U.S. patent application number 14/786395 was filed with the patent office on 2016-06-30 for color material, color material dispersion liquid, color resin composition for color filters, color filter, liquid crystal display device and organic light-emitting display device.
The applicant listed for this patent is DAI NIPPON PRINTING CO., LTD.. Invention is credited to Daisuke ENDO, Fumiyasu MURAKAMI, Tomoki MURATA, Michihiro OGURA, Masato OKADA, Hiroaki SEGAWA.
Application Number | 20160187547 14/786395 |
Document ID | / |
Family ID | 51791570 |
Filed Date | 2016-06-30 |
United States Patent
Application |
20160187547 |
Kind Code |
A1 |
MURATA; Tomoki ; et
al. |
June 30, 2016 |
COLOR MATERIAL, COLOR MATERIAL DISPERSION LIQUID, COLOR RESIN
COMPOSITION FOR COLOR FILTERS, COLOR FILTER, LIQUID CRYSTAL DISPLAY
DEVICE AND ORGANIC LIGHT-EMITTING DISPLAY DEVICE
Abstract
The present invention is to provide a color material dispersion
liquid which is able to form a high-luminance coating film having
excellent heat resistance, with adjusting the color tone of the
coating film to a desired color tone. Disclosed is a color material
dispersion liquid containing: (A) a color material, (B) a
dispersant and (C) a solvent, wherein the color material (A)
contains a color material (A-1) in which at least a cation
represented by the following general formula (I) and a monovalent
anion represented by the following general formula (II) form a
salt: ##STR00001## (symbols in the general formulae (I) and (II)
are as described in the Description.)
Inventors: |
MURATA; Tomoki; (Tokyo-to,
JP) ; OGURA; Michihiro; (Tokyo-to, JP) ;
OKADA; Masato; (Tokyo-to, JP) ; ENDO; Daisuke;
(Tokyo-to, JP) ; MURAKAMI; Fumiyasu; (Tokyo-to,
JP) ; SEGAWA; Hiroaki; (Tokyo-to, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DAI NIPPON PRINTING CO., LTD. |
Tokyo |
|
JP |
|
|
Family ID: |
51791570 |
Appl. No.: |
14/786395 |
Filed: |
March 28, 2014 |
PCT Filed: |
March 28, 2014 |
PCT NO: |
PCT/JP2014/059089 |
371 Date: |
January 4, 2016 |
Current U.S.
Class: |
349/106 ;
252/586; 257/40; 359/892; 549/390 |
Current CPC
Class: |
C07D 311/82 20130101;
C09B 69/06 20130101; H01L 27/322 20130101; C09B 11/24 20130101;
C09B 11/12 20130101; G02B 5/223 20130101; G03F 7/022 20130101; G02F
1/133514 20130101; G03F 7/105 20130101; G03F 7/0007 20130101 |
International
Class: |
G02B 5/22 20060101
G02B005/22; H01L 27/32 20060101 H01L027/32; G02F 1/1335 20060101
G02F001/1335; C07D 311/82 20060101 C07D311/82; C09B 69/06 20060101
C09B069/06 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 26, 2013 |
JP |
2013-094537 |
Oct 23, 2013 |
JP |
2013-220657 |
Claims
1. A color material dispersion liquid comprising: (A) a color
material, (B) a dispersant and (C) a solvent, wherein the color
material (A) contains a color material (A-1) in which at least a
cation represented by the following general formula (I) and a
monovalent anion represented by the following general formula (II)
form a salt: ##STR00017## wherein A is an "a"-valent organic group
in which a carbon atom directly bound to N has no .pi. bond, and
the organic group is an aliphatic hydrocarbon group having a
saturated aliphatic hydrocarbon group at least at a terminal
position directly bound to N, or an aromatic group having the
aliphatic hydrocarbon group, and O, S, N can be contained in a
carbon chain of the organic group; each of R.sup.i to R.sup.v is
independently a hydrogen atom, an alkyl group which can have a
substituent group, or an aryl group which can have a substituent
group; R.sup.i and R.sup.iii can be bound to form a ring structure,
and/or R.sup.iv and R.sup.v can be bound to form a ring structure;
Ar.sup.1 is a divalent aromatic group which can have a substituent
group; a plurality of R.sup.is can be the same or different; a
plurality of R.sup.iis can be the same or different; a plurality of
R.sup.iiis can be the same or different; a plurality of R.sup.ivs
can be the same or different; a plurality of R.sup.vs can be the
same or different; a plurality of Ar.sup.1s can be the same or
different; "a" is a number of 2 or more; "n" is 0 or 1, and there
is no bond when "n" is 0; and a plurality of "n"s can be the same
or different; and wherein each of R.sup.1 to R.sup.4 is
independently a hydrogen atom, an alkyl group which can have a
substituent group, an aryl group which can have a substituent
group, or an aralkyl group which can have a substituent group;
R.sup.1 and R.sup.2 can be bound to form a ring structure, and/or
R.sup.3 and R.sup.4 can be bound to form a ring structure; R.sup.5
is a halogen atom, an alkyl group which can have a substituent
group, a sulfonato group (--SO.sub.3.sup.- group) or a carboxylato
group (--COO.sup.- group); m is 0 to 5; when there are a plurality
of R.sup.5s, they can be the same or different; each of R.sup.6 and
R.sup.7 is independently a hydrogen atom, a halogen atom, or an
alkyl group which can have a substituent group; and in R.sup.1 to
R.sup.5, two sulfonato groups (--SO.sub.3.sup.- groups) are
contained, or one sulfonato group (--SO.sub.3.sup.- group) and one
carboxylato group (--COO.sup.- group) are contained.
2. The color material dispersion liquid according to claim 1,
wherein the color material (A-1) is a color material which further
contains a polyoxometalate anion and is represented by the
following general formula (III): ##STR00018## wherein A is an
"a"-valent organic group in which a carbon atom directly bound to N
has no .pi. bond, and the organic group is an aliphatic hydrocarbon
group having a saturated aliphatic hydrocarbon group at least at a
terminal position directly bound to N, or an aromatic group having
the aliphatic hydrocarbon group, and O, S, N can be contained in a
carbon chain of the organic group; each of R.sup.i to R.sup.v is
independently a hydrogen atom, an alkyl group which can have a
substituent group, or an aryl group which can have a substituent
group; R.sup.ii and R.sup.iii can be bound to form a ring
structure, and/or R.sup.iv and R.sup.v can be bound to form a ring
structure; Ar.sup.1 is a divalent aromatic group which can have a
substituent group; a plurality of R.sup.is can be the same or
different; a plurality of R.sup.iis can be the same or different; a
plurality of R.sup.iiis can be the same or different; a plurality
of R.sup.ivs can be the same or different; a plurality of R.sup.vs
can be the same or different; a plurality of Ar.sup.1s can be the
same or different; "a" is a number of 2 or more; b is a number of 1
or more; "n" is 0 or 1, and there is no bond when "n" is 0; a
plurality of "n"s can be the same or different; each of R.sup.1 to
R.sup.4 is independently a hydrogen atom, an alkyl group which can
have a substituent group, an aryl group which can have a
substituent group, or an aralkyl group which can have a substituent
group; R.sup.1 and R.sup.2 can be bound to form a ring structure,
and/or R.sup.3 and R.sup.4 can be bound to form a ring structure;
R.sup.5 is a halogen atom, an alkyl group which can have a
substituent group, a sulfonato group (--SO.sub.3.sup.- group) or a
carboxylato group (--COO.sup.- group); m is 0 to 5; when there are
a plurality of R.sup.5s, they can be the same or different; each of
R.sup.6 and R.sup.7 is independently a hydrogen atom, a halogen
atom, or an alkyl group which can have a substituent group; in
R.sup.1 to R.sup.5, two sulfonato groups (--SO.sub.3.sup.- groups)
are contained, or one sulfonato group (--SO.sub.3.sup.- group) and
one carboxylato group (--COO.sup.- group) are contained; B.sup.d-
is a "d"-valent polyoxometalate anion; and c and e are positive
numbers.
