coloring composition
of the embodiment of the present invention also has low
transparency to the light used for the exposure such as i-rays. As
a result, the development residue of the other coloring pixels
hardly occurs on the pixel formed by using the coloring composition
of the embodiment of the present invention and the pixel formed by
using the coloring composition of the embodiment of the present
invention can be suppressed from mixing color with the other
coloring pixels.
[0057] The coloring composition of the embodiment of the present
invention can also form a cured film excellent in light resistance.
The reason is presumed that the coloring composition of the
embodiment of the present invention has low transparency to
ultraviolet rays including i-rays so that the energy given to the
cured film at light irradiation is low.
[0058] The coloring composition of the embodiment of the present
invention can be preferably used as a coloring composition for
forming the magenta coloring pixel in a color filter.
[0059] The coloring composition of the embodiment of the present
invention preferably has a maximum absorption wavelength in a range
of 500 to 600 nm. In addition, in the coloring composition of the
embodiment of the present invention, in a case where an absorbance
of the maximum absorption wavelength in the range of 500 to 600 nm
is 1, a wavelength at which an absorbance is 0.5 is preferably 450
nm or more, more preferably 460 nm or more, and still more
preferably 470 nm or more on a side where the wavelength is shorter
than the maximum absorption wavelength. In addition, in the case
where the absorbance of the maximum absorption wavelength in the
range of 500 to 600 nm is 1, the wavelength at which the absorbance
is 0.5 is preferably 650 nm or less, more preferably 640 nm or
less, still more preferably 630 nm or less, and particularly
preferably 620 nm or less on a side where the wavelength is longer
than the maximum absorption wavelength. Hereinafter, in the case
where the absorbance of the maximum absorption wavelength is 1, the
wavelength at which the absorbance is 0.5 on the side where the
wavelength is shorter than the maximum absorption wavelength also
refers to as wavelength .lamda.1. In addition, in the case where
the absorbance of the maximum absorption wavelength is 1, the
wavelength at which the absorbance is 0.5 on the side where the
wavelength is longer than the maximum absorption wavelength also
refers to as wavelength .lamda.2.
[0060] In addition, a difference between the maximum absorption
wavelength and the wavelength .lamda.1 is preferably 110 nm or
less, more preferably 100 nm or less, and still more preferably 90
nm or less. In addition, a difference between the wavelength
.lamda.2 and the maximum absorption wavelength is preferably 110 nm
or less, more preferably 100 nm or less, and still more preferably
90 nm or less. In addition, in the coloring composition of the
embodiment of the present invention, a difference between the
wavelength .lamda.2 and the wavelength .lamda.1 (.lamda.2-.lamda.1)
is preferably 130 nm or less, more preferably 120 nm or less, still
more preferably 115 nm or less, and particularly preferably 110 nm
or less. A coloring composition having such spectral
characteristics is preferably used for forming the magenta coloring
pixel. Hereinafter, the respective components used for the coloring
composition of the embodiment of the present invention will be
described.
[0061] Magenta Pigment
[0062] The coloring composition of the embodiment of the present
invention includes a magenta pigment having a maximum absorption
wavelength in a range of 500 to 600 nm. The maximum absorption
wavelength of the magenta pigment can be measured by a method of
forming a film by using a composition including the magenta pigment
and a resin to measure spectral characteristics of the film by
using a spectrophotometer, or a method of preparing a dispersion
liquid containing only the magenta pigment to measure spectral
characteristics of the pigment dispersion liquid by using the
spectrophotometer.
[0063] The maximum absorption wavelength of the magenta pigment is
preferably in a range of 500 to 590 nm, more preferably in a range
of 500 to 585 nm, and still more preferably in a range of 500 to
580 nm.
[0064] In addition, in the magenta pigment used in the present
invention, in a case where an absorbance of the maximum absorption
wavelength in a range of 500 to 600 nm is 1, a wavelength at which
an absorbance is 0.5 is 450 nm or more, preferably 460 nm or more,
and more preferably 470 nm or more on the side where the wavelength
is shorter than the maximum absorption wavelength. In addition, in
the magenta pigment used in the present invention, in the case
where an absorbance of the maximum absorption wavelength in the
range of 500 to 600 nm is 1, a wavelength at which the absorbance
is 0.5 is 650 nm or less, preferably 640 nm or less, more
preferably 630 nm or less, and still more preferably 620 nm or less
on the side where the wavelength is longer than the maximum
absorption wavelength. In addition, in the magenta pigment used in
the present invention, a difference between the maximum absorption
wavelength and the wavelength .lamda.1 is preferably 110 nm or
less, more preferably 100 nm or less, and still more preferably 90
nm or less. In addition, a difference between the wavelength
.lamda.2 and the maximum absorption wavelength is preferably 110 nm
or less, more preferably 100 nm or less, and still more preferably
90 nm or less. In addition, in the magenta pigment used in the
present invention, a difference between the wavelength .lamda.2 and
the wavelength .lamda.1 (.lamda.2-.lamda.1) is preferably 130 nm or
less, more preferably 120 nm or less, still more preferably 115 nm
or less, and particularly preferably 110 nm or less.
[0065] The magenta pigment used in the present invention is
preferably a compound having a coloring agent skeleton selected
from a quinacridone skeleton, a dioxazine skeleton, and a naphthol
azo skeleton, more preferably a compound having a coloring agent
skeleton selected from the quinacridone skeleton and the dioxazine
skeleton, and still more preferably a compound having the
quinacridone skeleton as a coloring agent skeleton for a reason of
spectral performance and stability.
[0066] Specific examples of the magenta pigment used in the present
invention include Color Index (C. I.) Pigment Red 122, C. I.
Pigment Red 202, C. I. Pigment Red 209, C. I. Pigment Red 269, C.
I. Pigment Violet 19, and C. I. Pigment Violet 23. Among these, C.
I. Pigment Red 122, C. I. Pigment Red 202, C. I. Pigment Red 209,
and C. I. Pigment Violet 19 are compounds having the quinacridone
skeleton, C. I. Pigment Violet 23 is a compound having the
dioxazine skeleton, and C. I. Pigment Red 269 is a compound having
the naphthol azo skeleton.
[0067] An average primary particle diameter of the magenta pigment
used in the present invention is 50 nm or less, preferably 47 nm or
less, and still more preferably 45 nm or less. The lower limit is
not particularly limited, but is preferably 20 nm or more. In a
case where the average primary particle diameter of the magenta
pigment is 50 nm or less, a refined pattern excellent in linearity
can be formed. In addition, in the related art, in a case of using
a small average primary particle diameter of the magenta pigment,
developability is reduced and therefore the development residue
between patterns tends to easily generate. However, according to
the present invention, the generation of the development residue
between patterns can be effectively suppressed even though the
average primary particle diameter of the magenta pigment is small.
Therefore, the effect of the present invention is remarkable in a
case of using a magenta pigment having a smaller average primary
particle diameter. Furthermore, in the present specification, an
average primary particle diameter of a pigment refers to a
number-average particle diameter determined from an image obtained
by observing the pigment by using a transmission electron
microscope (for example, a device in accordance with a field
emission type transmission electron microscope manufactured by JEOL
Ltd., JEM-2100F Type). Specifically, a projected area of the
pigment is determined by the above-mentioned device, an equivalent
circle diameter of each pigment is determined therefrom, and then
the average primary particle diameter is calculated. More
specifically, equivalent circle diameters of 100 pigments are
measured, and then equivalent circle diameters are arithmetically
averaged for 80 pigments excluding 10 pigments from the largest
size and 10 pigments from the smallest size among the 100 pigments
to calculate the average primary particle diameter of the
pigment.
[0068] The magenta pigment having the average primary particle
diameter of 50 nm or less may be a commercially available product
or a magenta pigment which has an average primary particle diameter
of more than 50 nm and is subjected to a refining treatment. The
refining treatment method of the magenta pigment is not
particularly limited and can be performed using a known method in
the related art. Examples of the refining treatment method include
various milling methods such as a beads mill method or a salt
milling method, and the salt milling method is preferable for a
reason that primary particles can be efficiently refined.
[0069] The refining treatment in the salt milling method is
preferably performed by kneading the magenta pigment in the
presence of a water-soluble organic solvent and a water-soluble
inorganic salt. A blending amount of the water-soluble inorganic
salt is preferably 100 to 2,000 parts by mass and more preferably
500 to 2,000 parts by mass with respect to 100 parts by mass of the
magenta pigment. Examples of the water-soluble organic solvent
include alkylene glycol such as ethylene glycol and propylene
glycol, a condensate of alkylene glycol such as diethylene glycol,
triethylene glycol, dipropylene glycol, polyethylene glycol and
polyethylene-propylene glycol, alkyl ether of (poly)alkylene glycol
such as methoxy ethanol and polyethylene glycol monomethyl ether,
and glycerin. Examples of the water-soluble inorganic salt include
sodium chloride, potassium chloride, calcium chloride, sodium
sulfate, aluminum sulfate, and sodium hydrogen carbonate. A
kneading machine is not particularly limited as long as the machine
has a function capable of kneading the above-mentioned mixture. For
example, a double-arm type kneader, a flasher, a planetary mixer,
or the like can be used. The double-arm type kneader having a
strong shearing force for the refining is more preferable.
[0070] The temperature (milling temperature) at which the
above-mentioned mixture is kneaded is preferably 30.degree. C. to
150.degree. C. and more preferably 80.degree. C. to 100.degree. C.
In addition, the time (milling time) when the above-mentioned
mixture is kneaded is preferably 5 to 20 hours and more preferably
8 to 18 hours.
[0071] After kneading the mixture, the water-soluble organic
solvent and the water-soluble inorganic salt are removed from the
mixture. As necessary, a refined magenta pigment can be obtained by
performing a washing, a filtration, a drying, a pulverization, or
the like.
[0072] In the coloring composition of the embodiment of the present
invention, a content of the magenta pigment is preferably 20% to
80% by mass with respect to the total solid content of the coloring
composition. The upper limit is preferably 75% by mass or less and
more preferably 70% by mass or less. The lower limit is preferably
25% by mass or more and more preferably 30% by mass or more. The
magenta pigment may be of one kind or two or more kinds thereof. In
a case where two or more kinds of the magenta pigments are
included, the total amount thereof is preferably within the
above-mentioned range.
[0073] Other Colorants
[0074] The coloring composition of the embodiment of the present
invention can further use a colorant (other colorants) other than
the magenta pigment. Other colorants may be either a dye or a
pigment, or used in combination thereof. Examples of the pigment
include various inorganic pigments or organic pigments known in the
related art. In addition, in consideration of either the inorganic
pigment or organic pigment preferably having high transmittance, it
is preferable that a pigment having an average particle diameter as
small as possible is used. Furthermore, in consideration of
handleability, the average primary particle diameter of the
above-mentioned pigment is preferably 0.01 to 0.1 .mu.m and more
preferably 0.01 to 0.05 .mu.m.
[0075] Examples of the inorganic pigment include metal compounds
such as a metal oxide and a metal complex salt. In addition,
examples of the inorganic pigment include black pigments such as
carbon black and titanium black, oxides of metals such as iron,
cobalt, aluminum, cadmium, lead, copper, titanium, magnesium,
chromium, zinc, and antimony, and multiple oxides of the
above-mentioned metals.
[0076] Examples of the organic pigment include the following
organic pigments.
[0077] C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14,
15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1,
40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93,
94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115,
116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138,
147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166,
167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180,
181, 182, 187, 188, 193, 194, 199, 213, 214
[0078] C. I. Pigment Green 7, 10, 36, 37
[0079] C. I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43,
46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73
[0080] C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22,
23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2,
53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105,
112, 119, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171,
172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 206,
207, 208, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270,
272, 279
[0081] C. I. Pigment Violet 1, 27, 32, 37, 42
[0082] C. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6,
16, 22, 60, 64, 66, 79, 80
[0083] In addition, an aluminum phthalocyanine compound having a
phosphorus atom can also be used as the blue pigment. Specific
examples thereof include the compounds described in paragraph Nos.
0022 to 0030 of JP2012-247591A and paragraphs 0047 of
JP2011-157478A.
[0084] As the dye, for example, a coloring agent disclosed in
JP1989-090403A (JP-S64-090403A), JP1989-091102A (JP-S64-091102A),
JP1989-094301A (JP-H01-094301A), JP1994-011614A (JP-H06-011614A),
JP2592207B, U.S. Pat. Nos. 4,808,501A, 5,667,920A, JP1993-333207A
(JP-H05-333207A), JP1994-035183A (JP-H06-035183A), JP1994-051115A
(JP-H06-051115A), or JP1994-194828A (JP-H06-194828A) can be used.
In a case of being classified as chemical structures, pyrazolazo
compound, pyrromethene compound, anilinoazo compound,
triarylmethane compound, anthraquinone compound, benzylidene
compound, oxonol compound, pyrazolotriazolazo compound, pyridonazo
compound, cyanine compound, phenothiazine compound,
pyrrolopyrazolazomethine compound, or the like can be used.
[0085] A coloring agent multimer can also be used as other
colorants. The coloring agent multimer is preferably a dye that is
used after being dissolved in a solvent, but the coloring agent
multimer may form a particle. In a case where the coloring agent
multimer forms a particle, the coloring agent multimer is dispersed
in a solvent or the like and then used. The coloring agent multimer
in a particle state can be obtained by, for example, an emulsion
polymerization. Examples of the coloring agent multimer in the
particle state include compounds described in JP2015-214682A. In
addition, as the coloring agent multimer, the compounds described
in JP2011-213925A, JP2013-041097A, JP2015-028144A, JP2015-030742A,
or the like can also be used.
[0086] Furthermore, as other colorants, the quinophthalone
compounds described in paragraph Nos. 0011 to 0034 of
JP2013-054339A, the quinophthalone compounds described in
paragraphs 0013 to 0058 of JP2014-026228A, or the like can be
used.
[0087] In the case of forming the magenta coloring pixel using the
coloring composition of the embodiment of the present invention, it
is preferable that other colorants are not substantially contained.
In the present invention, the case where the coloring composition
does not substantially contain other colorants means that the
coloring composition does not contain other colorants or formed
pixels contain other colorants only to an extent in which the
formed pixels are practically recognized as magenta color. For
example, the content of other colorants is preferably 10 parts by
mass, more preferably 0.5 parts by mass, and still more preferably
0.1 parts by mass with respect to 100 parts by mass of the magenta
pigment, and the coloring composition is even still more preferably
not to contain other colorants.
[0088] In a case where the coloring composition of the embodiment
of the present invention contains other colorants, the kind of
other colorants may be one or two or more. In a case of including
two or more kinds of other colorants, the total amount thereof is
preferably within the range.
[0089] Polymerizable Compound
[0090] The coloring composition of the embodiment of the present
invention contains a polymerizable compound. Known compounds which
can be crosslinked by radical, acid, or heat can be used as the
polymerizable compound. In the present invention, the polymerizable
compound is preferably, for example, a compound having an
ethylenically unsaturated bonding group. Examples of the group
having an ethylenically unsaturated bonding group include a vinyl
group, a (meth)allyl group, and a (meth)acryloyl group. The
polymerizable compound used in the present invention is preferably
a radical polymerizable compound.
[0091] Any chemical forms of a monomer, a prepolymer, an oligomer,
or the like may be used as the polymerizable compound, but the
monomer is preferable. A molecular weight of the polymerizable
compound is preferably 100 to 3,000. The upper limit is more
preferably 2,000 or less and still more preferably 1,500 or less.
The lower limit is more preferably 150 or more and still more
preferably 250 or more.
[0092] The polymerizable compound is preferably a compound
including three or more ethylenically unsaturated bonding groups,
more preferably a compound including 3 to 15 ethylenically
unsaturated bonding groups, and still more preferably a compound
having 3 to 6 ethylenically unsaturated bonding groups. In
addition, the polymerizable compound is preferably a trifunctional
to pentadecafunctional (meth)acrylate compound and more preferably
a trifunctional to hexafunctional (meth)acrylate compound. Specific
examples of the polymerizable compound include compounds described
in paragraph Nos. 0095 to 0108 of JP2009-288705A, paragraph No.
0227 of JP2013-029760A, and paragraph Nos. 0254 to 0257 of
JP2008-292970A, and the contents of which are incorporated herein
by reference.
[0093] The polymerizable compound is preferably a compound such as
dipentaerythritol triacrylate (as a commercially available product,
KAYARAD D-330 manufactured by Nippon Kayaku Co., Ltd.);
dipentaerythritol tetraacrylate (as a commercially available
product, KAYARAD D-320 manufactured by Nippon Kayaku Co., Ltd.);
dipentaerythritol penta(meth)acrylate (as a commercially available
product, KAYARAD D-310 manufactured by Nippon Kayaku Co., Ltd.);
dipentaerythritol hexa(meth)acrylate (as a commercially available
product, KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., NK
ESTER A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.);
and a compound having a structure in which the (meth)acryloyl group
is bonded through an ethylene glycol and/or a propylene glycol
residue (for example, SR454 and SR499 which are commercially
available products from Sartomer). Oligomers of the above-described
examples can also be used. As the polymerizable compound, NK ESTER
A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) and
KAYARAD RP-1040 and DPCA-20 (manufactured by Nippon Kayaku Co.,
Ltd.) can also be used. In addition, as the polymerizable compound,
it is preferable to use a trifunctional (meth)acrylate compound
such as trimethylolpropane tri(meth)acrylate, trimethylolpropane
propyleneoxide-modified tri(meth)acrylate, trimethylolpropane
ethyleneoxide-modified tri(meth)acrylate, isocyanuric acid
ethyleneoxide-modified tri(meth)acrylate, and pentaerythritol
tri(meth)acrylate. Examples of a commercially available product of
the trifunctional (meth)acrylate compound include ARONIX M-309,
M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303,
M-452, and M-450 (manufactured by TOAGOSEI CO., LTD.), NK ESTER
A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT,
and TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd), and
KAYARAD GPO-303, TMPTA, THE-330, TPA-330, and PET-30 (manufactured
by Nippon Kayaku Co., Ltd.).
[0094] The polymerizable compound may have an acid group. By using
a polymerizable compound having an acid group, the polymerizable
compound in an unexposed portion is easily removed in development
and the generation of the development residue can be suppressed.
Examples of an acid group include a carboxyl group, a sulfo group,
and a phosphoric acid group, and a carboxyl group is preferable.
Examples of a commercially available product of the polymerizable
compound having an acid group include ARONIX M-510, M-520, ARONIX
TO-2349 (manufactured by TOAGOSEI CO., LTD.).
[0095] An acid value of the polymerizable compound having an acid
group is preferably 0.1 to 40 mgKOH/g and more preferably 5 to 30
mgKOH/g. In a case where an acid value of the polymerizable
compound is 0.1 mgKOH/g or more, solubility in a developer is good,
and in a case where an acid value of the polymerizable compound is
40 mgKOH/g or less, it is advantageous in production and
handling.
[0096] A polymerizable compound having a caprolactone structure can
also be used as the polymerizable compound. Examples of the
polymerizable compound having the caprolactone structure include
DPCA-20, DPCA-30, DPCA-60, and DPCA-120, each of which is
commercially available as KAYARAD DPCA series from Nippon Kayaku
Co., Ltd.
[0097] A polymerizable compound having an alkyleneoxy group can
also be used as the polymerizable compound. The polymerizable
compound having an alkyleneoxy group is preferably a polymerizable
compound having an ethyleneoxy group and/or a propyleneoxy group,
more preferably a polymerizable compound having an ethyleneoxy
group, and still more preferably a trifunctional to hexafunctional
(meth)acrylate compound having 4 to 20 ethyleneoxy groups. Examples
of a commercially available product of the polymerizable compound
having an alkyleneoxy group include SR-494 manufactured by
Sartomer, which is a tetrafunctional (meth)acrylate having four
ethyleneoxy groups, and KAYARAD TPA-330 manufactured by Nippon
Kayaku Co., Ltd., which is a trifunctional (meth)acrylate having
three isobutyleneoxy groups.
[0098] A polymerizable compound having a fluorene skeleton can also
be used as the polymerizable compound. Examples of a commercially
available product of the polymerizable compound having the fluorene
skeleton include OGSOL EA-0200, EA-0300 (manufactured by Osaka Gas
Chemicals Co., Ltd., (meth)acrylate monomer having a fluorene
skeleton), and the like.
[0099] The urethane acrylates described in JP1973-041708B
(JP-S48-041708B), JP1976-037193A (JP-S51-037193A), JP1990-032293B
(JP-H02-032293B), or JP1990-016765B (JP-H02-016765B), or the
urethane compounds having an ethylene oxide skeleton described in
JP1983-049860B (JP-S58-049860B), JP1981-017654B (JP-S56-017654B),
JP1987-039417B (JP-S62-039417B), or JP1987-039418B (JP-S62-039418B)
are also suitable as the polymerizable compound. In addition,
polymerizable compounds having an amino structure or a sulfide
structure in the molecule described in JP1988-277653A
(JP-S63-277653A), JP1988-260909A (JP-S63-260909A), or
JP1989-105238A (JP-H01-105238A) are preferably used. Examples of a
commercially available product include URETHANE OLIGOMER UAS-10 and
UAB-140 (manufactured by Sanyo-Kokusaku Pulp Co., Ltd.), UA-7200
(manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H
(manufactured by Nippon Kayaku Co., Ltd.), and UA-306H, UA-306T,
UA-3061, AH-600, T-600 and AI-600 (manufactured by Kyoeisha
Chemical Co., Ltd.).
[0100] The content of the polymerizable compound is preferably 0.1%
to 50% by mass with respect to the total solid content of the
coloring composition. The lower limit is more preferably 0.5% by
mass or more and still more preferably 1% by mass or more. The
upper limit is more preferably 45% by mass or less and still more
preferably 40% by mass or less. The polymerizable compound may be
used singly or in combination of two or more kinds thereof. In a
case where the polymerizable compounds are used in combination of
two or more kinds thereof, the total amount thereof is preferably
within the above-mentioned range.
[0101] Photopolymerization Initiator
[0102] The coloring composition of the embodiment of the present
invention contains a photopolymerization initiator. The
photopolymerization initiator is not particularly limited as long
as having an ability to initiate a polymerization of the
polymerizable compound and can be appropriately selected from known
photopolymerization initiators. For example, a compound having
photosensitivity to light in a range from the ultraviolet range to
the visible range is preferable. In addition, the
photopolymerization initiator may be a compound that produces an
active radical by causing some action with a photoexcited
sensitizer.
[0103] Examples of the photopolymerization initiator include
halogenated hydrocarbon derivatives (for example, a compound having
a triazine skeleton and a compound having an oxadiazole skeleton),
an acylphosphine compound, hexaaryl biimidazole, an oxime compound,
an organic peroxide, a thio compound, a ketone compound, an
aromatic onium salt, an .alpha.-hydroxyketone compound, and an
.alpha.-aminoketone compound. From the viewpoint of the exposure
sensitivity, as the photopolymerization initiator, a trihalomethyl
triazine compound, a benzyl dimethyl ketal compound, an
.alpha.-hydroxyketone compound, an .alpha.-aminoketone compound, an
acylphosphine compound, a phosphine oxide compound, a metallocene
compound, an oxime compound, a triarylimidazole dimer, an onium
compound, a benzothiazole compound, a benzophenone compound, an
acetophenone compound, a cyclopentadiene-benzene-iron complex, a
halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin
compound are preferable, a compound selected from an oxime
compound, the .alpha.-hydroxyketone compound, the
.alpha.-aminoketone compound, and an acylphosphine compound is more
preferable, and an oxime compound is still more preferable. With
regard to the photopolymerization initiator, reference can be made
to the description in paragraphs 0065 to 0111 of JP2014-130173A,
the contents of which are incorporated herein by reference.
[0104] Examples of a commercially available product of the
.alpha.-hydroxyketone compound include IRGACURE-184, DAROCUR-1173,
IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all manufactured by
BASF). Examples of a commercially available product of the
.alpha.-aminoketone compound include IRGACURE-907, IRGACURE-369,
IRGACURE-379, and IRGACURE-379EG (all manufactured by BASF).
Examples of a commercially available product of the acylphosphine
compound include IRGACURE-819 and DAROCUR-TPO (both manufactured by
BASF).
[0105] As the oxime compound, for example, the compounds described
in JP2001-233842A, the compounds described in JP2000-080068A. and
the compounds described in JP2006-342166A can be used. Specific
examples of the oxime compound include
3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one,
3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one,
2-acetoxyimino-1-phenylpropan-1-one,
2-benzoyloxyimino-1-phenylpropan-1-one,
3-(4-toluenesulfonyloxy)iminobutan-2-one, and
2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
[0106] As the oxime compound, the compounds described in J. C. S.
Perkin II (1979), pp. 1653 to 1660, J. C. S. Perkin II (1979), pp.
156 to 162, Journal of Photopolymer Science and Technology (1995),
pp. 202 to 232, each of the publications of JP2000-066385A,
JP2000-080068A, JP2004-534797A, and JP2006-342166A, or the like can
also be used. As a commercially available product of the oxime
compound, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and
IRGACURE-OXE04 (all manufactured by BASF) are also suitably used.
In addition, TRONLY TR-PBG-304, TRONLY TR-PBG-309, and TRONLY
TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC
MATERIALS CO., LTD.), or ADEKA ARKLS NCI-930 and ADEKA OPTOMER
N-1919 (all manufactured by ADEKA Corporation, a
photopolymerization initiator 2 described in JP2012-014052A) can
also be used.
[0107] Moreover, as oxime compounds other than the above-described
oxime compounds, the compounds described in JP2009-519904A in which
oxime is linked to N of a carbazole ring, the compounds described
in U.S. Pat. No. 7,626,957B in which a hetero-substituent is
introduced into a benzophenone moiety, the compounds described in
JP2010-015025A in which a nitro group is introduced into a coloring
agent site, the compounds described in US2009-0292039A, the
ketoxime compounds described in WO2009/131189A, the compounds
described in U.S. Pat. No. 7,556,910B, which contains a triazine
skeleton and an oxime skeleton in the same molecule, the compound
described in JP2009-221114A, which has a maximum absorption at 405
nm and has good sensitivity to a light source of g-rays, and the
like may be used. Preferably, reference can be made to, for
example, the descriptions in paragraph Nos. 0274 to 0306 of
JP2013-029760A, the contents of which are incorporated herein by
reference.
[0108] In the present invention, an oxime compound having a
fluorene ring can also be used as the photopolymerization
initiator. Specific examples of the oxime compound having a
fluorene ring include the compounds described in JP2014-137466A.
The contents of the publications are incorporated herein by
reference.
[0109] In the present invention, an oxime compound having a
benzofuran skeleton can also be used as the photopolymerization
initiator. Specific examples thereof include the compounds OE-01 to
OE-75 described in WO2015/036910A.
[0110] In the present invention, an oxime compound having a
fluorine atom can also be used as the photopolymerization
initiator. Specific examples of the oxime compound having a
fluorine atom include the compounds described in JP2010-262028A,
the compounds 24, and 36 to 40 described in JP2014-500852A, and the
compounds (C-3) described in JP2013-164471A. The contents of the
publications are incorporated herein by reference.
[0111] In the present invention, an oxime compound having a nitro
group can also be used as the photopolymerization initiator. The
oxime compound having a nitro group is also preferably used in the
form of a dimer. Specific examples of the oxime compound having a
nitro group include the compounds described in paragraph Nos. 0031
to 0047 of JP2013-114249A and paragraph Nos. 0008 to 0012 and 0070
to 0079 of JP2014-137466A, the compounds described in paragraph
Nos. 0007 to 0025 of JP4223071B, and ADEKA ARKLS NCI-831
(manufactured by ADEKA Corporation).
[0112] Specific examples of the oxime compound which is preferably
used in the present invention are shown below, but the present
invention is not limited thereto.
##STR00001## ##STR00002## ##STR00003##
[0113] As the oxime compound, the compound having a maximum
absorption wavelength in a range of 350 to 500 nm is preferable,
the compound having a maximum absorption wavelength in a range of
360 nm to 480 nm is more preferable. The oxime compound is
particularly preferably a compound showing a high absorbance at 365
nm and 405 nm.
[0114] From the viewpoint of sensitivity, the molar light
absorption coefficient at 365 nm or 405 nm of the oxime compound is
preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and
particularly preferably 5,000 to 200,000. The molar light
absorption coefficient of the compound can be measured using a
known method, but specifically, it is preferably measured, for
example, by means of an ultraviolet and visible light
spectrophotometer (Cary-5 spectrophotometer manufactured by Varian)
at a concentration of 0.01 g/L using an ethyl acetate solvent.
[0115] The content of the photopolymerization initiator is
preferably 0.1% to 50% by mass, more preferably 0.5% to 30% by
mass, and still more preferably 1% to 20% by mass, with respect to
the total solid content of the coloring composition. In a case
where the content of the photopolymerization initiator is within
the range, good sensitivity and good pattern forming properties are
obtained. The coloring composition of the embodiment of the present
invention may include only one kind or two or more kinds of the
photopolymerization initiators. In a case of including two or more
kinds of the photopolymerization initiators, the total amount
thereof is preferably within the above-mentioned range.
[0116] Ultraviolet Absorber
[0117] The coloring composition of the embodiment of the present
invention contains an ultraviolet absorber. The ultraviolet
absorber is preferably a compound having a maximum absorption
wavelength in a range of 300 to 400 nm and more preferably a
compound having a maximum absorption wavelength in a range of 320
to 380 nm. By using the compounds, the generation of the
development residue between the patterns can be effectively
suppressed. In addition, it is possible to form a pattern excellent
in rectangularity or linearity. Furthermore, it is possible to
effectively suppress the occurrence of mixed color between adjacent
pixels of other hues.
[0118] In the present invention, the molar light absorption
coefficient at 365 nm of the ultraviolet absorber is preferably
5,000 L.times.mol.sup.-1.times.cm.sup.-1 or more, more preferably
10,000 L.times.mol.sup.-1.times.cm.sup.-1 or more, and still more
preferably 30,000 L.times.mol.sup.-1.times.cm.sup.-1 or more. The
upper limit is preferably, for example, 100,000
L.times.mol.sup.-1.times.cm.sup.-1 or less. By using the compounds,
the generation of the development residue between the patterns can
be more effectively suppressed. Furthermore, it is possible to more
effectively suppress the occurrence of mixed color between adjacent
pixels of other hues.
[0119] As the ultraviolet absorber, a conjugated diene compound, a
methyldiebenzoyl compound, a coumarin compound, a salicylate
compound, a benzophenone compound, a benzotriazole compound, an
acrylonitrile compound, a triazine compound, a benzodithiazole
compound, or the like can be used. Among those, for the reason of
having high molar light absorption coefficient at 365 nm, a
conjugated diene compound, a methyldiebenzoyl compound, a
benzotriazole compound, a triazine compound, a benzophenone
compound, or a benzodithiazole compound is preferable, a conjugated
diene compound, a methyldiebenzoyl compound, or a triazine compound
is more preferable, a conjugated diene compound or a
methyldiebenzoyl compound is still more preferable, and a
conjugated diene compound is particularly preferable. In addition,
since the conjugated diene compound has high light-shielding of
i-rays and further has a function as a polymerization inhibitor,
the effects tend to be obtained more remarkably.
[0120] As the conjugated diene compound, a compound represented by
Formula (UV-1) is preferable.
##STR00004##
[0121] In Formula (UV-1), R.sup.1 and R.sup.2 each independently
represent a hydrogen atom, an alkyl group having 1 to 20 carbon
atoms, or an aryl group having 6 to 20 carbon atoms, and R.sup.1
and R.sup.2 may be the same as or different from each other, but
are not simultaneously a hydrogen atom.