3. The color material dispersion liquid according to claim 2,
wherein the polyoxometalate anion in the color material represented
by the general formula (III) contains at least tungsten, and a
molar ratio of the tungsten to molybdenum in the polyoxometalate
anion is 100:0 to 85:15.
4. A color resin composition for color filters, comprising: (A) a
color material, (B) a dispersant, (C) a solvent and (D) a binder
component, wherein the color material (A) contains a color material
(A-1) in which at least a cation represented by the following
general formula (I) and a monovalent anion represented by the
following general formula (II) form a salt: ##STR00019## wherein A
is an "a"-valent organic group in which a carbon atom directly
bound to N has no .pi. bond, and the organic group is an aliphatic
hydrocarbon group having a saturated aliphatic hydrocarbon group at
least at a terminal position directly bound to N, or an aromatic
group having the aliphatic hydrocarbon group, and O, S, N can be
contained in a carbon chain of the organic group; each of R.sup.i
to R.sup.v is independently a hydrogen atom, an alkyl group which
can have a substituent group, or an aryl group which can have a
substituent group; R.sup.ii and R.sup.iii can be bound to form a
ring structure, and/or R.sup.iv and R.sup.v can be bound to form a
ring structure; Ar.sup.1 is a divalent aromatic group which can
have a substituent group; a plurality of R.sup.is can be the same
or different; a plurality of R.sup.iis can be the same or
different; a plurality of R.sup.iiis can be the same or different;
a plurality of R.sup.ivs can be the same or different; a plurality
of R.sup.vs can be the same or different; a plurality of Ar.sup.1s
can be the same or different; "a" is a number of 2 or more; "n" is
0 or 1, and there is no bond when "n" is 0; and a plurality of "n"s
can be the same or different; and wherein each of R.sup.1 to
R.sup.4 is independently a hydrogen atom, an alkyl group which can
have a substituent group, an aryl group which can have a
substituent group, or an aralkyl group which can have a substituent
group; R.sup.1 and R.sup.2 can be bound to form a ring structure,
and/or R.sup.3 and R.sup.4 can be bound to form a ring structure;
R.sup.5 is a halogen atom, an alkyl group which can have a
substituent group, a sulfonato group (--SO.sub.3.sup.- group) or a
carboxylato group (--COO.sup.- group); m is 0 to 5; when there are
a plurality of R.sup.5s, they can be the same or different; each of
R.sup.6 and R.sup.7 is independently a hydrogen atom, a halogen
atom, or an alkyl group which can have a substituent group; and in
R.sup.1 to R.sup.5, two sulfonato groups (--SO.sub.3.sup.- groups)
are contained, or one sulfonato group (--SO.sub.3.sup.- group) and
one carboxylato group (--COO.sup.- group) are contained.
5. The color resin composition for color filters according to claim
4, wherein the color material (A-1) is a color material which
further contains a polyoxometalate anion and is represented by the
following general formula (III): ##STR00020## wherein A is an
"a"-valent organic group in which a carbon atom directly bound to N
has no .pi. bond, and the organic group is an aliphatic hydrocarbon
group having a saturated aliphatic hydrocarbon group at least at a
terminal position directly bound to N, or an aromatic group having
the aliphatic hydrocarbon group, and O, S, N can be contained in a
carbon chain of the organic group; each of R.sup.i to R.sup.v is
independently a hydrogen atom, an alkyl group which can have a
substituent group, or an aryl group which can have a substituent
group; R.sup.ii and R.sup.iii can be bound to form a ring
structure, and/or R.sup.iv and R.sup.v can be bound to form a ring
structure; Ar.sup.1 is a divalent aromatic group which can have a
substituent group; a plurality of R.sup.is can be the same or
different; a plurality of R.sup.iis can be the same or different; a
plurality of R.sup.iiis can be the same or different; a plurality
of R.sup.ivs can be the same or different; a plurality of R.sup.vs
can be the same or different; a plurality of Ar.sup.1s can be the
same or different; "a" is a number of 2 or more; b is a number of 1
or more; "n" is 0 or 1, and there is no bond when "n" is 0; a
plurality of "n"s can be the same or different; each of R.sup.1 to
R.sup.4 is independently a hydrogen atom, an alkyl group which can
have a substituent group, an aryl group which can have a
substituent group, or an aralkyl group which can have a substituent
group; R.sup.1 and R.sup.2 can be bound to form a ring structure,
and/or R.sup.3 and R.sup.4 can be bound to form a ring structure;
R.sup.5 is a halogen atom, an alkyl group which can have a
substituent group, a sulfonato group (--SO.sub.3.sup.- group) or a
carboxylato group (--COO.sup.- group); m is 0 to 5; when there are
a plurality of R.sup.5s, they can be the same or different; each of
R.sup.6 and R.sup.7 is independently a hydrogen atom, a halogen
atom, or an alkyl group which can have a substituent group; in
R.sup.1 to R.sup.5, two sulfonato groups (--SO.sub.3.sup.- groups)
are contained, or one sulfonato group (--SO.sub.3.sup.- group) and
one carboxylato group (--COO.sup.- group) are contained; B.sup.d-
is a "d"-valent polyoxometalate anion; and c and e are positive
numbers.
6. The color resin composition for color filters according to claim
5, wherein the polyoxometalate anion in the color material
represented by the general formula (III) contains at least
tungsten, and a molar ratio of the tungsten to molybdenum in the
polyoxometalate anion is 100:0 to 85:15.
7. A color filter comprising at least a transparent substrate and
color layers disposed on the substrate, wherein at least one of the
color layers contains a color material (A-1) in which at least a
cation represented by the following general formula (I) and a
monovalent anion represented by the following general formula (II)
form a salt: ##STR00021## wherein A is an "a"-valent organic group
in which a carbon atom directly bound to N has no .pi. bond, and
the organic group is an aliphatic hydrocarbon group having a
saturated aliphatic hydrocarbon group at least at a terminal
position directly bound to N, or an aromatic group having the
aliphatic hydrocarbon group, and O, S, N can be contained in a
carbon chain of the organic group; each of R.sup.i to R.sup.v is
independently a hydrogen atom, an alkyl group which can have a
substituent group, or an aryl group which can have a substituent
group; R.sup.ii and R.sup.iii can be bound to form a ring
structure, and/or R.sup.iv and R.sup.v can be bound to form a ring
structure; Ar.sup.1 is a divalent aromatic group which can have a
substituent group; a plurality of R.sup.is can be the same or
different; a plurality of R.sup.iis can be the same or different; a
plurality of R.sup.iiis can be the same or different; a plurality
of R.sup.ivs can be the same or different; a plurality of R.sup.vs
can be the same or different; a plurality of Ar.sup.1s can be the
same or different; "a" is a number of 2 or more; "n" is 0 or 1, and
there is no bond when "n" is 0; and a plurality of "n"s can be the
same or different; and wherein each of R.sup.1 to R.sup.4 is
independently a hydrogen atom, an alkyl group which can have a
substituent group, an aryl group which can have a substituent
group, or an aralkyl group which can have a substituent group;
R.sup.1 and R.sup.2 can be bound to form a ring structure, and/or
R.sup.3 and R.sup.4 can be bound to form a ring structure; R.sup.5
is a halogen atom, an alkyl group which can have a substituent
group, a sulfonato group (--SO.sub.3.sup.- group) or a carboxylato
group (--COO.sup.- group); m is 0 to 5; when there are a plurality
of R.sup.5 s, they can be the same or different; each of R.sup.6
and R.sup.7 is independently a hydrogen atom, a halogen atom, or an
alkyl group which can have a substituent group; and in R.sup.1 to
R.sup.5, two sulfonato groups (--SO.sub.3.sup.- groups) are
contained, or one sulfonato group (--SO.sub.3.sup.- group) and one
carboxylato group (--COO.sup.- group) are contained.