[0122] R.sup.1 and R.sup.2 may form a cyclic amino group with a
nitrogen atom to which R.sup.1 and R.sup.2 are bonded. Examples of
the cyclic amino group include a piperidino group, a morpholino
group, a pyrrolidino group, a hexahydroazepino group and a
piperazino group.
[0123] R.sup.1 and R.sup.2 each independently preferably represent
an alkyl group having 1 to 20 carbon atoms, more preferably
represent an alkyl group having 1 to 10 carbon atoms, and still
more preferably represent an alkyl group having 1 to 5 carbon
atoms.
[0124] R.sup.3 and R.sup.4 represent an electron withdrawing group.
R.sup.3 and R.sup.4 are preferably an acyl group, a carbamoyl
group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano
group, a nitro group, an alkylsulfonyl group, an arylsulfonyl
group, a sulfonyloxy group, or a sulfamoyl group, and more
preferably an acyl group, a carbamoyl group, an alkyloxycarbonyl
group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl
group, an arylsulfonyl group, a sulfonyloxy group, or a sulfamoyl
group. In addition, R.sup.3 and R.sup.4 may be bonded to each other
to form a cyclic electron withdrawing group. An example of the
cyclic electron withdrawing group formed by R.sup.3 and R.sup.4
being bonded to each other includes a six-membered ring including 2
carbonyl groups.
[0125] At least one of the R.sup.1, R.sup.2, R.sup.3, or R.sup.4
may be a polymer form derived from a monomer bonded with a vinyl
group through a linking group. The polymer may be a copolymer of
another monomer.
[0126] With regard to the explanation of a substituent of the
ultraviolet absorber represented by Formula (UV-1), reference can
be made to the description in paragraph Nos. 0024 to 0033 of
WO2009/123109 (paragraph Nos. <0040> to <0059> of the
corresponding US2011/0039195A), and the contents thereof are
incorporated herein by reference. Specific examples of the
ultraviolet absorber represented by Formula (UV-1) include the
following compounds. In addition, with regard to the preferred
specific examples of the compounds represented by Formula (UV-1),
reference can be made to the description in paragraph Nos. 0034 to
0037 of WO2009/123109 (paragraph No. <0060> of the
corresponding US2011/0039195A) which describes example compounds
(1) to (14), and the contents thereof are incorporated herein by
reference. Examples of a commercially available product of the
ultraviolet absorber represented by Formula (UV-1) include UV503
(manufactured by Daito Chemical Co., Ltd.) or the like.
##STR00005##
[0127] As a methyl dibenzoyl compound, compounds represented by the
Formula (UV-2) are preferable.
##STR00006##
[0128] In Formula (UV-2), R.sup.101 and R.sup.102 each
independently represent a substituent, and m1 and m2 each
independently represent an integer of 0 to 5.
[0129] Examples of the substituent represented by R.sup.101 and
R.sup.102 include a halogen atom, a cyano group, a nitro group, an
alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an
aryloxy group, a heteroaryloxy group, an alkylthio group, an
arylthio group, a heteroarylthio group, --NR.sup.U1R.sup.U2,
--COR.sup.U3, --COOR.sup.U4, --OCOR.sup.U5, --NHCOR.sup.U6,
--CONR.sup.U7R.sup.U8, --NHCONR.sup.U9R.sup.U10, --NHCOOR.sup.U11,
--SO.sub.2R.sup.U12, --SO.sub.2OR.sup.U3, --NHSO.sub.2R.sup.U4 or
--SO.sub.2NR.sup.U15R.sup.U16. R.sup.U1 to R.sup.U16 each
independently represent a hydrogen atom, an alkyl group or an aryl
group having 1 to 8 carbon atoms.
[0130] Each of substituents represented by R.sup.101 and R.sup.102
is independently preferably an alkyl group or an alkoxy group. The
alkyl group preferably has 1 to 20 carbon atoms and more preferably
has 1 to 10 carbon atoms. The alkyl group may be any of linear,
branched, or cyclic forms, and is preferably linear or branched and
more preferably branched. The alkoxy group preferably has 1 to 20
carbon atoms and more preferably has 1 to 10 carbon atoms. The
alkoxy group is preferably linear or branched and more preferably
branched.
[0131] In Formula (UV-2), a combination in which one of the
R.sup.101 or R.sup.102 is an alkyl group and the other is an alkoxy
group is preferable.
[0132] m1 and m2 each independently represent an integer of 0 to 5.
Each of m1 and m2 is independently preferably 0 to 2, more
preferably 0 to 1, and particularly preferably 1.
[0133] Specific example of the compound represented by Formula
(UV-2) includes avobenzone.
[0134] Examples of benzotriazole compound include
2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chloro-benzotriazole,
2-(2'-hydroxy-3'-tert
butyl-5'-methylphenyl)-5-chloro-benzotriazole,
2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chloro-benzotriazole,
2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chloro-benzotriazole,
2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chloro-benzotriazole,
2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole,
2-(2'-hydroxy-5'-methylphenyl) benzotriazole,
2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl] benzotriazole,
2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole,
3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy,
2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, or
2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethy-
lbutyl)phenol. Examples of a commercially available product include
TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 328, TINUVIN 384-2,
TINUVIN 900, TINUVIN 928, TINUVIN 171, or TINUVIN 1130 (all
manufactured by BASF). As the benzotriazole compound, MYUA series
manufactured by Miyoshi Oil & Fat Co., Ltd. (The Chemical
Daily, Feb. 1, 2016) may be used.
[0135] Examples of the triazine compound include TINUVIN 1577FF,
TINUVIN 400, or TINUVIN 411L (all manufactured by BASF).
[0136] Examples of the benzophenone compound include Uvinul A,
Uvinul 3049, or Uvinul 3050 (all manufactured by BASF).
[0137] Examples of the coumarin compound include
coumarin-4,4-hydroxycoumarin, or 7-hydroxycoumarin.
[0138] The content of the ultraviolet absorber of the coloring
composition of the embodiment of the present invention is
preferably 0.1% to 20% by mass with respect to the total solid
content of the coloring composition. The upper limit is preferably
15% by mass or less, more preferably 10% by mass or less, and still
more preferably 5% by mass or less. The lower limit is preferably
0.2% by mass or more, more preferably 0.5% by mass or more, and
still more preferably 1% by mass or more. In a case where the
content of the ultraviolet absorber is within the range, the
generation of the development residue between patterns or the
occurrence of mixed color between adjacent pixels of other hues can
be effectively suppressed without impairing the pattern shape.
[0139] In addition, the content of the ultraviolet absorber is
preferably 10 to 500 parts by mass with respect to 100 parts by
mass of the photopolymerization initiator. The upper limit is
preferably 450 parts by mass or less, more preferably 300 parts by
mass or less, and still more preferably 200 parts by mass or less.
The lower limit is preferably 15 parts by mass or more, more
preferably 20 parts by mass or more, and still more preferably 25
parts by mass or more. In a case where the content of the
ultraviolet absorber is within the range, the generation of the
development residue between patterns or the occurrence of mixed
color between adjacent pixels of other hues can be effectively
suppressed.
[0140] In addition, the content of the ultraviolet absorber is
preferably 1 to 40 parts by mass with respect to 100 parts by mass
of the magenta pigment. The upper limit is preferably 35 parts by
mass or less, more preferably 30 parts by mass or less, and still
more preferably 25 parts by mass or less. The lower limit is
preferably 1.1 parts by mass or more, more preferably 1.5 parts by
mass or more, and still more preferably 2 parts by mass or more. In
a case where the content of the ultraviolet absorber is within the
range, the generation of the development residue between patterns
or the occurrence of mixed color between adjacent pixels of other
hues can be effectively suppressed.
[0141] Resin
[0142] The coloring composition of the embodiment of the present
invention can include a resin. The resin is blended in, for
example, an application for dispersing a pigment in the composition
or an application as a binder. Incidentally, a resin which is used
for dispersing a pigment in a composition is also referred to as a
dispersant. However, such uses of the resin are only exemplary, and
the resin can also be used for other purposes, in addition to such
uses.
[0143] The weight-average molecular weight (Mw) of the resin is
preferably 2,000 to 2,000,000. The upper limit is preferably
1,000,000 or less and more preferably 500,000 or less. The lower
limit is preferably 3,000 or more and more preferably 5,000 or
more.
[0144] The content of the resin in the coloring composition of the
embodiment of the present invention is preferably 1% to 80/o by
mass with respect to the total solid content of the coloring
composition. The lower limit is more preferably 10% by mass or more
and still more preferably 20% by mass or more. The upper limit is
more preferably 60% by mass or less and still more preferably 40%
by mass or less.
[0145] The coloring composition of the embodiment of the present
invention can include a resin having an amine value. By using the
resin having an amine value, it is possible to improve the
dispersibility of the magenta pigment in the composition. An
example of the resin having an amine value includes a resin
including a nitrogen atom in at least one of a main chain or a side
chain. Furthermore, from the viewpoint of the dispersibility of the
magenta pigment or the like, the resin having a nitrogen atom in
the main chain is preferable. Examples of the resin having a
nitrogen atom in the main chain include oligoimine-based resins as
described later. The resin having an amine value can be preferably
used as a dispersant.
[0146] In addition, the resin having an amine value preferably
further has an acid value. That is, the resin having an amine value
preferably further has an acid group. By using the resin, excellent
photolithographic properties are easily obtained while improving
the dispersibility of the magenta pigment. Furthermore, the
occurrence of mixed color between other layers after forming
patterns can be effectively suppressed.
[0147] An amine value of the resin having an amine value is
preferably 10 to 200 mgKOH/g. The upper limit of the amine value is
preferably 180 mgKOH/g or less and more preferably 150 mgKOH/g or
less. The lower limit of the amine value is preferably 15 mgKOH/g
or more and more preferably 20 mgKOH/g or more.
[0148] An acid value of the resin having an amine value is
preferably 10 mgKOH/g or more. The upper limit of the acid value is
preferably 200 mgKOH/g or less and more preferably 150 mgKOH/g or
less. The lower limit of the acid value is preferably 12 mgKOH/g or
more, more preferably 15 mgKOH/g or more, and still more preferably
30 mgKOH/g or more.
[0149] The coloring composition of the embodiment of the present
invention preferably includes a resin having an acid value of 50
mgKOH/g or more and more preferably includes a resin having an acid
value of 80 mgKOH/g or more. According to this aspect, a resin
having more excellent photolithographic properties is obtained. The
upper limit of the acid value of the above-mentioned resin is
preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or
less, and still more preferably 250 mgKOH/g or less. The resin
having an acid value of 50 mgKOH/g or more can be used as a binder
or a dispersant. Among those, for the reason that more excellent
photolithographic properties can be easily obtained, the resin
having an acid value of 50 mgKOH/g or more is preferably a resin
used as the dispersant.
[0150] (Dispersant)
[0151] The coloring composition of the embodiment of the present
invention preferably includes a dispersant as a resin. Examples of
the dispersant include polymer dispersants (for example, polyamide
amine or a salt thereof, polycarboxylic acid or a salt thereof,
high molecular weight unsaturated acid ester, modified
polyurethane, modified polyester, modified poly(meth)acrylate, a
(meth)acrylic copolymer, or a naphthalene sulfonic acid formalin
condensate), polyoxyethylene alkylphosphate ester, polyoxyethylene
alkyl amine, or alkanolamine.
[0152] The polymer dispersant can be further classified into a
linear polymer, a terminal-modified polymer, a graft polymer, and a
block polymer according to the structure thereof. The polymeric
dispersant adsorbs on a surface of a pigment and acts to prevent
reaggregation. Therefore, examples of a preferred structure of the
polymer dispersant include a terminal-modified polymer, a graft
polymer, and a block polymer, each of which has an anchor site for
adsorbing on the pigment surface. In addition, dispersants
described in paragraph Nos. 0028 to 0124 of JP2011-070156A or
dispersants described in JP2007-277514A are preferably used. The
contents of the publications are incorporated herein by
reference.
[0153] In the present invention, the resin is preferably a resin
including a repeating unit having a graft chain as a side chain
(hereinafter also referred to as a graft resin). According to this
aspect, the dispersibility of the pigment can be further improved.
Here, the graft chain means a polymer chain branched from a main
chain of the repeating unit. The length of the graft chain is not
particularly limited, and in a case where the graft chain gets
longer, a steric repulsion effect is enhanced, and thus, the
dispersibility of the pigment or the like can be increased. In the
graft chain, the number of atoms excluding the hydrogen atoms is
preferably 40 to 10,000, the number of atoms excluding the hydrogen
atoms is more preferably 50 to 2,000, and the number of atoms
excluding the hydrogen atoms is still more preferably 60 to
500.
[0154] The graft chain preferably includes at least one structure
selected from a polyester chain, a polyether chain, a
poly(meth)acryl chain, a polyurethane chain, a polyurea chain, or a
polyamide chain, more preferably includes at least one structure
selected from a polyester chain, a polyether chain, or a
poly(meth)acryl chain, and still more preferably includes a
polyester chain.
[0155] A terminal structure of the graft chain is not particularly
limited. The terminal structure of the graft chain may be a
hydrogen atom or a substituent. Examples of the substituent include
an alkyl group, an aryl group, a heteroaryl group, an alkoxy group,
an aryloxy group, a heteroaryloxy group, an alkylthioether group,
an arylthioether group, and a heteroarylthioether group. Among
those, from the viewpoint of improvement of the dispersibility of
the pigment or the like, a group having a steric repulsion effect
is preferable, and an alkyl group or alkoxy group having 5 to 24
carbon atoms is preferable. The alkyl group and the alkoxy group
may be any of linear, branched, and cyclic forms, and are
preferably linear or branched.
[0156] An example of the graft resin includes a resin having a
repeating unit represented by any one of the following Formulae (1)
to (4).
##STR00007##
[0157] In Formulae (1) to (4), W.sup.1, W.sup.2, W.sup.3, and
W.sup.4 each independently represent an oxygen atom or NH, X.sup.1,
X.sup.2, X.sup.3, X.sup.4, and X.sup.5 each independently represent
a hydrogen atom, a monovalent organic group, or a halogen atom,
Y.sup.1, Y.sup.2, Y.sup.3, and Y.sup.4 each independently represent
a divalent linking group, Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4
each independently represent a monovalent organic group, R.sup.3
represents an alkylene group, R.sup.4 represents a hydrogen atom or
a monovalent organic group, n, m, p, and q each independently
represent an integer of 1 to 500, and j and k each independently
represent an integer of 2 to 8. In Formula (3), in a case where p
is 2 to 500, a plurality of R.sup.3's may be the same or different
from each other. In Formula (4), in a case where q is 2 to 500, a
plurality of X.sup.5's and R.sup.4's may be the same or different
from each other.
[0158] W.sup.1, W.sup.2, W.sup.3, and W.sup.4 are preferably an
oxygen atom. X.sup.1, X.sup.2, X.sup.3, X.sup.4, and X.sup.s are
preferably a hydrogen atom or an alkyl group having 1 to 12 carbon
atoms, more preferably a hydrogen atom or a methyl group, and
particularly preferably a methyl group. Y.sup.1, Y.sup.2, Y.sup.3,
and Y.sup.4 each independently represent a divalent linking group
and the linking group is not particularly restricted in the
structure. Examples of the divalent linking group include an
alkylene group (preferably an alkylene group having 1 to 12 carbon
atoms), an arylene group (preferably an arylene group having 6 to
20 carbon atoms), --NH--, --SO--, --SO.sub.2--, --CO--, --O--,
--COO--, --OCO--, --S--, and a group formed by combination of two
or more of these groups. A structure of a monovalent organic group
represented by Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 is not
particularly limited, and specific examples thereof include an
alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a
heteroaryloxy group, an alkylthioether group, an arylthioether
group, a heteroarylthioether group, and an amino group. From the
viewpoint of improving dispersibility, the organic group
represented by Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 preferably
has a steric repulsion effect, is each independently preferably an
alkyl group or alkoxy group having 5 to 24 carbon atoms, and in
particular, still more preferably a branched alkyl group having 5
to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon
atoms, or an alkoxy group having 5 to 24 carbon atoms. An alkyl
group included in the alkoxy group may be any of linear, branched
chain, or cyclic forms.
[0159] In Formulae (1) to (4), n, m, p and q each independently
represent an integer of 1 to 500. In addition, in Formulae (1) and
(2), j and k each independently represent an integer of 2 to 8. j
and k in Formulae (1) and (2) are preferably an integer of 4 to 6
and most preferably 5 from the viewpoint of dispersion stability
and developability.
[0160] In Formula (3), R.sup.3 represents an alkylene group, an
alkylene group having 1 to 10 carbon atoms is preferable, and an
alkylene group having 2 or 3 carbon atoms is more preferable. In a
case where p is 2 to 500, a plurality of R.sup.3's may be the same
or different from each other.
[0161] In Formula (4), R.sup.4 represents a hydrogen atom or a
monovalent organic group. The monovalent organic group is not
particularly limited in the structure. Examples of the monovalent
organic group include a hydrogen atom, an alkyl group, an aryl
group, and a heteroaryl group, and preferably the hydrogen atom or
the alkyl group. In Formula (4), in a case where q is 2 to 500, a
plurality of X.sup.5's and R.sup.4's may independently be the same
or different from each other.
[0162] Examples of the graft resin include a resin having the
following structure. In addition, with regard to details of the
graft resin, reference can be made to the description in paragraph
Nos. 0025 to 0094 of JP2012-255128A, and the contents thereof are
incorporated herein by reference.
##STR00008##
[0163] In addition, in the present invention, a resin including a
nitrogen atom in the main chain is preferably used. The resin
including a nitrogen atom in the main chain (hereinafter, also
referred to as oligoimine-based resin) is preferable to include at
least one repeating unit having a nitrogen atom selected from a
poly(lower alkyleneimine)-based repeating unit, a
polyallylamine-based repeating unit, a polydiallylamine-based
repeating unit, a metaxylene diamine-epichlorohydrin
polycondensate-based repeating unit, or a polyvinylamine-based
repeating unit.
[0164] In addition, as an oligoimine-based resin, a resin which has
a repeating unit having a partial structure X composed of a
functional group with pKa of 14 or less and a repeating unit having
a side chain including an oligomer chain or a polymer chain Y
having 40 to 10,000 atoms is preferable.
[0165] For example, an oligoimine-based resin is preferably a resin
including a repeating unit represented by Formula (I-1), a
repeating unit represented by Formula (I-2), and/or a repeating
unit represented by Formula (I-2a).
##STR00009##
[0166] R.sup.1 and R.sup.2 each independently represent a hydrogen
atom, a halogen atom, or an alkyl group (preferably 1 to 6 carbon
atoms). Each a independently represents an integer of 1 to 5. *
represents a linking site between repeating units.
[0167] R.sup.8 and R.sup.9 are groups having the same definition as
R.sup.1.
[0168] L is a linking group which consists of a single bond, an
alkylene group (preferably 1 to 6 carbon atoms), an alkenylene
group (preferably 2 to 6 carbon atoms), an arylene group
(preferably 6 to 24 carbon atoms), a heteroarylene group
(preferably 1 to 6 carbon atoms), an imino group (preferably 0 to 6
carbon atoms), an ether group, a thioether group, a carbonyl group,
or a combination thereof. Among those, a single bond or
--CR.sup.5R.sup.6--NR.sup.7-- (an imino group is located on the X
or Y side) is preferable. Here, R.sup.5 and R.sup.6 each
independently represent a hydrogen atom, a hydrogen atom, or an
alkyl group (preferably 1 to 6 carbon atoms). R.sup.7 represents a
hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
[0169] L is a structural site that forms a ring structure together
with CR.sup.8CR.sup.9, and N, and is preferably a structural site
forming a non-aromatic heterocycle having 3 to 7 carbon atoms
together with the carbon atom of CR.sup.8CR.sup.9. Furthermore,
L.sup.a is preferably a structural site forming a five- to
seven-membered non-aromatic heterocycle together with the carbon
atom of CR.sup.8CR.sup.9 and N (nitrogen atom), more preferably a
structural site forming five-membered non-aromatic heterocycle, and
particularly preferably a structural site forming pyrrolidine.
Furthermore, the structural site may have a substituent such as an
alkyl group.
[0170] X represents a group having a functional group with pKa of
14 or less.
[0171] Y represents a side chain having 40 to 10,000 atoms.
[0172] Furthermore, an oligoimine-based resin may contain one or
more repeating units selected from the repeating units represented
by Formulae (I-3), (I-4), and (I-5), as a copolymerization
component. By the oligoimine-based resin containing the repeating
units, dispersibility of the magenta pigment can be further
improved.
##STR00010##
[0173] R.sup.1, R.sup.2, R.sup.8, R.sup.9, L, L.sup.a, a, and *
have the same definitions defined in Formulae (I-1), (I-2), and
(I-2a). Ya represents a side chain which has an anionic group
having 40 to 10,000 atoms. A repeating unit represented by Formula
(I-3) can be formed by adding an oligomer or polymer which has a
group reacting with an amine to form a salt to a resin which has a
primary or secondary amino group in the main chain and then
reacting with each other.
[0174] With regard to the oligoimine-based resin, reference can be
made to the description in paragraph Nos. 0102 to 0166 of
JP2012-255128A, and the contents thereof are incorporated herein by
reference. Specific examples of the oligoimine-based resin include
resins shown below. In addition, the resins described in paragraph
Nos. 0168 to 0174 of JP2012-255128A can be used.
##STR00011##
[0175] A commercially available product can also be used as the
resin for the dispersant. For example, a product described in
paragraph No. 0129 of JP2012-137564A can be used as the dispersant.
An example thereof includes Disperbyk-111 (manufactured by
BYK-Chemie). The resin demonstrated as the dispersant can also be
used for other applications in addition to the dispersant. For
example, the resin can also be used for a binder.
[0176] A content of the dispersant is preferably 1 to 200 parts by
mass with respect to 100 parts by mass of the pigment. The lower
limit is preferably 5 parts by mass or more and more preferably 10
parts by mass or more. The upper limit is preferably 150 parts by
mass or less and more preferably 100 parts by mass or less.
[0177] (Alkali-Soluble Resin)
[0178] The coloring composition of the embodiment of the present
invention can contain an alkali-soluble resin as a resin. By
containing the alkali-soluble resin, developability is improved.
The alkali-soluble resin can also be used as a dispersant or a
binder.
[0179] The alkali-soluble resin can be appropriately selected from
resins having a group promoting an alkali dissolution. Examples of
the group promoting an alkali dissolution (hereinafter also
referred to as an acid group) include a carboxyl group, a
phosphoric acid group, a sulfo group, and a phenolic hydroxyl
group, and preferably the carboxyl group. The acid groups included
in the alkali-soluble resin may be of one kind or two or more kinds
thereof.
[0180] The weight-average molecular weight (Mw) of the
alkali-soluble resin is preferably 5,000 to 100,000. In addition,
the number-average molecular weight (Mn) of the alkali-soluble
resin is preferably 1,000 to 20,000.
[0181] As the alkali-soluble resin, from the viewpoint of heat
resistance, a polyhydroxystyrene-based resin, a polysiloxane-based
resin, an acrylic-based resin, an acrylamide-based resin, or an
acrylic/acrylamide copolymer resin is preferable. In addition, from
the viewpoint of suppressing developability, an acrylic-based
resin, an acrylamide-based resin, or an acrylic/acrylamide
copolymer resin is preferable.
[0182] The alkali-soluble resin is preferably a polymer having a
carboxyl group in the side chain. Examples thereof include
copolymers having a repeating unit derived from a monomer such as a
methacrylic acid, an acrylic acid, an itaconic acid, an crotonic
acid, a maleic acid, a 2-carboxyethyl(meth)acrylic acid, a
vinylbenzoic acid, and a partially esterified maleic acid,
alkali-soluble phenol resins such as a novolac type resin, an
acidic cellulose derivative having a carboxyl group in the side
chain, and a polymer obtained by adding an acid anhydride to a
polymer having a hydroxyl group. In particular, a copolymer of a
(meth)acrylic acid and another monomer copolymerizable therewith is
suitable as the alkali-soluble resin. Examples of another monomer
copolymerizable with the (meth)acrylic acid include alkyl
(meth)acrylate, aryl (meth)acrylate, and a vinyl compound. Examples
of the alkyl (meth)acrylate and the aryl (meth)acrylate include
methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate,
butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl
(meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl
(meth)acrylate, benzyl (meth)acrylate, tolyl (meth)acrylate,
naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl
methacrylate, and tetrahydrofurfuryl methacrylate. Examples of the
vinyl compound include styrene, .alpha.-methylstyrene,
vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, a
polystyrene macromonomer, and a polymethyl methacrylate
macromonomer. Further, examples of other monomer include the
N-position-substituted maleimide monomers described in
JP1998-300922A (JP-H10-300922A), such as N-phenylmaleimide and
N-cyclohexylmaleimide. Such other monomers copolymerizable with
(meth)acrylic acids may be of one kind or of two or more kinds
thereof.
[0183] As the alkali-soluble resin, a benzyl
(meth)acrylate/(meth)acrylic acid copolymer, a benzyl
(meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth)acrylate
copolymer, or a multicomponent copolymer including benzyl
(meth)acrylate/(meth)acrylic acid/other monomers can be preferably
used. Further, a copolymer obtained by copolymerizing
2-hydroxyethyl (meth)acrylate and other monomers, the
2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl
methacrylate/methacrylic acid copolymer described in JP1995-140654A
(JP-H07-140654A), a 2-hydroxy-3-phenoxypropylacrylate/polymethyl
methacrylate macromonomer/benzyl methacrylate/methacrylic acid
copolymer, a 2-hydroxyethyl methacrylate/polystyrene
macromonomer/methyl methacrylate/methacrylic acid copolymer, a
2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl
methacrylate/methacrylic acid copolymer, and the like can also be
preferably used. Furthermore, as a commercially available product,
for example, FF-426 (manufactured by Fujikura Kasei Co., Ltd.) can
also be used.
[0184] An alkali-soluble resin having a polymerizable group can
also be used as the alkali-soluble resin. Examples of the
polymerizable group include a (meth)allyl group and a
(meth)acryloyl group. An alkali-soluble resin having a
polymerizable group is preferably an alkali-soluble resin having a
polymerizable group in the side chain. Specific examples of the
alkali-soluble resin having a polymerizable group include a resin
having the following structure. Examples of a commercially
available product of the alkali-soluble resin having a
polymerizable group include Dianal NR Series (manufactured by
Mitsubishi Rayon Co., Ltd.), Photomer 6173 (polyurethane acrylate
oligomer, manufactured by Diamond Shamrock Corp.), Viscoat R-264
and KS Resist 106 (all manufactured by Osaka Organic Chemical
Industry Ltd.), Cyclomer P series (for example, ACA230AA) and
Placcel CF 200 series (all manufactured by Daicel Corporation),
Ebecryl 3800 (manufactured by Daicel UCB Company, Ltd.), Acrycure
RD-F8 (manufactured by Nippon Shokubai Co., Ltd.), and DP-1305
(manufactured by Fuji Fine Chemicals.).
##STR00012## ##STR00013##
[0185] The alkali-soluble resin is preferable to include a polymer
obtained by polymerizing monomer components including at least one
compound (hereinafter, in some case, the compound is also referred
to as an "ether dimer") selected from compounds represented by
following Formula (ED1) or compounds represented by Formula (1) of
JP2010-168539A.
##STR00014##
[0186] In Formula (ED1), R.sup.1 and R.sup.2 each independently
represent a hydrogen atom or a hydrocarbon group having 1 to 25
carbon atoms, which may have a substituent.
[0187] With regard to the specific examples of the ether dimer,
reference can be made to paragraph No. 0317 of JP2013-029760A, and
the contents thereof are incorporated herein by reference. The
ether dimers may be used singly or in combination of two or more
kinds thereof.
[0188] The alkali-soluble resin may include a repeating unit
derived from a compound represented by Formula (X).
##STR00015##
[0189] In Formula (X), R.sub.1 represents a hydrogen atom or a
methyl group, R.sub.2 represents an alkylene group having 2 to 10
carbon atoms, and R.sub.3 represents a hydrogen atom or an alkyl
group having 1 to 20 carbon atoms, which may include a benzene
ring. n represents an integer of 1 to 15.
[0190] In Formula (X), the number of carbon atoms of the alkylene
group represented by R.sub.2 is preferably 2 to 3. In addition, the
number of carbon atoms of the alkyl group represented by R.sub.3 is
preferably 1 to 10. The alkyl group represented by R.sub.3 may
include a benzene ring. Examples of the alkyl group including a
benzene ring represented by R.sub.3 include a benzyl group, a
2-phenyl (iso)propyl group and the like.
[0191] With regard to the alkali-soluble resin, reference can be
made to the description in paragraph Nos. 0558 to 0571 of
JP2012-208494A (paragraph Nos. 0685 to 0700 of the corresponding
US2012/0235099A), and the contents thereof are incorporated herein
by reference. In addition, a copolymer (B) described in paragraph
Nos. 0029 to 0063 of JP2012-032767A and the alkali-soluble resins
used in Examples, binder resins described in paragraph Nos. 0088 to
0098 of JP2012-208474A and binder resins used in Examples, binder
resins described in paragraph Nos. 0022 to 0032 of JP2012-137531A
and binder resins used in Examples, binder resins described in
paragraph Nos. 0132 to 0143 of JP2013-024934A and binder resins
used in Examples, binder resins described in paragraph Nos. 0092 to
0098 of JP2011-242752A and Examples, and binder resins described in
paragraph Nos. 0030 to 0072 of JP2012-032770A can also be used. The
contents of the publications are incorporated herein by
reference.
[0192] An acid value of the alkali-soluble resin is preferably 30
to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or
more, still more preferably 70 mgKOH/g or more, and particularly
preferably 80 mgKOH/g or more. The upper limit is more preferably
400 mgKOH/g or less and still more preferably 250 mgKOH/g or
less.
[0193] The content of the alkali-soluble resin is preferably 1% to
80% by mass with respect to the total solid content of the coloring
composition. The lower limit is more preferably 10% by mass or more
and still more preferably 20% by mass or more. The upper limit is
more preferably 60% by mass or less and still more preferably 40%
by mass or less. The coloring composition of the embodiment of the
present invention may include only one kind or two or more kinds of
the alkali-soluble resin. In a case where two or more kinds of the
magenta pigments are included, the total amount thereof is
preferably within the above-mentioned range.
[0194] Solvent
[0195] The coloring composition of the embodiment of the present
invention preferably contains a solvent. The solvent is preferably
an organic solvent. The solvent is not particularly limited as long
as it satisfies the solubility of the respective components or the
coatability of the coloring composition.
[0196] Examples of the organic solvent include the following
organic solvents. Examples of esters include ethyl acetate, n-butyl
acetate, isobutyl acetate, cyclohexyl acetate, amyl formate,
isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl
butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl
alkyloxyacetate esters (for example, methyl alkyloxyacetate, ethyl
alkyloxyacetate, and butyl alkyloxyacetate (for example, methyl
methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl
ethoxyacetate, and ethyl ethoxyacetate)), alkyl
3-alkyloxypropionate esters (for example, methyl
3-alkyloxypropionate and ethyl 3-alkyloxypropionate (for example,
methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl
3-ethoxypropionate, and ethyl 3-ethoxypropionate)), alkyl
2-alkyloxypropionate esters (for example, methyl
2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl
2-alkyloxypropionate (for example, methyl 2-methoxypropionate,
ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl
2-ethoxypropionate, and ethyl 2-ethoxypropionate)), methyl
2-alkyloxy-2-methyl propionate and ethyl 2-alkyloxy-2-methyl
propionate (for example, methyl 2-methoxy-2-methyl propionate and
ethyl 2-ethoxy-2-methyl propionate), methyl pyruvate, ethyl
pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate,
methyl 2-oxobutanoate, and ethyl 2-oxobutanoate. Examples of ethers
include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene
glycol monomethyl ether, ethylene glycol monoethyl ether, methyl
cellosolve acetate, ethyl cellosolve acetate, diethylene glycol
monomethyl ether, diethylene glycol monoethyl ether, diethylene
glycol monobutyl ether, propylene glycol monomethyl ether,
propylene glycol monomethyl ether acetate, propylene glycol
monoethyl ether acetate, and propylene glycol monopropyl ether
acetate. Examples of the ketones include methyl ethyl ketone,
cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.