8. A liquid crystal display device comprising the color filter
defined by claim 7, a counter substrate, and a liquid crystal layer
disposed between the color filter and the counter substrate.
9. An organic light-emitting display device comprising the color
filter defined by claim 7 and an organic light-emitting
material.
10. A color material represented by the following general formula
(III'): ##STR00022## wherein A is an "a"-valent organic group in
which a carbon atom directly bound to N has no .pi. bond, and the
organic group is an aliphatic hydrocarbon group having a saturated
aliphatic hydrocarbon group at least at a terminal position
directly bound to N, or an aromatic group having the aliphatic
hydrocarbon group, and O, S, N can be contained in a carbon chain
of the organic group; each of R.sup.i to R.sup.v is independently a
hydrogen atom, an alkyl group which can have a substituent group,
or an aryl group which can have a substituent group; R.sup.ii and
R.sup.iii can be bound to form a ring structure, and/or R.sup.iv
and R.sup.v can be bound to form a ring structure; Ar.sup.1 is a
divalent aromatic group which can have a substituent group; a
plurality of R.sup.is can be the same or different; a plurality of
R.sup.iis can be the same or different; a plurality of R.sup.iiis
can be the same or different; a plurality of R.sup.ivs can be the
same or different; a plurality of R.sup.vs can be the same or
different; a plurality of Ar.sup.1s can be the same or different;
"a" is a number of 2 or more; b is a number of 1 or more; "n" is 0
or 1, and there is no bond when "n" is 0; a plurality of "n"s can
be the same or different; each of R.sup.1 to R.sup.4 is
independently a hydrogen atom, an alkyl group which can have a
substituent group, an aryl group which can have a substituent
group, or an aralkyl group which can have a substituent group;
R.sup.1 and R.sup.2 can be bound to form a ring structure, and/or
R.sup.3 and R.sup.4 can be bound to form a ring structure; R.sup.5
is a halogen atom, an alkyl group which can have a substituent
group, a sulfonato group (--SO.sub.3.sup.- group) or a carboxylato
group (--COO.sup.- group); m is 0 to 5; when there are a plurality
of R.sup.5s, they can be the same or different; each of R.sup.6 and
R.sup.7 is independently a hydrogen atom, a halogen atom, or an
alkyl group which can have a substituent group; in R.sup.1 to
R.sup.5, two sulfonato groups (--SO.sub.3.sup.- groups) are
contained, or one sulfonato group (--SO.sub.3.sup.- group) and one
carboxylato group (--COO.sup.- group) are contained; B.sup.d- is a
"d"-valent polyoxometalate anion; c and e are positive numbers; and
c:(d.times.e) is 5:95 to 50:50.
Description
TECHNICAL FIELD
[0001] The present invention relates to a color material, a color
material dispersion liquid, a color resin composition for color
filters, a color filter, a liquid crystal display device, and an
organic light-emitting display device.
BACKGROUND ART
[0002] Many thin image display devices as typified by displays,
i.e., flat panel displays, have been released on the market,
because they are thinner than cathode-ray tube displays and they do
not occupy much space in depth. Their market price has decreased
year by year with advances in production techniques, resulting in a
further increase in demand and a yearly increase in production.
Especially, color LCD TVs have almost become the mainstream of TVs.
Also in recent years, organic light-emitting display devices such
as organic EL displays, which emit light by themselves and thereby
have high visibility, have received attention as the next
generation of image display devices. In relation to the performance
of these image display devices, there is a strong demand for a
further increase in image quality, such as an increase in contrast
and color reproducibility, and a decrease in power consumption.
[0003] A color filter is used in these liquid crystal display
devices and organic light-emitting display devices. For example, in
the case of color LCDs, the amount of light is controlled by using
a back light as the light source and electrically driving the
liquid crystal. Colors are represented by the light that passed
through the color filter. Accordingly, the color filter is
indispensable for color representation in LCD TVs and plays a large
role in determining display performance. In organic light-emitting
display devices, a color image is formed in the same manner as
liquid crystal display devices, when the color filter is used in
combination with an organic, white light-emitting element.
[0004] A recent trend is that there is a demand for power-saving
image display devices. To increase backlight use efficiency, there
is a very high demand for high-luminance color filters. This is a
major issue especially for mobile displays such as mobile phones,
smart phones and tablet PCs.
[0005] Even though technological advances have increased battery
capacity, there is still a limit on battery capacity of mobile
devices. Meanwhile, there is a trend that power consumption has
grown with the increase in screen size. Image display devices
containing a color filter determine the design and performance of
mobile terminal devices, because they are directly linked to the
usable time and charging frequency of mobile terminal devices.
[0006] In general, a color filter has a transparent substrate,
color layers made of color patterns of the three primary colors
(red, green and blue), and a light shielding part formed on the
transparent substrate so as to define each color pattern.
[0007] To form such color layers, a pigment dispersion method in
which pigments with excellent heat resistance and light resistance
are used as color materials, has been widely used. However, it is
difficult for color filters produced by use of pigments to satisfy
the latest demand for higher luminance.
[0008] As a means to achieve higher luminance, color resin
compositions for color filters, which contain dyes, have been
studied. Compared to pigments, dyes generally have a higher
transmittance and are able to produce a high-luminance color
filter. However, dyes are problematic in that they are inferior in
heat resistance and light resistance to pigments and the
chromaticity is likely to change when they are heated at high
temperature in color filter production process, for example. Also,
color resin compositions containing dyes have such a problem that
aggregates are likely to be precipitated during drying process.
Aggregates precipitated in a coating film lead to a remarkable
deterioration in contrast and make it difficult to use the coating
film as a color layer.
[0009] As a means to improve various kinds of resistance properties
of dyes, a method for producing a salt-forming dye is known.
[0010] In Patent Literature 1, a color composition for color
filters is disclosed as a color resin composition for color filters
which is excellent in color characteristics, heat resistance, light
resistance and solvent resistance, the color composition containing
a salt-forming compound formed from a basic dye and an anion
component having a molecular weight of 200 to 3,500. However, a
color layer using the color composition for color filters disclosed
in Patent Literature 1 shows insufficient heat resistance during a
high-temperature heating step in a color filter production
step.
[0011] In Patent Literature 2, a salt is disclosed as a dye with an
excellent molar absorbance coefficient, the salt being formed from
a cation having a xanthene skeleton and an anion having a
triphenylmethane skeleton. In Patent Literature 2, the salt is
described to be soluble in organic solvents, and it is not
dispersed in resin compositions for use.
[0012] A color filter and so on are disclosed in Patent Literature
3 by the inventors of the present invention, which use specific
color materials containing divalent or higher anions and divalent
or higher cations, in which dye skeletons are crosslinked by
crosslinking groups. It is disclosed that the color materials are
excellent in heat resistance since, due to containing the divalent
or higher anions, molecular associations are formed therein, and
color filters using the color materials have high contrast and are
excellent in solvent resistance and electric reliability.
CITATION LIST
[0013] Patent Literature 1: International Publication No.
WO2011/037195
[0014] Patent Literature 2: Japanese Patent Application Laid-Open
No. 2012-233033
[0015] Patent Literature 3: International Publication No.
WO2012/144521
SUMMARY OF INVENTION
Technical Problem
[0016] Since excellent heat resistance and high luminance can be
expected, the inventors of the present invention studied the use of
color materials described in Patent Literature 3. However, to
adjust the color tones of the color materials to desired color
tones, it is needed to use the color materials in combination with
other color materials.