Suitable examples of the aromatic hydrocarbons include toluene and
xylene. However, it is preferable in some cases to reduce aromatic
hydrocarbons (benzene, toluene, xylene, ethylbenzene, and the like)
(for example, the amount can be set to 50 ppm (parts per million)
by mass or less, 10 ppm by mass or less, or 1 ppm by mass or less
with respect to the total amount of the organic solvent) as a
solvent for a reason such as an environmental aspect.
[0197] The organic solvents may be used singly or in combination of
two or more kinds thereof. In a case where the organic solvents are
used in combination of two or more kinds thereof, the solvent is
particularly preferably a mixed solution formed of two or more
kinds selected from methyl 3-ethoxypropionate, ethyl
3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate,
diethylene glycol dimethyl ether, butyl acetate, methyl
3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol
acetate, butyl carbitol acetate, propylene glycol methyl ether, and
propylene glycol monomethyl ether acetate.
[0198] In the present invention, the organic solvent preferably has
the content of peroxides of 0.8 mmol/L or less, and more
preferably, it does not substantially include peroxides. Further,
it is preferable to use an organic solvent having a small metal
content, and for example, the metal content of the organic solvent
is preferably 10 ppb (parts per billion) by mass or less. The metal
content of the organic solvent is at a level of ppt (parts per
trillion) by mass, as desired, and such a high-purity solvent is
provided by, for example, Toyo Kasei Kogyo Co., Ltd. (The Chemical
Daily, Nov. 13, 2015).
[0199] The content of the solvent is preferably an amount such that
the total solid content of the coloring composition is 5% to 80% by
mass. The lower limit is preferably 10% by mass or more. The upper
limit is preferably 60% by mass or less, more preferably 50% by
mass or less, and still more preferably 40% by mass or less.
[0200] Compound Having Epoxy Group
[0201] The coloring composition of the embodiment of the present
invention can contain a compound having an epoxy group (hereinafter
also referred to as an epoxy compound). The epoxy compound is
preferably a compound having 1 to 100 epoxy groups per molecule.
The lower limit of the number of the epoxy groups is more
preferably 2 or more. The upper limit of the number of the epoxy
groups can be set to, for example, 10 or less, or to 5 or less.
[0202] The epoxy equivalent (=the molecular weight of the epoxy
compound/the number of epoxy groups) of the epoxy compound is
preferably 500 g/equivalent or less, more preferably 100 to 400
g/equivalent, and still more preferably 100 to 300
g/equivalent.
[0203] The epoxy compound may be either a low-molecular-weight
compound (for example, a molecular weight of less than 1,000) or a
polymer compound (macromolecule) (for example, a molecular weight
of 1,000 or more, and in a case of a polymer, a weight-average
molecular weight of 1,000 or more). The weight-average molecular
weight of the epoxy compound is preferably 200 to 100,000 and more
preferably 500 to 50,000. The upper limit of the weight-average
molecular weight is more preferably 10,000 or less, still more
preferably 5,000 or less, and even still more preferably 3,000 or
less.
[0204] As the epoxy compound, the compounds described in paragraph
Nos. 0034 to 0036 of JP2013-011869A, paragraph Nos. 0147 to 0156 of
JP2014-043556A, and paragraph Nos. 0085 to 0092 of JP2014-089408A
can also be used. The contents of the publications are incorporated
herein by reference.
[0205] In a case where the coloring composition of the embodiment
of the present invention contains an epoxy compound, the content of
the epoxy compound is preferably 0.1% to 40% by mass with respect
to the total solid content of the coloring composition. The lower
limit is, for example, more preferably 0.5% by mass or more, and
still more preferably 1% by mass or more. The upper limit is, for
example, more preferably 30% by mass or less, and still more
preferably 20% by mass or less. These epoxy compounds may be used
singly or in combination of two or more kinds thereof. In a case
where the polymerizable compounds are used in combination of two or
more kinds thereof, the total amount thereof is preferably within
the range.
[0206] The coloring composition of the embodiment of the present
invention can also substantially contain no epoxy compound. In a
case where the coloring composition of the embodiment of the
present invention does not substantially contain the epoxy
compound, the content of the epoxy compound is preferably 0.05% by
mass or less, more preferably 0.01% by mass or less with respect to
the total solid content of the coloring composition, and the
coloring composition even still more preferably contains no epoxy
compound.
[0207] Curing Accelerator
[0208] The coloring composition of the embodiment of the present
invention may include a curing accelerator for the purpose of
improving the hardness of a pattern or lowering a curing
temperature. Examples of the curing accelerator include a thiol
compound.
[0209] Examples of the thiol compound include a polyfunctional
thiol compound having two or more mercapto groups in a molecule
thereof. The polyfunctional thiol compound may also be added for
the purpose of alleviating problems in stability, smell,
developability, adhesiveness, or the like. The polyfunctional thiol
compound is preferably a secondary alkanethiol and more preferably
a compound having a structure represented by Formula (T1).
##STR00016##
[0210] In Formula (T1), n represents an integer of 2 to 4 and L
represents a divalent to tetravalent linking group.
[0211] In Formula (T1), it is preferable that L is an aliphatic
group having 2 to 12 carbon atoms. In Formula (T1), it is more
preferable that n is 2 and L is an alkylene group having 2 to 12
carbon atoms. Specific examples of the polyfunctional thiol
compounds include compounds represented by Structural Formulae (T2)
to (T4), and the compound represented by Formula (T2) is
preferable. These thiol compounds can be used singly or in
combination of two or more kinds thereof.
##STR00017##
[0212] Moreover, as the curing accelerator, a methylol-based
compound (for example, the compounds exemplified as a crosslinking
agent in paragraph No. 0246 of JP2015-034963A), amines, phosphonium
salts, amidine salts, amide compounds (each of which are the curing
agents described in, for example, paragraph No. 0186 of
JP2013-041165A), base generators (for example, the ionic compounds
described in JP2014-055114A), isocyanate compounds (for example,
the compounds described in paragraph No. 0071 of JP2012-150180A),
alkoxysilane compounds (for example, the alkoxysilane compounds
having epoxy groups, described in JP2011-253054A), onium salt
compounds (for example, the compounds exemplified as an acid
generator in paragraph No. 0216 of JP2015-034963A, and the
compounds described in JP2009-180949A), or the like can be
used.
[0213] In a case where the coloring composition of the embodiment
of the present invention contains the curing accelerator, the
content of the curing accelerator is preferably 0.3% to 8.9% by
mass, and more preferably 0.8% to 6.4% by mass, with respect to the
total solid content of the coloring composition.
[0214] Pigment Derivative
[0215] The coloring composition of the embodiment of the present
invention preferably contains a pigment derivative. Examples of the
pigment derivative include a compound having a structure in which a
part of a chromophore is substituted with an acid group, a basic
group, or a phthalimidemethyl group.
[0216] Examples of a chromophore constituting the pigment
derivative include a quinoline-based skeleton, a
benzimidazolone-based skeleton, a diketopyrrolopyrrole-based
skeleton, an azo-based skeleton, a phthalocyanine-based skeleton,
an anthraquinone-based skeleton, a quinacridone-based skeleton, a
dioxazine-based skeleton, a perinone-based skeleton, a
perylene-based skeleton, a thioindigo-based skeleton, an
isoindoline-based skeleton, an isoindolinone-based skeleton, a
quinophthalone-based skeleton, a threne-based skeleton, and a metal
complex-based skeleton, the quinoline-based skeleton, the
benzimidazolone-based skeleton, the diketopyrrolopyrrole-based
skeleton, the azo-based skeleton, the quinophthalone-based
skeleton, the isoindoline-based skeleton, and the
phthalocyanine-based skeleton are preferable, and the azo-based
skeleton and the benzimidazolone-based skeleton are more
preferable. As the acid group contained in the pigment derivative,
a sulfo group or a carboxyl group is preferable and the sulfo group
is more preferable. As the basic group contained in the pigment
derivative, an amino group is preferable and a tertiary amino group
is more preferable. With regard to specific examples of the pigment
derivative, reference can be made to the description in paragraph
Nos. 0162 to 0183 of JP2011-252065A, and the contents thereof are
incorporated herein by reference.
[0217] In a case where the coloring composition of the embodiment
of the present invention contains a pigment derivative, the content
of the pigment derivative is preferably 1 to 30 parts by mass, and
more preferably 3 to 20 parts by mass, with respect to 100 parts by
mass of the pigment. The pigment derivative may be used singly or
in combination of two or more kinds thereof.
[0218] Surfactant
[0219] The coloring composition of the embodiment of the present
invention preferably contains a surfactant. As the surfactant,
various surfactants such as a fluorine-based surfactant, a nonionic
surfactant, a cationic surfactant, an anionic surfactant, and a
silicone-based surfactant can be used, and the fluorine-based
surfactant is preferable for a reason that coatability can be
further improved.
[0220] By incorporating the fluorine-based surfactant into the
coloring composition of the embodiment of the present invention,
liquid characteristics in a case of preparation of a coating liquid
are further improved, and thus, the evenness of coating thickness
can be further improved. That is, in a case where a film is formed
using the coating liquid to which a coloring composition containing
the fluorine-based surfactant has been applied, the interface
tension between a surface to be coated and the coating liquid is
reduced to improve uniformity of the drying with respect to the
film. Therefore, formation of a film with a uniform thickness which
exhibits little coating unevenness can be more suitably
performed.
[0221] The fluorine content in the fluorine-based surfactant is
preferably 3% to 40% by mass, more preferably 5% to 30% by mass,
and particularly preferably 7% to 25% by mass. The fluorine-based
surfactant in which the fluorine content falls within this range is
effective in terms of the evenness of the thickness of the coating
film or liquid saving properties and the solubility of the
surfactant in the coloring composition is also good.
[0222] Examples of the fluorine-based surfactant include MEGAFACE
F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437,
F475, F479, F482, F554, and F780 (all manufactured by DIC
Corporation), FLUORAD FC430, FC431, and FC171 (all manufactured by
Sumitomo 3M), SURFLON S-382, SC-101, SC-103, SC-104, SC-105,
SC-1068, SC-381, SC-383, and S-393, and KH-40 (all manufactured by
Asahi Glass Co., Ltd.), and PF636, PF656, PF6320, PF6520, and
PF7002 (all manufactured by OMNOVA). Further, as the fluorine-based
surfactant, the compounds described in paragraph Nos. 0015 to 0158
of JP2015-117327A, and the compounds described in paragraph Nos.
0117 to 0132 of JP2011-132503A can be used. As the fluorine-based
surfactant, a block polymer can also be used, and specific examples
thereof include the compounds described in JP2011-089090A.
[0223] As the fluorine-based surfactant, an acrylic compound, which
has a molecular structure having a functional group containing a
fluorine atom and in which by application of heat to the molecular
structure, the functional group containing a fluorine atom is cut
to volatilize a fluorine atom, can also be suitably used. Examples
of the fluorine-based surfactant include MEGAFACE DS series
(manufactured by DIC Corporation, The Chemical Daily, Feb. 22,
2016, Nikkei Business Daily, Feb. 23, 2016), for example, MEGAFACE
DS-21, which may also be used.
[0224] As the fluorine-based surfactant, a fluorine-containing
polymer compound including a repeating unit derived from a
(meth)acrylate compound having a fluorine atom and a repeating unit
derived from a (meth)acrylate compound having 2 or more (preferably
5 or more) alkyleneoxy groups (preferably ethyleneoxy groups or
propyleneoxy groups) can also be preferably used, and the following
compounds are also exemplified as a fluorine-based surfactant for
use in the present invention. In General Formula below, %
representing the ratio of the repeating unit is % by mole.
##STR00018##
[0225] The weight-average molecular weight of the compounds is
preferably 3,000 to 50,000, and is, for example, 14,000.
[0226] A fluorine-containing polymer having an ethylenically
unsaturated bonding group in a side chain can also be used as the
fluorine-based surfactant. Specific examples thereof include the
compounds described in paragraph Nos. 0050 to 0090 and paragraph
Nos. 0289 to 0295 of JP2010-164965A. Examples of commercially
available products thereof include MEGAFACE RS-101, RS-102,
RS-718-K, and RS-72-K, all of which are manufactured by DIC
Corporation.
[0227] Examples of the nonionic surfactant include glycerol,
trimethylolpropane, trimethylolethane, and ethoxylate and
propoxylate thereof (for example, glycerol propoxylate and glycerol
ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl
ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl
ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol
dilaurate, polyethylene glycol distearate, sorbitan fatty acid
esters, PLURONIC L10, L31, L61, L62, 10R5, 17R2, and 25R2
(manufactured by BASF), TETRONIC 304, 701, 704, 901, 904, and 150R1
(manufactured by BASF), SOLSPERSE 20000 (manufactured by Lubrizol
Japan Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako
Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, and
D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), and
OLFINE E1010, and SURFYNOL 104, 400, and 440 (manufactured by
Nissin Chemical Industry Co., Ltd.).
[0228] Specific examples of the cationic surfactant include an
organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical
Co., Ltd.), a (meth)acrylic acid-based (co)polymer POLYFLOW No. 75,
No. 90, and No. 95 (manufactured by KYOEISHA CHEMICAL CO., LTD.),
and WO01 (manufactured by Yusho Co., Ltd.).
[0229] Examples of the anionic surfactant include W004, W005, and
W017 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured
by Sanyo Chemical Industries, Ltd.).
[0230] Examples of the silicone-based surfactant include TORAY
SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY
SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA,
TORAY SILICONE SH30PA, and TORAY SILICONE SH8400 (all manufactured
by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445,
TSF-4460, and TSF-4452 (all manufactured by Momentive Performance
Materials Co., Ltd.), KP-341, KF6001, and KF6002 (all manufactured
by Shin-Etsu Chemical Co., Ltd.), and BYK307, BYK323, and BYK330
(all manufactured by BYK Chemie).
[0231] The content of the surfactant is preferably 0.001% to 2.0%
by mass, and more preferably 0.005% to 1.0% by mass, with respect
to the total solid content of the coloring composition. The
surfactant may be used singly or in combination of two or more
kinds thereof. In a case where two or more kinds of surfactants are
included, the total amount thereof is preferably within the
range.
[0232] Silane Coupling Agent
[0233] The coloring composition of the embodiment of the present
invention can contain a silane coupling agent. In the present
invention, the silane coupling agent means a silane compound having
a hydrolyzable group and another functional group. Further, the
hydrolyzable group refers to a substituent that can be directly
linked to a silicon atom to generate a siloxane bond by a
hydrolysis reaction and/or a condensation reaction. Examples of the
hydrolyzable group include a halogen atom, an alkoxy group, and an
acyloxy group.