[0017] In the case of using conventionally-used dioxazine-based
violet pigments as other color materials, due to low transmittance
of the pigments, there is a problem of a decrease in luminance. In
the case of using dyes, there is a problem of a decrease in heat
resistance and light resistance, resulting in a decrease in
luminance. In the case of using metal lake pigments, although the
pigments have higher heat resistance than dyes, the pigments are
still insufficient in heat resistance and result in a problem of a
decrease in luminance.
[0018] The present invention was achieved in light of the above
circumstances. An object of the present invention is to provide: a
color material dispersion liquid which is able to form a
high-luminance coating film having excellent heat resistance, with
adjusting the color tone of the coating film to a desired color
tone; a color resin composition for color filters, which is able to
form a high-luminance color layer having excellent heat resistance,
with adjusting the color tone of the color layer to a desired color
tone; a high-luminance color filter using the color resin
composition; a liquid crystal display device and an organic
light-emitting display device each having the color filter; and a
color material which has excellent heat resistance and is able to
increase the temporal stability of the color resin composition.
Solution to Problem
[0019] The color material dispersion liquid according to the
present invention includes: (A) a color material, (B) a dispersant
and (C) a solvent, wherein the color material (A) includes a color
material (A-1) in which at least a cation represented by the
following general formula (I) and a monovalent anion represented by
the following general formula (II) form a salt:
##STR00002##
[0020] wherein A is an "a"-valent organic group in which a carbon
atom directly bound to N has no .pi. bond, and the organic group is
an aliphatic hydrocarbon group having a saturated aliphatic
hydrocarbon group at least at a terminal position directly bound to
N, or an aromatic group having the aliphatic hydrocarbon group, and
O, S, N can be contained in a carbon chain of the organic group;
each of R.sup.i to R.sup.v is independently a hydrogen atom, an
alkyl group which can have a substituent group, or an aryl group
which can have a substituent group; R.sup.ii and R.sup.iii can be
bound to form a ring structure, and/or R.sup.iv and R.sup.v can be
bound to form a ring structure; Ar.sup.1 is a divalent aromatic
group which can have a substituent group; a plurality of R.sup.is
can be the same or different; a plurality of R.sup.iis can be the
same or different; a plurality of R.sup.iiis can be the same or
different; a plurality of R.sup.ivs can be the same or different; a
plurality of R.sup.vs can be the same or different; a plurality of
Ar.sup.1s can be the same or different;
[0021] "a" is a number of 2 or more; "n" is 0 or 1, and there is no
bond when "n" is 0; and a plurality of "n"s can be the same or
different; and
[0022] wherein each of R.sup.1 to R.sup.4 is independently a
hydrogen atom, an alkyl group which can have a substituent group,
an aryl group which can have a substituent group, or an aralkyl
group which can have a substituent group; R.sup.1 and R.sup.2 can
be bound to form a ring structure, and/or R.sup.3 and R.sup.4 can
be bound to form a ring structure; R.sup.5 is a halogen atom, an
alkyl group which can have a substituent group, a sulfonato group
(--SO.sub.3.sup.- group) or a carboxylato group (--COO.sup.-
group); m is 0 to 5; when there are a plurality of R.sup.5s, they
can be the same or different; each of R.sup.6 and R.sup.7 is
independently a hydrogen atom, a halogen atom, or an alkyl group
which can have a substituent group; and
[0023] in R.sup.1 to R.sup.5, two sulfonato groups
(--SO.sub.3.sup.- groups) are contained, or one sulfonato group
(--SO.sub.3.sup.- group) and one carboxylato group (--COO.sup.-
group) are contained.
[0024] The color resin composition for color filters according to
the present invention includes: (A) a color material, (B) a
dispersant, (C) a solvent and (D) a binder component, wherein the
color material (A) contains a color material (A-1) in which at
least a cation represented by the general formula (I) and a
monovalent anion represented by the general formula (II) form a
salt.
[0025] The color filter according to the present invention includes
at least a transparent substrate and color layers disposed on the
substrate, wherein at least one of the color layers contains a
color material (A-1) in which at least a cation represented by the
general formula (I) and a monovalent anion represented by the
general formula (II) form a salt:
[0026] In the color material dispersion liquid according to the
present invention, the color resin composition for color filters
according to the present invention, and the color filter according
to the present invention, from the viewpoint of heat resistance and
dispersibility, it is preferable that the color material (A-1) is a
color material which further contains a polyoxometalate anion and
is represented by the following general formula (III):
##STR00003##
[0027] wherein A is an "a"-valent organic group in which a carbon
atom directly bound to N has no .pi. bond, and the organic group is
an aliphatic hydrocarbon group having a saturated aliphatic
hydrocarbon group at least at a terminal position directly bound to
N, or an aromatic group having the aliphatic hydrocarbon group, and
O, S, N can be contained in a carbon chain of the organic group;
each of R.sup.i to R.sup.v is independently a hydrogen atom, an
alkyl group which can have a substituent group, or an aryl group
which can have a substituent group; R.sup.ii and R.sup.iii can be
bound to form a ring structure, and/or R.sup.iv and R.sup.v can be
bound to form a ring structure; Ar.sup.1 is a divalent aromatic
group which can have a substituent group; a plurality of R.sup.is
can be the same or different; a plurality of R.sup.iis can be the
same or different; a plurality of R.sup.iiis can be the same or
different; a plurality of R.sup.ivs can be the same or different; a
plurality of R.sup.vs can be the same or different; a plurality of
Ar.sup.1s can be the same or different;
[0028] "a" is a number of 2 or more; b is a number of 1 or more;
"n" is 0 or 1, and there is no bond when "n" is 0; a plurality of
"n"s can be the same or different;
[0029] each of R.sup.1 to R.sup.4 is independently a hydrogen atom,
an alkyl group which can have a substituent group, an aryl group
which can have a substituent group, or an aralkyl group which can
have a substituent group; R.sup.1 and R.sup.2 can be bound to form
a ring structure, and/or R.sup.3 and R.sup.4 can be bound to form a
ring structure; R.sup.5 is a halogen atom, an alkyl group which can
have a substituent group, a sulfonato group (--SO.sub.3.sup.-
group) or a carboxylato group (--COO.sup.- group); m is 0 to 5;
when there are a plurality of R.sup.5s, they can be the same or
different; each of R.sup.6 and R.sup.7 is independently a hydrogen
atom, a halogen atom, or an alkyl group which can have a
substituent group;
[0030] in R.sup.1 to R.sup.5, two sulfonato groups
(--SO.sub.3.sup.- groups) are contained, or one sulfonato group
(--SO.sub.3.sup.- group) and one carboxylato group (--COO.sup.-
group) are contained;
[0031] B.sup.d- is a "d"-valent polyoxometalate anion; and c and e
are positive numbers.
[0032] In the color material dispersion liquid according to the
present invention, the color resin composition for color filters
according to the present invention, and the color filter according
to the present invention, from the viewpoint of achieving both heat
resistance and light resistance, it is preferable that the
polyoxometalate anion in the color material represented by the
general formula (III) contains at least tungsten, and a molar ratio
of the tungsten to molybdenum in the polyoxometalate anion is 100:0
to 85:15.
[0033] The present invention provides a liquid crystal display
device including the color filter according to the present
invention, a counter substrate, and a liquid crystal layer disposed
between the color filter and the counter substrate.
[0034] Also, the present invention provides an organic
light-emitting display device including the color filter according
to the present invention and an organic light-emitting
material.