[0234] The silane coupling agent is preferably a silane compound
having at least one selected from a vinyl group, an epoxy group, a
styrene group, a methacryl group, an amino group, an isocyanurate
group, a ureido group, a mercapto group, a sulfide group, or an
isocyanate group, or an alkoxy group. Specific examples of the
silane coupling agent include
N-.beta.-aminoethyl-.gamma.-aminopropyl methyldimethoxysilane
(KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.),
N-.beta.-aminoethyl-.gamma.-aminopropyl trimethoxysilane (KBM-603,
manufactured by Shin-Etsu Chemical Co., Ltd.),
N-.beta.-aminoethyl-.gamma.-aminopropyl triethoxysilane (KBE-602,
manufactured by Shin-Etsu Chemical Co., Ltd.), .gamma.-aminopropyl
trimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co.,
Ltd.), .gamma.-aminopropyl triethoxysilane (KBE-903, manufactured
by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyl
trimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co.,
Ltd.), and 3-glycidoxypropyl trimethoxysilane (KBM-403,
manufactured by Shin-Etsu Chemical Co., Ltd.). With regard to
details of the silane coupling agent, reference can be made to the
description in paragraph Nos. 0155 to 0158 of JP2013-254047A, and
the contents thereof are incorporated herein by reference.
[0235] In a case where the coloring composition of the embodiment
of the present invention contains a silane coupling agent, the
content of the silane coupling agent is preferably 0.001% to 20% by
mass, more preferably 0.01% to 10% by mass, and particularly
preferably 0.1% to 5% by mass, with respect to the total solid
content of the coloring composition. The coloring composition of
the embodiment of the present invention may include one kind or two
or more kinds of the silane coupling agents. In a case where the
coloring composition includes two or more kinds of the silane
coupling agent, the total amount thereof is preferably within the
range.
[0236] Polymerization Inhibitor
[0237] The coloring composition of the embodiment of the present
invention can contain a polymerization inhibitor. Examples of the
polymerization inhibitor include hydroquinone, p-methoxyphenol,
di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone,
4,4'-thiobis(3-methyl-6-t-butylphenol),
2,2'-methylenebis(4-methyl-6-t-butylphenol), and an
N-nitrosophenylhydroxylamine salt (an ammonium salt, a cerous salt,
or the like).
[0238] In a case where the coloring composition of the embodiment
of the present invention contains a polymerization inhibitor, the
content of the polymerization inhibitor is preferably 0.01% to 5%
by mass with respect to the total solid content of the coloring
composition. The coloring composition of the embodiment of the
present invention may include one kind or two or more kinds of the
polymerization inhibitor. In a case where two or more kinds of
polymerization inhibitors are included, the total amount thereof is
preferably within the range.
[0239] Other Additives
[0240] Various additives such as a filler, an adhesion promoter, an
antioxidant, and an aggregation inhibitor can be blended into the
coloring composition of the embodiment of the present invention, as
desired. Examples of these additives include the additives
described in paragraph Nos. 0155 and 0156 of JP2004-295116A, and
the contents thereof are incorporated herein by reference. Further,
as the antioxidant, for example, a phenol compound, a
phosphorus-based compound (for example, the compounds described in
paragraph No. 0042 of JP2011-090147A), a thioether compound, or the
like can be used. Examples of a commercially available product
thereof include ADEKA STAB series (AO-20, AO-30, AO-40, AO-50,
AO-50F, AO-60, AO-60G, AO-80, AO-330, and the like), all of which
are manufactured by ADEKA. The antioxidant may be used singly or in
combination of two or more kinds thereof. The coloring composition
of the embodiment of the present invention can contain the
sensitizers or the light stabilizers described in paragraph No.
0078 of JP2004-295116A, or the thermal polymerization inhibitors
described in paragraph No. 0081 of the same publication.
[0241] There are some cases where a metal element is included in
the coloring composition according to raw materials and the like,
but from the viewpoint of suppression of generation of defects, or
the like, the content of Group 2 elements (calcium, magnesium, and
the like) in the coloring composition is preferably 50 ppm by mass
or less, and more preferably 0.01 to 10 ppm by mass. Further, the
total amount of the inorganic metal salts in the coloring
composition is preferably 100 ppm by mass or less and more
preferably 0.5 to 50 ppm by mass.
[0242] The moisture content in the coloring composition of the
embodiment of the present invention is usually 3% by mass or less,
preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by
mass. The moisture content can be measured by a Karl Fischer
method.
[0243] The coloring composition of the embodiment of the present
invention can be used after its viscosity is adjusted for the
purposes of adjusting the state of a film surface (flatness or the
like), adjusting a film thickness, or the like. The value of the
viscosity can be appropriately selected as desired, and is, for
example, preferably 0.3 mPas to 50 mPas, and more preferably 0.5
mPas to 20 mPas at 25.degree. C. As for a method for measuring the
viscosity, the viscosity can be measured, for example, with a
temperature being adjusted to 25.degree. C., using a viscometer
RE85L (rotor: 1.degree. 34'_R24, measurement range of 0.6 to 1,200
mPas) manufactured by Toki Sangyo Co., Ltd.
[0244] A storage container for the coloring composition of the
embodiment of the present invention is not particularly limited,
and a known storage container can be used. Further, as the storage
container, it is also preferable to use a multilayer bottle having
an inner wall constituted with six layers from six kinds of resins
or a bottle having a 7-layer structure from 6 kinds of resins for
the purpose of suppressing incorporation of impurities into raw
materials or compositions. Examples of such a container include the
containers described in JP2015-123351A.
[0245] The coloring composition of the embodiment of the present
invention can be preferably used for forming of a coloring pixel
(preferably red coloring pixel) in a color filter, or the like. For
example, the coloring composition of the embodiment of the present
invention can be preferably used for a color filter which is used
for a solid-state imaging element such as a charge coupled device
(CCD) and a complementary metal-oxide semiconductor (CMOS), an
image display device, or the like.
[0246] In a case where the coloring composition of the embodiment
of the present invention is used as a color filter in applications
for a liquid crystal display device, the voltage holding ratio of a
liquid crystal display element comprising a color filter is
preferably 70% or more, and more preferably 90% or more. Known
means for obtaining a high voltage holding ratio can be
incorporated as appropriate, and examples of typical means include
use of high-purity materials (for example, reduction in ionic
impurities) and control of the amount of acidic functional groups
in a composition. The voltage holding ratio can be measured by, for
example, the methods described in paragraph 0243 of JP2011-008004A
and paragraphs 0123 to 0129 of JP2012-224847A.
[0247] <Method for Preparing Coloring Composition>
[0248] The coloring composition of the embodiment of the present
invention can be prepared by mixing the above-mentioned components.
In the preparation of the coloring composition, all the components
may be dissolved and/or dispersed at the same time in a solvent to
prepare the coloring composition, or the respective components may
be appropriately left in two or more solutions or dispersion
liquids and mixed to prepare the coloring composition upon use
(during coating), as desired.
[0249] Furthermore, in the preparation of the coloring composition,
a process for dispersing the pigment is preferably included. In the
process for dispersing the pigment, examples of a mechanical force
that is used for dispersion of the pigment include compression,
pressing, impact, shear, and cavitation. Specific examples of these
processes include a beads mill, a sand mill, a roll mill, a ball
mill, a paint shaker, a microfluidizer, a high-speed impeller, a
sand grinder, a flow jet mixer, high-pressure wet atomization, and
ultrasonic dispersion. Further, in the pulverization of the pigment
in a sand mill (beads mill), it is preferable to perform a
treatment under the condition for increasing a pulverization
efficiency by using beads having small diameters; increasing the
filling rate of the beads; or the like. Incidentally, it is
preferable to remove coarse particles by filtration,
centrifugation, or the like after the pulverization treatment. In
addition, as the process and the dispersing machine for dispersing
the pigment, the process and the dispersing machine described in
"Dispersion Technology Comprehension, published by Johokiko Co.,
Ltd., Jul. 15, 2005", "Actual comprehensive data collection on
dispersion technology and industrial application centered on
suspension (solid/liquid dispersion system), published by
Publication Department, Management Development Center, Oct. 10,
1978", and paragraph No. 0022 of JP2015-157893A can be suitably
used. In addition, in the process for dispersing the pigment, a
refining treatment of particles in a salt milling process may be
performed. With regard to the materials, the equipment, the process
conditions, and the like used in the salt milling process,
reference can be made to, for example, the description in
JP2015-194521A and JP2012-046629A.
[0250] It is preferable that in the preparation of the coloring
composition, a composition formed by mixing the respective
components is filtered through a filter for the purpose of removing
foreign matters, reducing defects, or the like. As the filter, any
filters that have been used in the related art for filtration use
and the like may be used without particular limitation. Examples of
the filter include filters formed of materials including, for
example, a fluorine resin such as polytetrafluoroethylene (PTFE), a
polyamide-based resin such as nylon (for example, nylon-6 and
nylon-6,6), and a polyolefin resin (including a polyolefin resin
having a high density and/or an ultrahigh molecular weight) such as
polyethylene and polypropylene (PP). Among these materials,
polypropylene (including a high-density polypropylene) and nylon
are preferable.
[0251] The pore diameter of the filter is suitably approximately
0.01 to 7.0 .mu.m, preferably approximately 0.01 to 3.0 .mu.m, and
more preferably approximately 0.05 to 0.5 .mu.m.
[0252] In addition, a fibrous filter material is also preferably
used as the filter. Examples of the fibrous filter material include
a polypropylene fiber, a nylon fiber, and a glass fiber. Examples
of a filter using the fibrous filter material include filter
cartridges of SBP type series (SBP008 and the like), TPR type
series (TPR002, TPR005, and the like), or SHPX type series (SHPX003
and the like), all of which are manufactured by Roki Techno Co.,
Ltd.
[0253] In a case of using a filter, different filters may be
combined. Here, the filtration with each of the filters may be
performed once or may be performed twice or more times.
[0254] For example, filters having different pore diameters within
the above-mentioned range may be combined. With regard to the pore
diameter of the filter herein, reference can be made to nominal
values of filter manufacturers. A commercially available filter can
be selected from, for example, various filters provided by Nihon
Pall Corporation (DFA4201NIEY and the like), Toyo Roshi Kaisha.,
Ltd., Nihon Entegris K.K. (formerly Nippon Microlith Co., Ltd.),
Kitz Micro Filter Corporation, and the like.
[0255] In addition, the filtration through the first filter may be
performed with only a dispersion liquid, the other components may
be mixed therewith, and then the filtration through the second
filter may be performed. As the second filter, a filter formed of
the same material as that of the first filter, or the like can be
used.
[0256] <Cured Film>
[0257] The cured film of an embodiment of the present invention is
a cured film obtained from the above-mentioned coloring composition
of the embodiment of the present invention. The cured film of the
embodiment of the present invention can be preferably used as a
color filter. In particular, the cured film of the embodiment of
the present invention can be preferably used as a magenta coloring
pixel of a color filter. The film thickness of the cured film can
be appropriately adjusted depending on purposes. For example, the
film thickness is preferably 5 .mu.m or less, more preferably 3
.mu.m or less, and still more preferably 1 .mu.m or less. The lower
limit of the film thickness is preferably 0.1 .mu.m or more, more
preferably 0.2 .mu.m or more, and still more preferably 0.3 .mu.m
or more.
[0258] <Color Filter>
[0259] Next, the color filter of an embodiment of the present
invention will be described.
[0260] The color filter of the embodiment of the present invention
has the above-mentioned cured film of the embodiment of the present
invention.
[0261] A preferred aspect of the color filter of the embodiment of
the present invention includes a color filter having a magenta
coloring pixel obtained from the photosensitive coloring
composition, a cyan coloring pixel, and a yellow coloring
pixel.
[0262] In the case where the color filter of the embodiment of the
present invention has the magenta coloring pixel, the cyan coloring
pixel, and the yellow coloring pixel, a ratio of an area (an area
ratio) of the magenta coloring pixel, the cyan coloring pixel, and
the yellow coloring pixel is not particularly limited. The area
ratio of each pixel may be the same or different from each other.
With regard to the cyan coloring pixel and the yellow coloring
pixel, reference can be made to the description in JP2006-098684A,
and the content thereof is incorporated herein by reference.
Examples of colorants contained in the cyan coloring pixel include
C. I. Pigment Blue 15:6, C. I. Pigment Blue 16, C.I. Pigment Green
7, and aluminum phthalocyanine. Examples of colorants contained in
the yellow coloring pixel include C.I. Pigment Yellow 138, C.I.
Pigment Yellow 139, C.I. Pigment Yellow 150, and C.I. Pigment
Yellow 185.
[0263] In the color filter of the embodiment of the present
invention, a pattern size of the magenta coloring pixel is
preferably 0.7 to 2.0 .mu.m, more preferably 0.7 to 1.4 .mu.m, and
still more preferably 0.7 to 1.1 .mu.m. In addition, a thickness of
the magenta coloring pixel is preferably 5 .mu.m or less, more
preferably 3 .mu.m or less, and still more preferably 1 .mu.m or
less. The lower limit of the film thickness is preferably 0.1 .mu.m
or more, more preferably 0.2 .mu.m or more, and still more
preferably 0.3 .mu.m or more.
[0264] In the color filter of the embodiment of the present
invention, a pattern size of the cyan coloring pixel is preferably
0.7 to 2.0 .mu.m, more preferably 0.7 to 1.4 .mu.m, and still more
preferably 0.7 to 1.1 .mu.m. In addition, a thickness of the cyan
coloring pixel is preferably 5 .mu.m or less, more preferably 3
.mu.m or less, and still more preferably 1 .mu.m or less. The lower
limit of the film thickness is preferably 0.1 .mu.m or more, more
preferably 0.2 .mu.m or more, and still more preferably 0.3 .mu.m
or more.
[0265] In the color filter of the embodiment of the present
invention, a pattern size of the yellow coloring pixel is
preferably 0.7 to 2.0 .mu.m, more preferably 0.7 to 1.4 .mu.m, and
still more preferably 0.7 to 1.1 .mu.m. In addition, a thickness of
the yellow coloring pixel is preferably 5 .mu.m or less, more
preferably 3 .mu.m or less, and still more preferably 1 .mu.m or
less. The lower limit of the film thickness is preferably 0.1 .mu.m
or more, more preferably 0.2 .mu.m or more, and still more
preferably 0.3 .mu.m or more.
[0266] The color filter of the embodiment of the present invention
can be used for a solid-state imaging element such as a charge
coupled device (CCD) and a complementary metal-oxide semiconductor
(CMOS), an image display device, or the like. In addition, a
solid-state imaging element including the color filter having the
cyan coloring pixel, the magenta coloring pixel, and the yellow
coloring pixel can be used in combination with a solid-state
imaging element including a color filter having a red coloring
pixel, a green coloring pixel, and a blue coloring pixel.
[0267] <Pattern Forming Method>
[0268] Next, a pattern forming method using the coloring
composition of the embodiment of the present invention will be
described. The pattern forming method includes a step of forming a
coloring composition layer on a support using the coloring
composition of the embodiment of the present invention and a step
of forming a pattern onto the coloring composition layer by
photolithography.
[0269] Pattern formation by the photolithography preferably
includes a step of patternwise exposing the coloring composition
layer and a step of removing unexposed areas by development to form
a pattern. A step of baking the coloring composition layer
(pre-baking step) and a step of baking the developed pattern
(post-baking step) may be provided, as desired. Hereinafter, the
respective steps will be described.
[0270] Step of Forming Coloring Composition Layer
[0271] In the step of forming a coloring composition layer, the
coloring composition layer is formed on a support, using the
coloring composition.
[0272] The support is not particularly limited, and can be
appropriately selected depending on applications. Examples of the
support include a glass base material, a base material for a
solid-state imaging element, on which a solid-state imaging element
(light-receiving element) such as a CCD and a CMOS is provided, and
a silicon base material. Further, an undercoat layer may be
provided on the base materials, as desired, so as to improve
adhesion to a layer above the base material, to prevent diffusion
of substance, or to flatten a surface of the base materials.
[0273] As a method for applying the coloring composition onto the
support, various coating methods such as slit coating, an ink jet
method, spin coating, cast coating, roll coating, and a screen
printing method can be used.