[0035] Also, the present invention provides a color material
represented by the following general formula (III'):
##STR00004##
[0036] wherein A is an "a"-valent organic group in which a carbon
atom directly bound to N has no .pi. bond, and the organic group is
an aliphatic hydrocarbon group having a saturated aliphatic
hydrocarbon group at least at a terminal position directly bound to
N, or an aromatic group having the aliphatic hydrocarbon group, and
O, S, N can be contained in a carbon chain of the organic group;
each of R.sup.i to R.sup.v is independently a hydrogen atom, an
alkyl group which can have a substituent group, or an aryl group
which can have a substituent group; R.sup.ii and R.sup.iii can be
bound to form a ring structure, and/or R.sup.ii and R.sup.v can be
bound to form a ring structure; Ar.sup.1 is a divalent aromatic
group which can have a substituent group; a plurality of R.sup.is
can be the same or different; a plurality of R.sup.iis can be the
same or different; a plurality of R.sup.iiis can be the same or
different; a plurality of R.sup.ivs can be the same or different; a
plurality of R.sup.vs can be the same or different; a plurality of
Ar.sup.1s can be the same or different;
[0037] "a" is a number of 2 or more; b is a number of 1 or more;
"n" is 0 or 1, and there is no bond when "n" is 0; a plurality of
"n"s can be the same or different;
[0038] each of R.sup.1 to R.sup.4 is independently a hydrogen atom,
an alkyl group which can have a substituent group, an aryl group
which can have a substituent group, or an aralkyl group which can
have a substituent group; R.sup.1 and R.sup.2 can be bound to form
a ring structure, and/or R.sup.3 and R.sup.4 can be bound to form a
ring structure; R.sup.5 is a halogen atom, an alkyl group which can
have a substituent group, a sulfonato group (--SO.sub.3.sup.-
group) or a carboxylato group (--COO.sup.- group); m is 0 to 5;
when there are a plurality of R.sup.5s, they can be the same or
different; each of R.sup.6 and R.sup.7 is independently a hydrogen
atom, a halogen atom, or an alkyl group which can have a
substituent group;
[0039] in R.sup.1 to R.sup.5, two sulfonato groups
(--SO.sub.3.sup.- groups) are contained, or one sulfonato group
(--SO.sub.3.sup.- group) and one carboxylato group (--COO.sup.-
group) are contained;
[0040] B.sup.d- is a "d"-valent polyoxometalate anion; c and e are
positive numbers; and c:(d.times.e) is 5:95 to 50:50.
Advantageous Effects of Invention
[0041] According to the present invention, the following can be
provided: a color material dispersion liquid which is able to form
a high-luminance coating film having excellent heat resistance,
with adjusting the color tone of the coating film to a desired
color tone; a color resin composition for color filters, which is
able to form a high-luminance color layer having excellent heat
resistance, with adjusting the color tone of the color layer to a
desired color tone; a high-luminance color filter using the color
resin composition; a liquid crystal display device and an organic
light-emitting display device each having the color filter; and a
color material which has excellent heat resistance and is able to
increase the temporal stability of the color resin composition.
BRIEF DESCRIPTION OF DRAWINGS
[0042] FIG. 1 is a schematic sectional view of an example of the
color filter of the present invention.
[0043] FIG. 2 is a schematic sectional view of an example of the
liquid crystal display device of the present invention.
[0044] FIG. 3 is a schematic sectional view of an example of the
organic light-emitting display device of the present invention.
[0045] FIG. 4 is a schematic view of an example of a color material
(A-1).
[0046] FIG. 5 is a schematic view of a different example of the
color material (A-1).
[0047] FIG. 6 is a schematic view of an example of a color material
in which a cation represented by the general formula (I) and a
polyoxometalate anion form a salt.
[0048] FIG. 7 is a schematic view of an example of a color material
represented by the general formula (III').
DESCRIPTION OF EMBODIMENTS
[0049] Hereinafter, a color material dispersion liquid, a color
material, a color resin composition for color filters, a color
filter, a liquid crystal display device, and an organic
light-emitting display device, which are according to the present
invention, will be described in order.
[0050] In the present invention, "light" encompasses
electromagnetic waves in visible and non-visible wavelength ranges
and radial rays. Radial rays include microwaves and electron beams,
more specifically, electromagnetic waves having a wavelength of 5
.mu.m or less and electron beams.
[0051] Also in the present invention, "(meth)acrylic" means any of
acrylic and methacrylic, and "(meth)acrylate" means any of acrylate
and methacrylate.
[0052] Also in the present invention, "organic group" means a group
having one or more carbon atoms.
1. Color Material Dispersion Liquid
[0053] The color material dispersion liquid according to the
present invention includes: (A) a color material, (B) a dispersant
and (C) a solvent, wherein the color material (A) contains a color
material (A-1) in which at least a cation represented by the
following general formula (I) and a monovalent anion represented by
the following general formula (II) form a salt:
##STR00005##
[0054] wherein A is an "a"-valent organic group in which a carbon
atom directly bound to N has no .pi. bond, and the organic group is
an aliphatic hydrocarbon group having a saturated aliphatic
hydrocarbon group at least at a terminal position directly bound to
N, or an aromatic group having the aliphatic hydrocarbon group, and
O, S, N can be contained in a carbon chain of the organic group;
each of R.sup.i to R.sup.v is independently a hydrogen atom, an
alkyl group which can have a substituent group, or an aryl group
which can have a substituent group; R.sup.ii and R.sup.iii can be
bound to form a ring structure, and/or R.sup.iv and R.sup.v can be
bound to form a ring structure; Ar.sup.1 is a divalent aromatic
group which can have a substituent group; a plurality of R.sup.is
can be the same or different; a plurality of R.sup.iis can be the
same or different; a plurality of R.sup.iiis can be the same or
different; a plurality of R.sup.ivs can be the same or different; a
plurality of R.sup.vs can be the same or different; a plurality of
Ar.sup.1s can be the same or different;
[0055] "a" is a number of 2 or more; "n" is 0 or 1, and there is no
bond when "n" is 0; and a plurality of "n"s can be the same or
different; and
[0056] wherein each of R.sup.1 to R.sup.4 is independently a
hydrogen atom, an alkyl group which can have a substituent group,
an aryl group which can have a substituent group, or an aralkyl
group which can have a substituent group; R.sup.1 and R.sup.2 can
be bound to form a ring structure, and/or R.sup.3 and R.sup.4 can
be bound to form a ring structure; R.sup.5 is a halogen atom, an
alkyl group which can have a substituent group, a sulfonato group
(--SO.sub.3.sup.- group) or a carboxylato group (--COO.sup.-
group); m is 0 to 5; when there are a plurality of R.sup.5s, they
can be the same or different; each of R.sup.6 and R.sup.7 is
independently a hydrogen atom, a halogen atom, or an alkyl group
which can have a substituent group; and
[0057] in R.sup.1 to R.sup.5, two sulfonato groups
(--SO.sub.3.sup.- groups) are contained, or one sulfonato group
(--SO.sub.3.sup.- group) and one carboxylato group (--COO.sup.-
group) are contained.
[0058] In the color material dispersion liquid of the present
invention, the above-specified color material (A-1) is used as the
color material (A) and dispersed in the solvent (C). Therefore, the
color material dispersion liquid becomes a color material
dispersion liquid which is able to form a high-luminance coating
film having excellent heat resistance, with adjusting the color
tone of the coating film to a desired color tone.
[0059] The mechanism that the above-described effects are exerted
by the above-specified combination is not clear yet; however, it is
presumed as follows.
[0060] The cation represented by the general formula (I) has a
plurality of color-forming moieties, and the color-forming moieties
have a similar basic skeleton to that of basic dyes. Therefore, as
with conventional dyes, the cation represented by the general
formula (I) has excellent transmittance; meanwhile, the cation has
a higher molecular weight and better heat resistance than
conventional basic dyes. In the color material (A-1), such a cation
represented by the general formula (I) and the monovalent anion
represented by the general formula (II) form a salt. Therefore, it
is presumed that the molecular weight and heat resistance of the
color material are further increased, with adjusting the color tone
of the color material dispersion liquid to a desired color tone,
and high luminance can be achieved even after going through a
high-temperature heating step included in a color filter production
step.
[0061] A xanthene-based dye or lake pigment is less likely to be
dispersed solely, so that a large amount of dispersant has been
used. In the present invention, the color material (A-1) is
dispersed by the dispersant (B) while the cation and the anion form
a salt. Accordingly, compared to the case of separately dispersing
a color material containing the cation represented by the general
formula (I) and a color material containing the anion represented
by the general formula (II), the amount of the dispersant used can
be reduced. Therefore, the color material dispersion liquid of the
present invention can be sufficiently dispersed even in the case
where the content of the color material is increased; moreover, the
color material dispersion liquid can become a color material
dispersion liquid with high color density. Due to this reason, the
range of design can be extended by the use of the color material
dispersion liquid of the present invention, such as increasing the
content of the binder component or other component in the color
resin composition for color filters. Also, even in the case where
the color material dispersion liquid is formed into a thinner
coating film than ever before, a desired color tone can be
obtained.
[0062] The color material dispersion liquid of the present
invention contains at least the color material (A), the dispersant
(B) and the solvent (C). It can further contain other components,
as long as the effects of the present invention are not
impaired.
[0063] Hereinafter, the components of such a color material
dispersion liquid of the present invention will be described in
detail.
[Color Material (A)]
[0064] The color material (A) used in the present invention
contains the color material (A-1) in which at least the cation
represented by the general formula (I) and the monovalent anion
represented by the general formula (II) form a salt. It can further
contain other color material, as long as the effects of the present
invention are not impaired. In the present invention, by dispersing
the color material (A-1) in which the cation represented by the
general formula (I) and the monovalent anion represented by the
general formula (II) form a salt, excellent dispersibility and heat
resistance can be obtained; color density can be increased; and a
high-luminance color filter can be obtained.
<Color Material (A-1)>
[0065] In the present invention, by using the color material (A-1)
in which the cation represented by the following general formula
(I) and the monovalent anion represented by the following general
formula (II) form a salt as a color material, a higher-luminance
color filter can be obtained; moreover, a color layer with
excellent solvent resistance and electric reliability can be
formed:
##STR00006##
[0066] wherein A is an "a"-valent organic group in which a carbon
atom directly bound to N has no .pi. bond, and the organic group is
an aliphatic hydrocarbon group having a saturated aliphatic
hydrocarbon group at least at a terminal position directly bound to
N, or an aromatic group having the aliphatic hydrocarbon group, and
O, S, N can be contained in a carbon chain of the organic group;
each of R.sup.i to R.sup.v is independently a hydrogen atom, an
alkyl group which can have a substituent group, or an aryl group
which can have a substituent group; R.sup.ii and R.sup.iii can be
bound to form a ring structure, and/or R.sup.iv and R.sup.v can be
bound to form a ring structure; Ar.sup.1 is a divalent aromatic
group which can have a substituent group; a plurality of R.sup.is
can be the same or different; a plurality of R.sup.iis can be the
same or different; a plurality of R.sup.iiis can be the same or
different; a plurality of R.sup.ivs can be the same or different; a
plurality of R.sup.vs can be the same or different; a plurality of
Ar.sup.1s can be the same or different;
[0067] "a" is a number of 2 or more; "n" is 0 or 1, and there is no
bond when "n" is 0; and a plurality of "n"s can be the same or
different; and
[0068] wherein each of R.sup.1 to R.sup.4 is independently a
hydrogen atom, an alkyl group which can have a substituent group,
an aryl group which can have a substituent group, or an aralkyl
group which can have a substituent group; R.sup.1 and R.sup.2 can
be bound to form a ring structure, and/or R.sup.3 and R.sup.4 can
be bound to form a ring structure; R.sup.5 is a halogen atom, an
alkyl group which can have a substituent group, a sulfonato group
(--SO.sub.3.sup.- group) or a carboxylato group (--COO.sup.-
group); m is 0 to 5; when there are a plurality of R.sup.5s, they
can be the same or different; each of R.sup.6 and R.sup.7 is
independently a hydrogen atom, a halogen atom, or an alkyl group
which can have a substituent group; and
[0069] in R.sup.1 to R.sup.5, two sulfonato groups
(--SO.sub.3.sup.- groups) are contained, or one sulfonato group
(--SO.sub.3.sup.- group) and one carboxylato group (--COO.sup.-
group) are contained.
[0070] A schematic view of the color material (A-1) is shown in
FIG. 4. In a color material 110, which is the color material (A-1),
a cation 103 represented by the general formula (I), in which a
plurality of color-forming moieties 101 are connected through a
linking group A (102), and monovalent anions 104 represented by the
general formula (II) form a salt. Since the color-forming moieties
101 of the cation 103 represented by the general formula (I) are
cationic moieties, it is presumed that the monovalent anions 104
represented by the general formula (II) form ion pairs with the
color-forming moieties 101. Since the color-forming moieties 101
and the monovalent anions 104 represented by the general formula
(II) are similar in carbon skeleton, such as having an aromatic
ring, it is presumed that ion pair dissociation is inhibited by an
interaction such as n-n interaction. As a result, it is presumed
that heat resistance is further increased.
(Cation Represented by the General Formula (I))
[0071] The color material (A-1) used in the present invention has
the cation represented by the following general formula (I). Due to
containing the cation, the color material (A-1) has excellent heat
resistance.
##STR00007##
(Symbols in the General Formula (I) are as Described Above.)
[0072] In the general formula (I), A is an "a"-valent organic group
in which a carbon atom directly bound to N (nitrogen atom) has no
.pi. bond. The organic group is an aliphatic hydrocarbon group
having a saturated aliphatic hydrocarbon group at least at a
terminal position directly bound to N, or an aromatic group having
the aliphatic hydrocarbon group, and O (oxygen atom), S (sulfur
atom), N (nitrogen atom) can be contained in a carbon chain of the
organic group. Since the carbon atom directly bound to N has no
.pi. bond, the color characteristics of the cationic color-forming
moiety, such as color tone and transmittance, are not affected by
the linking group A and other color-forming moieties, thereby
allowing the same color as that of a single color-forming
moiety.
[0073] In A, as long as the carbon atom being at the terminal
position and directly bound to N has no .pi. bond, the aliphatic
hydrocarbon group having a saturated aliphatic hydrocarbon group at
least at a terminal position directly bound to N, can be in a
straight-chain, branched-chain or cyclic form, have an unsaturated
bond in carbon atoms except the one in the terminal position, have
a substituent group, or contain O, S, N in the carbon chain. For
example, a carbonyl group, a carboxyl group, an oxycarbonyl group
and/or an amide group can be contained, and a hydrogen atom can be
substituted by a halogen atom, etc.
[0074] Also in A, as the aromatic group having an aliphatic
hydrocarbon group, there may be exemplified a monocyclic or
polycyclic aromatic group which has an aliphatic hydrocarbon group
having a saturated aliphatic hydrocarbon group at least at the
terminal position directly bound to N. The aromatic group can have
a substituent group, and it can be a heterocyclic ring containing
O, S, N.
[0075] Particularly, from the viewpoint of skeleton toughness, it
is preferable that A contains a cyclic aliphatic hydrocarbon group
or an aromatic group.