[0274] The coloring composition layer formed on the support may be
dried (pre-baked). In a case of forming a pattern by a
low-temperature process, pre-baking may not be performed. In a case
of performing the pre-baking, the pre-baking temperature is
preferably 150.degree. C. or lower, more preferably 120.degree. C.
or lower, and still more preferably 110.degree. C. or lower. The
lower limit may be set to, for example, 50.degree. C. or higher, or
to 80.degree. C. or higher. By setting the pre-baking temperature
to 150.degree. C. or lower, these characteristics can be more
effectively maintained in a case of a configuration in which a
photo-electric conversion film of an image sensor is formed of
organic materials. The pre-baking time is preferably 10 seconds to
300 seconds, more preferably 40 to 250 seconds, and still more
preferably 80 to 220 seconds. Drying can be performed using a hot
plate, an oven, or the like.
[0275] Exposing Step
[0276] Next, the coloring composition layer formed on the support
is patternwise exposed (exposing step). For example, the coloring
composition layer can be subjected to patternwise exposure by
performing exposure using an exposure device such as a stepper
through a mask having a predetermined mask pattern. Thus, the
exposed portion can be cured. As the radiation (light) which can be
used during the exposure, ultraviolet rays such as g-rays and
i-rays (particularly preferably i-rays) are preferably used. The
irradiation dose (exposure dose) is, for example, preferably 0.03
to 2.5 J/cm.sup.2 and more preferably 0.05 to 1.0 J/cm.sup.2. The
oxygen concentration during the exposure can be appropriately
selected, and the exposure may also be performed, for example, in a
low-oxygen atmosphere having an oxygen concentration of 19% by
volume or less (for example, 15% by volume, 5% by volume, and
substantially oxygen-free) or in a high-oxygen atmosphere having an
oxygen concentration of more than 21% by volume (for example, 22%
by volume, 30% by volume, and 50% by volume), in addition to an
atmospheric air. Further, the exposure illuminance can be
appropriately set, and can be usually selected from a range of
1,000 W/m.sup.2 to 100,000 W/m.sup.2 (for example, 5,000 W/m.sup.2,
15,000 W/m.sup.2, or 35,000 W/m.sup.2). Appropriate conditions of
each of the oxygen concentration and the illuminance of exposure
energy may be combined, and for example, a combination of the
oxygen concentration of 10% by volume and the illuminance of 10,000
W/m.sup.2, a combination of the oxygen concentration of 35% by
volume and the illuminance of 20,000 W/m.sup.2, or the like is
available.
[0277] Developing Step
[0278] Next, the unexposed areas are removed by development to form
a pattern. The removal of the unexposed areas by development can be
carried out using a developer. Thus, the coloring composition layer
of the unexposed areas in the exposing step is eluted into the
developer, and as a result, only a photocured portion remains. As
the developer, an organic alkali developer causing no damage on the
underlying solid-state imaging element, circuit, or the like is
preferable. The temperature of the developer is preferably, for
example, 20.degree. C. to 30.degree. C., and the development time
is preferably 20 to 180 seconds. Further, in order to improve
residue removing properties, a step of removing the developer by
shaking per 60 seconds and supplying a fresh developer may be
repeated multiple times.
[0279] As the developer, an aqueous alkaline solution obtained by
diluting an alkali agent with pure water is preferably used.
Examples of the alkali agent include aqueous ammonia, organic
alkaline compounds such as ethylamine, diethylamine,
dimethylethanolamine, diglycol amine, diethanolamine, hydroxyamine,
ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium
hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium
hydroxide, ethyltrimethylammonium hydroxide,
benzyltrimethylammonium hydroxide,
dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole,
piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene, and inorganic
alkaline compounds such as sodium hydroxide, potassium hydroxide,
sodium carbonate, sodium hydrogen carbonate, sodium silicate, and
sodium metasilicate. The concentration of the alkali agent in the
aqueous alkaline solution is preferably 0.001% to 10% by mass and
more preferably 0.01% to 1% by mass. Moreover, the developer may
further include a surfactant. Examples of the surfactant include
the surfactants described above, and the surfactant is preferably a
nonionic surfactant. From the viewpoints of transportation,
storage, and the like, the developer may be first produced as a
concentrated liquid and then diluted to a concentration required
upon the use. The dilution ratio is not particularly limited, and
can be set to, for example, a range of 1.5 to 100 times. In
addition, in a case where a developer including such an aqueous
alkaline solution is used, it is preferable to perform washing
(rinsing) with pure water after development.
[0280] After the development, a heating treatment (post-baking) can
also be performed after carrying out drying. The post-baking is a
heating treatment after development so as to complete the curing of
the film. In a case of performing the post-baking, the post-baking
temperature is preferably, for example, 100 to 240.degree. C. From
the viewpoint of curing of the film, the post-baking temperature is
more preferably 200 to 230.degree. C. The Young's modulus of the
film after post-baking is preferably 0.5 to 20 GPa and more
preferably 2.5 to 15 GPa. In addition, in a case where a support is
formed of a material having low heat resistance (for example, in a
case where the support includes an organic electroluminescence
(organic EL) element, an image sensor having a photo-electric
conversion film formed of organic materials, or the like), the
post-baking temperature is preferably 150.degree. C. or lower, more
preferably 120.degree. C. or lower, still more preferably
100.degree. C. or lower, and particularly preferably 90.degree. C.
or lower. The lower limit can be set to, for example, 50.degree. C.
or higher. The post-baking can be performed continuously or
batchwise by using a heating means such as a hot plate, a
convection oven (hot-air circulating dryer), and a high-frequency
heater so that the film after development (cured film) satisfies
the conditions.
[0281] The cured film preferably has high flatness. Specifically,
the surface roughness Ra is preferably 100 nm or less, more
preferably 40 nm or less, and still more preferably 15 nm or less.
The lower limit is not specified, but is preferably, for example
0.1 nm or more. The surface roughness can be measured, for example,
using an atomic force microscope (AFM) Dimension 3100 manufactured
by Veeco Instruments, Inc. In addition, the contact angle of water
on the cured film can be appropriately set to a preferred value and
is typically in the range of 50 to 110.degree.. The contact angle
can be measured, for example, using a contact angle meter CV-DT-A
Model (manufactured by Kyowa Interface Science Co., Ltd.).
[0282] A higher volume resistivity value of a pattern (pixel) is
desired. Specifically, the volume resistivity value of the pixel is
preferably 10.sup.9 .OMEGA.cm or more and more preferably 10.sup.11
.OMEGA.cm or more. The upper limit is not defined, but is, for
example, preferably 10.sup.14 .OMEGA.cm or less. The volume
resistivity value of the pixel can be measured, for example, using
an ultra high resistance meter 5410 (manufactured by Advantest
Corporation).
[0283] <Solid-State Imaging Element>
[0284] The solid-state imaging element of an embodiment of the
present invention has the above-mentioned color filter of the
embodiment of the present invention. The configuration of the
solid-state imaging element of the embodiment of the present
invention is not particularly limited as long as the solid-state
imaging element is configured to include the color filter in the
embodiment of the present invention and function as a solid-state
imaging element.
[0285] The solid-state imaging element is configured to have a
plurality of photodiodes constituting a light receiving area of the
solid-state imaging element (a charge coupled device (CCD) image
sensor, a complementary metal-oxide semiconductor (CMOS) image
sensor, or the like), and a transfer electrode formed of
polysilicon or the like on a base material; a light-shielding film
having openings only over the light receiving portion of the
photodiode, on the photodiodes and the transfer electrodes; a
device-protective film formed of silicon nitride or the like, which
is formed to coat the entire surface of the light-shielding film
and the light receiving portion of the photodiodes, on the
light-shielding film; and a color filter on the device-protective
film. In addition, the solid-state imaging element may also be
configured, for example, such that it has a light collecting means
(for example, a microlens, which is the same hereinafter) on a
device-protective film under a color filter (a side closer to the
base material), or has a light collecting means on a color filter.
Further, the color filter may have a structure in which a cured
film forming each coloring pixel is embedded in a space partitioned
in a lattice shape by a partition wall. The partition wall in this
case preferably has a low refractive index for each coloring pixel.
Examples of an imaging device having such a structure include the
devices described in JP2012-227478A and JP2014-179577A. An imaging
device comprising the solid-state imaging element of the embodiment
of the present invention can also be used as a vehicle camera or a
monitoring camera, in addition to a digital camera or electronic
equipment (mobile phones or the like) having an imaging
function.
[0286] <Image Display Device>
[0287] The color filter of the embodiment of the present invention
can be used for an image display device such as a liquid crystal
display device and an organic electroluminescence display device.
The definitions of image display devices or the details of the
respective image display devices are described in, for example,
"Electronic Display Device (Akio Sasaki, Kogyo Chosakai Publishing
Co., Ltd., published in 1990)", "Display Device (Sumiaki Ibuki,
Sangyo Tosho Co., Ltd., published in 1989)", and the like. In
addition, the liquid crystal display device is described in, for
example, "Liquid Crystal Display Technology for Next Generation
(edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd.,
published in 1994)". The liquid crystal display device to which the
present invention can be applied is not particularly limited, and
can be applied to, for example, liquid crystal display devices
employing various systems described in the "Liquid Crystal Display
Technology for Next Generation".
EXAMPLES
[0288] Hereinbelow, the present invention will be described in more
detail with reference to Examples. The materials, the amounts of
materials to be used, the proportions, the treatment details, the
treatment procedure, or the like shown in the Examples below may be
modified appropriately as long as the modifications do not depart
from the spirit of the present invention. Therefore, the scope of
the present invention is not limited to the specific Examples shown
below. In addition, "parts" and "%" are on a mass basis unless
otherwise specified.
[0289] <Measurement of Average Primary Particle Diameter of
Pigment>
[0290] Projected areas of a pigment were determined by a
transmission electron microscope (a device in accordance with a
field emission type transmission electron microscope, manufactured
by JEOL Ltd., JEM-2100F Type), and then an equivalent circle
diameter of the pigment was determined therefrom to calculate an
average primary particle diameter. More specifically, equivalent
circle diameters of 100 pigments were measured, and then the
equivalent circle diameters were arithmetically averaged for 80
pigments excluding 10 pigments from the largest size and 10
pigments from the smallest size among the 100 pigments to calculate
the average primary particle diameter of the pigment.
[0291] <Measurement of Weight-Average Molecular Weight>
[0292] The weight-average molecular weight (Mw) of a resin is
measured by the following method.
[0293] Types of columns: Columns formed by connection of TOSOH
TSKgel Super HZM-H,
TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000
[0294] Developing solvent: Tetrahydrofuran [0295] Column
temperature: 40.degree. C. [0296] Flow amount (amount of a sample
to be injected): 1.0 .mu.L (sample concentration: 0.1% by mass)
[0297] Device name: HLC-8220GPC manufactured by Tosob Corporation
[0298] Detector: Refractive index (RI) detector [0299] Calibration
curve base resin: Polystyrene resin
[0300] <Production of Refined Pigment>
Production Example 1
[0301] 50 parts by mass of a magenta pigment (C. I. Pigment Red
122), 500 parts by mass of sodium chloride (OSHIO MICRON MS-5,
manufactured by Ako Kasei Co., Ltd.), and 100 parts by mass of
diethylene glycol were introduced into a 1-gallon kneader made by
stainless steel (manufactured by INOUE MFG., INC.) and kneaded for
9 hours. Next, the mixture was poured into about 3 liters of water,
stirred by a high-speed mixer for 1 hour. Thereafter, the mixture
is filtered and washed with water to remove sodium chloride and
diethylene glycol, and then dried to obtain a refined magenta
pigment 1. An average primary particle diameter of the refined
magenta pigment 1 was 45 nm.
Production Example 2
[0302] In the same manner as Production Example 1, refined magenta
pigments 2 to 7 described in the following table were produced.
TABLE-US-00001 TABLE 1 Average primary particle diameter Type (nm)
Refined magenta pigment 1 C.I. Pigment Red 122 45 Refined magenta
pigment 2 C.I. Pigment Red 122 35 Refined magenta pigment 3 C.I.
Pigment Red 122 25 Refined magenta pigment 4 C.I. Pigment Red 202
45 Refined magenta pigment 5 C.I. Pigment Red 209 45 Refined
magenta pigment 6 C.I. Pigment Violet 23 45 Refined magenta pigment
7 C.I. Pigment Violet 19 45
[0303] A maximum absorption wavelength of C. I. Pigment Red 122 was
565 nm, and in a case where an absorbance of the maximum absorption
wavelength was 1, a wavelength at which an absorbance is 0.5 was
510 nm on a side where the wavelength was shorter than the maximum
absorption wavelength, and in a case where the absorbance of the
maximum absorption wavelength was 1, a wavelength at which an
absorbance is 0.5 was 585 nm on a side where the wavelength was
longer than the maximum absorption wavelength.
[0304] A maximum absorption wavelength of C. I. Pigment Red 202 was
575 nm, and in a case where an absorbance of the maximum absorption
wavelength was 1, a wavelength at which an absorbance is 0.5 was
555 nm on a side where the wavelength was shorter than the maximum
absorption wavelength, and in a case where the absorbance of the
maximum absorption wavelength was 1, a wavelength at which an
absorbance is 0.5 was 615 nm on a side where the wavelength was
longer than the maximum absorption wavelength.
[0305] A maximum absorption wavelength of C. I. Pigment Red 209 was
510 nm, and in a case where an absorbance of the maximum absorption
wavelength was 1, a wavelength at which an absorbance is 0.5 was
480 nm on a side where the wavelength was shorter than the maximum
absorption wavelength, and in a case where the absorbance of the
maximum absorption wavelength was 1, a wavelength at which an
absorbance is 0.5 was 590 nm on a side where the wavelength was
longer than the maximum absorption wavelength.
[0306] A maximum absorption wavelength of C. I. Pigment Violet 23
was 535 nm, and in a case where an absorbance of the maximum
absorption wavelength was 1, a wavelength at which an absorbance is
0.5 was 505 nm on a side where the wavelength was shorter than the
maximum absorption wavelength, and in a case where the absorbance
of the maximum absorption wavelength was 1, a wavelength at which
an absorbance is 0.5 was 590 nm on a side where the wavelength was
longer than the maximum absorption wavelength.
[0307] A maximum absorption wavelength of C. I. Pigment Violet 19
was 565 nm, and in a case where an absorbance of the maximum
absorption wavelength was 1, a wavelength at which an absorbance is
0.5 was 510 nm on a side where the wavelength was shorter than the
maximum absorption wavelength, and in a case where the absorbance
of the maximum absorption wavelength was 1, a wavelength at which
an absorbance is 0.5 was 585 nm on a side where the wavelength was
longer than the maximum absorption wavelength.
[0308] <Preparation of Pigment Dispersion Liquid>
[0309] Raw materials described in the following table were mixed to
obtain a mixed solution. The obtained mixed solution was subjected
to a dispersion treatment by using Ultra apex mill (trade name)
manufactured by Kotobuki Industries Co., Ltd. as a circulation type
dispersion apparatus (beads mill) to obtain a dispersion liquid.
The solid content of the obtained dispersion liquid was 20.0% by
mass.
TABLE-US-00002 TABLE 2 Pigment Pigment Pigment Pigment Pigment
Pigment Pigment Pigment Pigment Pigment Pigment dispersion
dispersion dispersion dispersion dispersion dispersion dispersion
dispersion dispersion dispersion dispersion liquid 1 liquid 2
liquid 3 liquid 4 liquid 5 liquid 6 liquid 7 liquid 8 liquid 9
liquid 10 liquid 11 Refined magenta 142.9 142 .9 pigment 1 Refined
magenta 142.9 pigment 2 Refined magenta 14 2.9 pigment 3 Refined
magenta 142.9 pigment 4 Refined magenta 142.9 pigment 3 Refined
magenta 142.9 pigment 6 Refined magenta 142.9 142.9 142.9 pigment 7
Dispersant 1 57.1 57.1 57.1 57.1 57.1 57.1 57.1 Dispermnt 2 57.1
Dispersant 3 57.1 Dispersant 4 57.1 Dispersant 5 57.1 PGMEA 680.0
680.0 680.0 680.0 680.0 680.0 680.0 680.0 680.0 680.0 680.0 PGME
120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0 120.0
Total amount 1000.0 1000.0 1000.0 1000.0 1000.0 1000.0 1000.0
1000.0 1000.0 1000.0 1000.0
[0310] The numerical values described in the above table are parts
by mass and the raw materials described in the above table are as
follows.