[0076] As the cyclic aliphatic hydrocarbon group, a bridged
alicyclic hydrocarbon group is particularly preferable from the
viewpoint of skeleton toughness. The bridged alicyclic hydrocarbon
group refers to a polycyclic aliphatic hydrocarbon group having a
bridged structure in the aliphatic ring and having a polycyclic
structure. The examples include norbornane, bicyclo[2,2,2]octane
and adamantane. Of bridged alicyclic hydrocarbon groups, norbornane
is preferable. Examples of the aromatic group include groups
containing a benzene ring and those containing a naphthalene ring.
Of them, groups containing a benzene ring are preferable. In A, the
valence "a" refers to the number of cationic color-forming moieties
constituting the cation, and "a" is a number of 2 or more. Because
the valence "a" of the cation is 2 or more, the color material of
the present invention has excellent heat resistance. The upper
limit of "a" is not particularly limited. From the viewpoint of
ease of production, "a" is preferably 2 to 4, more preferably 2 to
3, still more preferably 2. For example, when A is a divalent
organic group, examples of the divalent organic group include a
straight-chain, branched-chain or cyclic alkylene group having 1 to
20 carbon atoms, and an aromatic group in which two alkylene groups
each having 1 to 20 carbon atoms are bound by substitution, such as
a xylylene group.
[0077] The alkyl group as each of R.sup.i to R.sup.v is not
particularly limited. Examples of the alkyl group include a
straight- or branched-chain alkyl group having 1 to 20 carbon
atoms. Of them, preferred is a straight- or branched-chain alkyl
group having 1 to 8 carbon atoms, and more preferred is a straight-
or branched-chain alkyl group having 1 to 5 carbon atoms, from the
viewpoint of luminance and heat resistance. Of them, still more
preferred is an ethyl group or a methyl group. A substituent group
that the alkyl group can have is not particularly limited. The
examples include an aryl group, a halogen atom and a hydroxyl
group. As the substituted alkyl group, a benzyl group can be
exemplified.
[0078] The aryl group as each of R.sup.i to R.sup.v is not
particularly limited. The examples include a phenyl group and a
naphthyl group. As a substituent group that the aryl group can
have, an alkyl group and a halogen atom can be exemplified.
[0079] "R.sup.ii and R.sup.iii can be bound to form a ring
structure, and/or R.sup.iv and R.sup.v can be bound to form a ring
structure" means that R.sup.ii and R.sup.iii form a ring structure
through a nitrogen atom, and/or R.sup.iv and R.sup.v form a ring
structure through a nitrogen atom. The ring structure is not
particularly limited, and the examples include a pyrrolidine ring,
a piperidine ring and a morpholine ring.
[0080] Particularly, from the viewpoint of chemical stability, it
is preferable that each of R.sup.i to R.sup.v is independently a
hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a
phenyl group. Or, it is preferable that R.sup.ii and R.sup.iii are
bound to form a pyrrolidine ring, a piperidine ring or a morpholine
ring, and/or R.sup.iv and R.sup.v are bound to form a pyrrolidine
ring, a piperidine ring or a morpholine ring.
[0081] Each of R.sup.i to R.sup.v can independently have the above
structure. Particularly, from the viewpoint of color purity, it is
preferable that R.sup.i is a hydrogen atom. From the viewpoint of
ease of production and availability of raw materials, it is more
preferable that all of R.sup.ii to R.sup.v are the same.
[0082] The divalent aromatic group as Ar.sup.1 is not particularly
limited. The aromatic group as Ar.sup.1 can be the same as those
described above as the aromatic group as A.
[0083] Ar.sup.1 is preferably an aromatic group having 6 to 20
carbon atoms, more preferably an aromatic group having a condensed
polycyclic carbon ring having 10 to 14 carbon atoms. Still more
preferred are a phenylene group and a naphthylene group, from the
point of view that the structure is simple and the raw materials
are low-cost.
[0084] A plurality of R.sup.is per molecule can be the same or
different; a plurality of R.sup.iis per molecule can be the same or
different; a plurality of R.sup.iiis per molecule can be the same
or different; a plurality of R.sup.ivs per molecule can be the same
or different; a plurality of R.sup.vs per molecule can be the same
or different; and a plurality of Ar.sup.1s per molecule can be the
same or different. Depending on the combination of R.sup.i to
R.sup.v and Ar.sup.1, it is possible to produce a desired
color.
[0085] In the general formula (I), "n" is an integer of 0 or 1. In
the general formula (I), "n=0" indicates a triarylmethane skeleton,
and "n=1" indicates a xanthene skeleton. In the general formula
(I), a plurality of "n"s can be the same or different. The examples
include a cation having a plurality of triarylmethane or xanthene
skeletons only, and a cation having both triarylmethane and
xanthene skeletons per molecule. From the viewpoint of color
purity, the cation having the same skeletons only is preferred. On
the other hand, by having the cation including both triarylmethane
and xanthene skeletons, it is possible to adjust the color of the
cation represented by the general formula (I) to a desired
color.
[0086] The method for producing the cation represented by the
general formula (I) can be appropriately selected from
conventionally-known methods. For example, it can be obtained by
the production method described in International Publication No.
WO2012/144521.
(Monovalent Anion Represented by the General Formula (II))
[0087] The color material (A-1) used in the present invention has
the monovalent anion represented by the following general formula
(II). By allowing the monovalent anion to form a salt with the
cation represented by the general formula (I), it is possible to
increase heat resistance, to adjust the color tone of a color layer
to a desired color tone, and to achieve higher luminance.
##STR00008##
(Symbols in the General Formula (II) are as Described Above.)
[0088] Examples of the alkyl group as each of R.sup.1 to R.sup.4
include a straight- or branched-chain alkyl group having 1 to 12
carbon atoms. Of them, preferred is a straight- or branched-chain
alkyl group having 1 to 8 carbon atoms, and more preferred is a
straight- or branched-chain alkyl group having 1 to 5 carbon atoms,
from the viewpoint of luminance and heat resistance. Of them, still
more preferred is an ethyl group or a methyl group. A substituent
group that the alkyl group can have is not particularly limited.
The examples include an aryl group, a halogen atom, a hydroxyl
group, a substituent group containing a sulfonato group
(--SO.sub.3.sup.- group), and a substituent group containing a
carboxylato group (--COO.sup.- group). As the substituted alkyl
group, a benzyl group can be exemplified. The substituted alkyl
group can further have a sulfonato group or carboxylato group.
[0089] Examples of the aryl group as each of R.sup.1 to R.sup.4
include an aryl group having 6 to 12 carbon atoms. Concrete
examples of the aryl group include a phenyl group and a naphthyl
group. As a substituent group that the aryl group can have, an
alkyl group and a halogen atom can be exemplified. The alkyl group
can further have a sulfonato group or carboxylato group.
[0090] Examples of the aralkyl group as each of R.sup.1 to R.sup.4
include an aralkyl group having 7 to 16 carbon atoms. Concrete
examples thereof include a benzyl group, a phenethyl group, a
naphthylmethyl group and a biphenylmethyl group. The aralkyl group
can further have a sulfonato group or carboxylato group.
[0091] "R.sup.1 and R.sup.2 can be bound to form a ring structure,
and/or R.sup.3 and R.sup.4 can be bound to form a ring structure"
means that R.sup.1 and R.sup.2 form a ring structure through a
nitrogen atom, and/or R.sup.3 and R.sup.4 form a ring structure
through a nitrogen atom. The ring structure is not particularly
limited, and the examples include a pyrrolidine ring, a piperidine
ring and a morpholine ring.
[0092] The alkyl group as each of R.sup.6 and R.sup.7 can be the
same as the above-mentioned alkyl group as each of R.sup.1 to
R.sup.4. Examples of the halogen atom as each of R.sup.6 and
R.sup.7 include a fluorine atom, a chlorine atom, a bromine atom
and an iodine atom.