[0311] Refined Magenta Pigments 1 to 7: Above-Mentioned Refined
Magenta Pigments 1 to 7
[0312] Dispersant 1: Resin of the following structure (Mw=20,000,
acid value=36.0 mgKOH/g, amine value=47.0 mgKOH/g, the numerical
value described together with the main chain is a molar ratio and
the numerical value together with the repeating unit is the
repeating number)
##STR00019##
[0313] Dispersant 2: Resin of the following structure (Mw=20,000,
acid value=32.3 mgKOH/g, amine value=45.0 mgKOH/g, the numerical
value described together with the main chain is a molar ratio and
the numerical value together with the repeating unit is the
repeating number)
##STR00020##
[0314] Dispersant 3: Resin of the following structure (Mw=24,000,
acid value=49.4 mgKOH/g, amine value=0.0 mgKOH/g, the numerical
value described together with the main chain is a molar ratio and
the numerical value together with the repeating unit is the
repeating number)
##STR00021##
[0315] Dispersant 4: Resin of the following structure (Mw=21,000,
acid value=72.0 mgKOH/g, amine value=0.0 mgKOH/g, the numerical
value described together with the main chain is a molar ratio and
the numerical value together with the repeating unit is the
repeating number)
##STR00022##
[0316] Dispersant 5: Resin of the following structure (Mw=21,000,
acid value=94.8 mgKOH/g, amine value=0.0 mgKOH/g, the numerical
value described together with the main chain is a molar ratio and
the numerical value together with the repeating unit is the
repeating number)
##STR00023##
[0317] PGMEA: Propylene glycol monomethyl ether acetate
[0318] PGME: Propylene glycol monomethyl ether
[0319] <Preparation of Coloring Composition>
[0320] The raw materials described in the following table were
mixed to prepare a coloring composition (a magenta coloring
composition).
TABLE-US-00003 TABLE 3 Ex- Ex- Ex- Ex- Ex- Ex- Ex- Ex- Ex- Ex- Ex-
Ex Ex- Ex- Comparative ample ample ample ample ample ample ample
ample ample ample ample ample ample ample Example 1 2 3 4 5 6 7 8 9
10 11 12 13 14 1 Pigment- 67.69 67.69 67.69 dispersion liquid 1
Pigment 67.69 dispersion liquid 2 Pigment 67.69 dispersion liquid 3
Pigment 67.69 dispersion liquid 4 Pigment 67.69 dispersion liquid 5
Pigment 67.69 dispersion liquid 6 Pigment 67.69 dispersion liquid 7
Pigment 67.69 dispersion liquid 8 Pigment 67.69 dispersion liquid 9
Pigment 67.69 dispersion liquid 10 Pigment 67.69 67.69 67.69
dispersion liquid 11 Alkali-soluble 0.65 0.65 0.65 0.65 0.65 0.65
0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 resin 1 Alkali-soluble 0.65
resin 2 Polymerizable 1.86 1.86 1.86 1.86 1.86 1.86 1.86 1.86 1.86
1.86 1.86 1.86 1.86 compound 1 Polymerizable 1.86 1.86 compound 2
Photo- 0.67 0.67 0.67 0.67 0.67 0.67 0.67 0.67 0.67 0.67 0.67 0.67
0 .67 0.67 0.67 polymerization initiator 1 Ultraviolet 0.43 0.43
0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 absorber 1
Ultraviolet 0.43 absorber 2 Polymerization 0.01 0.01 0.01 0.01 0.01
0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 inhibitor 1
Surfactant 1 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
0.01 0.01 0.01 0.01 PGMEA 28.68 28.68 28.68 28.68 28.68 28.68 28.68
28.68 28.68 28.68 28.68 28.68 28.68 28.68 28.68
[0321] The numerical values described in the above table are parts
by mass and the raw materials described in the above table are as
follows.
[0322] Pigment Dispersion Liquids 1 to 11: Above-Mentioned Pigment
Dispersion Liquids 1 to 11
[0323] Alkali-soluble resin 1: Acrycure RD-F8 (manufactured by
Nippon Shokubai Co., Ltd., an alkali-soluble resin having
polymerizable group)
[0324] Alkali-soluble resin 2: Resin of the following structure
(Mw=11,000, acid value=216.6 mgKOH/g, the numerical value described
together with the main chain is a molar ratio and the numerical
value together with the repeating unit is the repeating number)
##STR00024##
[0325] Polymerizable compound 1: NK ESTER A-TMMT (manufactured by
Shin-Nakamura Chemical Co., Ltd.)
[0326] Polymerizable compound 2: OGSOL EA-0300 (manufactured by
Osaka Gas Chemicals Co., Ltd.)
[0327] Photopolymerization initiator 1: IRGACURE OXE-02
(manufactured by BASF)
[0328] Ultraviolet absorber 1: Compound having the following
structure
##STR00025##
[0329] Ultraviolet absorber 2: Compound having the following
structure
##STR00026##
[0330] Polymerization inhibitor 1: p-Methoxyphenol
[0331] Surfactant 1: Following compound (Mw=14,000, % representing
the ratio of the repeating unit is % by mole.)
##STR00027##
[0332] PGMEA: Propylene glycol monomethyl ether acetate
[0333] <Preparation of Cyan Coloring Composition>
[0334] A refined cyan pigment was obtained in the same manner as
Production Example 1 except that an aluminum phthalocyanine pigment
(cyan pigment) was used instead of C. I. Pigment Red 122. An
average primary particle diameter of the refined cyan pigment was
45 nm.
[0335] A cyan pigment dispersion liquid was prepared in the same
manner as the preparation of the pigment dispersion liquid 1 except
that the refined cyan pigment was used instead of the refined
magenta pigment 1 in the preparation of the pigment dispersion
liquid 1.
[0336] A cyan coloring composition 1 was prepared in the same
manner as the preparation of the coloring composition in Example 1
(magenta coloring composition) except that the cyan pigment
dispersion liquid was used instead of the pigment dispersion liquid
1 in the preparation of the coloring composition in Example 1
(magenta coloring composition).
[0337] In addition, a cyan coloring composition 2 was prepared in
the same manner as the preparation of the cyan coloring composition
1 except that C. I. Pigment Blue 16 was used instead of aluminum
phthalocyanine pigment.
[0338] <Preparation of Yellow Coloring Composition>
[0339] A refined yellow pigment was obtained in the same manner as
Production Example 1 except that C. I. Pigment Yellow 150 (yellow
pigment) was used instead of C. I. Pigment Red 122. An average
primary particle diameter of the refined yellow pigment was 45
nm.
[0340] A yellow pigment dispersion liquid was prepared in the same
manner as the preparation of the pigment dispersion liquid 1 except
that the refined yellow pigment was used instead of the refined
magenta pigment 1 in the preparation of the pigment dispersion
liquid 1.
[0341] A yellow coloring composition was prepared in the same
manner as the preparation of the coloring composition in Example 1
(magenta coloring composition) except that the yellow pigment
dispersion liquid was used instead of the pigment dispersion liquid
1 in the preparation of the coloring composition in Example 1
(magenta coloring composition).
[0342] <Evaluation Test of Photolithographic Properties>
[0343] The coloring compositions (the magenta coloring
compositions) described in Examples and Comparative Example
obtained by the above-mentioned method were applied onto an 8
inches (203.2 mm) silicon wafer with an undercoat layer by a spin
coating method using Act 8 manufactured by Tokyo Electron Limited.
so that the film thickness after the coating was 0.5 .mu.m, and
then heated at 100.degree. C. for 2 minutes using a hot plate to
form a composition layer. Next, the obtained composition layer was
exposed to light (exposure dose: 50 to 1,700 mJ/cm.sup.2) by using
an i-rays stepper exposure device (FPA-3000 i5+, manufactured by
Canon Inc.) through a mask having a pattern of 1.0 .mu.m square.
Next, the exposed composition layer was shower-developed at
23.degree. C. for 60 seconds using a 0.3% by mass of aqueous
solution of tetramethylammonium hydroxide (TMAH) as a developer.
Thereafter, rinsing was performed with pure water by spin shower to
form a pattern (a magenta coloring pixel).
[0344] The obtained pattern was observed at 20,000 times
magnification by using a scanning electron microscope (S-4800H,
manufactured by Hitachi High-Technologies Corporation.). Based on
the observed image, photolithographic properties were evaluated by
the following standard. The evaluation test of photolithographic
properties was performed 3 times for each coloring composition and
the result was collected and determined.
[0345] 5: The pattern is clear and there is no residue between the
patterns.
[0346] 4: The pattern is clear and there is a small residue between
the patterns.
[0347] 3: The pattern is slightly taper shaped, but there is a
small residue between the patterns.
[0348] 2: The pattern is taper shaped, and there is a lot of
residue between the patterns.
[0349] 1: The pattern is not formed.
[0350] <Evaluation Test of Photolithographic Properties
2>
[0351] The coloring compositions (the magenta coloring
compositions) described in Examples and Comparative Example
obtained by the above-mentioned method were applied onto an 8
inches (203.2 mm) silicon wafer with an undercoat layer by a spin
coating method using Act 8 manufactured by Tokyo Electron Limited,
so that the film thickness after the coating was 0.5 .mu.m, and
then heated at 100.degree. C. for 2 minutes using a hot plate to
form a composition layer. Next, the obtained composition layer was
exposed to light (exposure dose: 50 to 1,700 mJ/cm.sup.2) through a
mask having a pattern of 0.9 .mu.m square by using an i-rays
stepper exposure device (FPA-3000 i5+, manufactured by Canon Inc.).
Next, the exposed composition layer was shower-developed at
23.degree. C. for 60 seconds using a 0.3% by mass of aqueous
solution of tetramethylammonium hydroxide (TMAH) as a developer.
Thereafter, rinsing was performed with pure water by spin shower to
form a pattern (a magenta coloring pixel).
[0352] The obtained pattern was observed at 20,000 times
magnification by using a scanning electron microscope (S-4800H,
manufactured by Hitachi High-Technologies Corporation.). Based on
the observed image, photolithographic properties were evaluated by
the following standard. The evaluation test of photolithographic
properties was performed 3 times for each coloring composition and
the result was collected and determined.
[0353] 5: The pattern is clear and there is no residue between the
patterns.
[0354] 4: The pattern is clear and there is a small residue between
the patterns.
[0355] 3: The pattern is slightly taper shaped, but there is a
small residue between the patterns.
[0356] 2: The pattern is taper shaped, and there is a lot of
residue between the patterns.
[0357] 1: The pattern is not formed.
[0358] <Evaluation Test of Mixed Color>
[0359] A pattern (magenta coloring pixel) was formed on the 8
inches (203.2 mm) silicon wafer with the undercoat layer in the
same manner as the evaluation test of photolithographic properties
using the coloring composition (magenta coloring composition)
described in Examples and Comparative Example obtained by the
above-mentioned method. Transmittance (spectrum 1) of the pattern
in a range of 400 to 700 nm was measured by using a spectrometer
system (LVmicro V, manufactured by Lambda Vision Inc.).
[0360] Next, each of the cyan coloring pattern (cyan coloring
pixel) and yellow coloring pattern (yellow coloring pixel) was
formed on a pixel omission part of the magenta coloring pixel on
the silicon wafer of a glass wafer on which the magenta coloring
pixel was formed, by using the cyan coloring composition 1 and the
yellow coloring composition in the same manner as the evaluation
test of photolithographic properties, and then transmittance of the
magenta coloring pixel was measured (spectrum 2).
[0361] A maximum value of the variation of transmittance was
determined by using the spectrums 1 and 2 of the magenta coloring
pixel, and the mixed color was evaluated by the following
standard.
[0362] In addition, the measurement of transmittance was performed
5 times for each sample, and the average value of the 3 times
result except the maximum value and the minimum value was adopted.
Furthermore, the maximum value of the variation of transmittance
means a variation of transmittance of the magenta coloring pixel in
a wavelength which has the largest variation of transmittance in a
range of 400 to 700 nm before and after forming other coloring
pixels.
[0363] 5: Maximum value of variation of transmittance is less than
2%
[0364] 4: Maximum value of variation of transmittance is 2% or more
and less than 3%
[0365] 3: Maximum value of variation of transmittance is 3% or more
and less than 4%
[0366] 2: Maximum value of variation of transmittance is 4% or more
and less than 5%
[0367] 1: Maximum value of variation of transmittance is 5% or
more
[0368] <Light Resistance Evaluation>
[0369] The coloring compositions (magenta coloring compositions)
described in Examples and Comparative Example were applied onto a
soda glass (75 mm.times.75 mm square, 1.1 mm thickness) by a spin
coater (H-360S, manufactured by MIKASA CO., LTD.). Next, the
coloring composition was prebaked at 100.degree. C. for 2 minutes
by using a hot plate to obtain a coating film. The obtained coating
film was exposed to light in an exposure dose 1,000 mJ/cm.sup.2 by
an ultra-high pressure mercury lamp (USH-500BY, manufactured by
USHIO INC.). Subsequently, the coating film after exposure was
heated at 200.degree. C. for 5 minutes on a hot plate in an air
atmosphere to obtain a cured film having a film thickness of 0.5
.mu.m. Light transmittance (transmittance) of the obtained cured
film in a range of 400 to 700 nm was measured by using MCPD-3000
manufactured by OTSUKA ELECTRONICS Co., LTD.
[0370] Next, a UV cut filter (manufactured by AS ONE Corporation,
KU-1000100) was mounted on the produced cured film and a light
resistance test was performed by using a weather meter
(manufactured by Suga Test Instruments Co., Ltd., Xenon Weather
Meter SX75) to irradiating light of 100,000 lx for 50 hours
(cumulative irradiation dose: 5,000,000 lxh). The temperature of
the cured film (temperature in test apparatus) was set to
63.degree. C. The relative humidity in the test apparatus was set
to 50%. After performing the light resistance test, the
transmittance of the cured film was measured, the maximum value of
variation of transmittance was determined, and then the light
resistance was evaluated based on the following standard.
[0371] In addition, the measurement of transmittance was performed
5 times for each sample, and the average value of the 3 times
result except the maximum value and the minimum value was adopted.
Furthermore, the maximum value of the variation of transmittance
means a variation of transmittance of the cured film in a
wavelength which has the largest variation of transmittance in a
range of 400 to 700 nm before and after the light resistance
test.
[0372] 5: Maximum value of variation of transmittance is 3% or
less
[0373] 4: Maximum value of variation of transmittance is more than
3% and 5% or less
[0374] 3: Maximum value of variation of transmittance is more than
5% and 7% or less
[0375] 2: Maximum value of variation of transmittance is more than
7% and 10% or less
[0376] 1: Maximum value of variation of transmittance is more than
10%
TABLE-US-00004 TABLE 4 Photo- Photo- lithographic Mixed Light
lithographic properties color resistance properties 2 Example 1 4 5
5 3 Example 2 5 5 5 4 Example 3 5 5 4 4 Example 4 4 5 4 3 Example 5
4 5 4 3 Example 6 4 5 4 3 Example 7 3 5 5 3 Example 8 4 5 5 3
Example 9 4 5 5 3 Example 10 4 5 5 3 Example 11 5 5 5 4 Example 12
5 5 5 5 Example 13 5 5 5 5 Example 14 5 5 5 5 Comparative 1 2 2 1
Example 1
[0377] As shown in the above table, the coloring compositions of
Examples were excellent in photolithographic properties and capable
of suppressing an occurrence of mixed color between adjacent pixels
of other hues.
[0378] The same result was obtained in a case where the same test
was performed using the cyan coloring composition 2 instead of the
cyan coloring composition 1.
[0379] In the coloring composition of each example, the same effect
can be obtained by using two or more of the ultraviolet absorbers
in combination described in the present specification.
* * * * *