[0093] R.sup.5 is a halogen atom, an alkyl group which can have a
substituent group, a sulfonato group (--SO.sub.3.sup.- group) or a
carboxylato group (--COO.sup.- group). The alkyl group which can
have a substituent group can be the same as the above-mentioned
alkyl group as each of R.sup.1 to R.sup.4. The alkyl group can have
a sulfonato group or carboxylato group.
[0094] In the general formula (II), from the viewpoint of
stability, the substitution position of the substituent group
R.sup.5 in the benzene ring attached to the xanthene skeleton, is
preferably the ortho- or para-position, more preferably in the
ortho-position, with respect to the xanthene skeleton. It is
presumed that when the substituent group R.sup.5 is in the
ortho-position, it resonates with the carbon atoms of the xanthene
skeleton to which the benzene ring attaches, thus being able to
form a ring structure and increasing heat resistance and light
resistance.
[0095] In the anion represented by the general formula (II) of the
present invention, a total of two sulfonato groups
(--SO.sub.3.sup.- groups) per molecule are contained in R.sup.1 to
R.sup.5 per molecule, or one sulfonato group (--SO.sub.3.sup.-
group) and one carboxylato group (--COO.sup.- group) are contained
in R.sup.1 to R.sup.5 per molecule. Accordingly, the anion
represented by the general formula (II) is a monovalent anion.
Because the anion represented by the general formula (II) is a
monovalent anion, the molecular weight of the color material (A-1)
is an appropriate weight, as shown in FIG. 4, and the color
material (A-1) is excellent in dispersibility.
[0096] Concrete examples of the monovalent anion represented by the
general formula (II) include anions such as anions of Acid Red 50,
52 and 289, Acid Violet 9 and 30, and Acid Blue 19. From the
viewpoint of excellent heat resistance, being able to form a
high-luminance coating film, and availability, Acid Red 52 and 289
are preferably used.
(Other Ions)
[0097] The color material (A-1) can further contain other cation or
anion and be a double salt, to the extent that does not impair the
effect of the present invention. Concrete examples of such a cation
include other basic dyes, organic compounds containing a functional
group which is able to form a salt with an anion, such as an amino
group, pyridine group or imidazole group, metal ions such as a
sodium ion, potassium ion, magnesium ion, calcium ion, copper ion,
iron ion, aluminum ion and zirconium ion, and inorganic polymers
such as polyaluminum chloride. Concrete examples of such an anion
include halide ions such as a fluoride ion, chloride ion and
bromide ion, and inorganic acid anions. Examples of the inorganic
acid anions include oxo acid anions such as a phosphate ion,
sulfate ion, chromate ion, tungstate ion (WO.sub.4.sup.2- and
molybdate ion (MoO.sub.4.sup.2-), and polyoxometalate anion. In the
present invention, it is particularly preferable that the color
material (A-1) is a color material which further contains a
polyoxometalate anion and is represented by the following general
formula (III), because a high-luminance coating film having
excellent heat resistance can be formed:
##STR00009##
[0098] wherein A is an "a"-valent organic group in which a carbon
atom directly bound to N has no .pi. bond, and the organic group is
an aliphatic hydrocarbon group having a saturated aliphatic
hydrocarbon group at least at a terminal position directly bound to
N, or an aromatic group having the aliphatic hydrocarbon group, and
O, S, N can be contained in a carbon chain of the organic group;
each of R.sup.i to R.sup.v is independently a hydrogen atom, an
alkyl group which can have a substituent group, or an aryl group
which can have a substituent group; R.sup.ii and R.sup.iii can be
bound to form a ring structure, and/or R.sup.iv and R.sup.v can be
bound to form a ring structure; Ar.sup.1 is a divalent aromatic
group which can have a substituent group; a plurality of R.sup.is
can be the same or different; a plurality of R.sup.iis can be the
same or different; a plurality of R.sup.iiis can be the same or
different; a plurality of R.sup.ivs can be the same or different; a
plurality of R.sup.vs can be the same or different; a plurality of
Ar.sup.1s can be the same or different;
[0099] "a" is a number of 2 or more; b is a number of 1 or more;
"n" is 0 or 1, and there is no bond when "n" is 0; a plurality of
"n"s can be the same or different;
[0100] each of R.sup.1 to R.sup.4 is independently a hydrogen atom,
an alkyl group which can have a substituent group, an aryl group
which can have a substituent group, or an aralkyl group which can
have a substituent group; R.sup.1 and R.sup.2 can be bound to form
a ring structure, and/or R.sup.3 and R.sup.4 can be bound to form a
ring structure; R.sup.5 is a halogen atom, an alkyl group which can
have a substituent group, a sulfonato group (--SO.sub.3.sup.-
group) or a carboxylato group (--COO.sup.- group); m is 0 to 5;
when there are a plurality of R.sup.5s, they can be the same or
different; each of R.sup.6 and R.sup.7 is independently a hydrogen
atom, a halogen atom, or an alkyl group which can have a
substituent group;
[0101] in R.sup.1 to R.sup.5, two sulfonato groups
(--SO.sub.3.sup.- groups) are contained, or one sulfonato group
(--SO.sub.3.sup.- group) and one carboxylato group (--COO.sup.-
group) are contained;
[0102] B.sup.d- is a "d"-valent polyoxometalate anion; and c and e
are positive numbers.
[0103] FIG. 5 is a schematic view of the color material represented
by the general formula (III). In a color material 120 represented
by the general formula (III), a cation 103 represented by the
general formula (I), in which a plurality of color-forming moieties
101 are connected through a linking group A (102), a monovalent
anion 104 represented by the general formula (II), and a
polyoxometalate anion 105 form a salt. Due to containing the
divalent or higher polyoxometalate anion 105 and the divalent or
higher cation 103, it is presumed that a molecular association is
formed in the color material represented by the general formula
(III), in which a plurality of molecules associate through the
polyoxometalate anion 105. Therefore, it is presumed that the
apparent molecular weight of the color material represented by the
general formula (III) is increased much higher than the molecular
weight of conventional lake pigments, and the cohesion in a solid
state is further increased; ion pair dissociation and dye skeleton
decomposition can be inhibited; and heat resistance is increased.
It is also presumed that by the use of the polyoxometalate anion
105, which is an inorganic anion, as the divalent or higher anion,
connections between the molecular associations are consolidated, so
that heat resistance is further increased.
[0104] On the other hand, the cation represented by the general
formula (I) also forms a salt with the monovalent anion 104
represented by the general formula (II), and the salt-forming
moiety constitutes a terminal position of the molecular
association. Therefore, the size of the molecular associations are
prevented from becoming too large, and the color material
represented by the general formula (III) obtains excellent heat
resistance and a size excellent for dispersion. As a result, it is
presumed that the amount of the dispersant used can be decreased;
the concentration of the color material in the color material
dispersion liquid can be relatively increased; and even if a thin
color layer is formed, the color tone of the color layer can be
adjusted to a desired color tone.
[0105] R.sup.i to R.sup.v, A, Ar.sup.1, "a" and "n" in the general
formula (III) can be the same as those in the general formula (I).
R.sup.1 to R.sup.7 and "m" in the general formula (III) can be the
same as those in the general formula (II).
[0106] In the general formula (III), the polyoxometalate anion
(B.sup.d-) can be isopolyoxometalate ion (M.sub.mO.sub.n).sup.d- or
heteropolyoxometalate ion (X.sub.1M.sub.mO.sub.n).sup.d-. In the
ionic formulae, M is a polyatom; X is a heteroatom; "m" is the
compositional ratio of the polyatom; and "n" is the compositional
ratio of an oxygen atom. As the polyatom (M), there may be
mentioned Mo, W, V, Ti, Nb, etc. As the heteroatom (X), there may
be mentioned Si, P, As, S, Fe, Co, etc. A counter cation such as
Na.sup.+ or H.sup.+ can be contained in a part of the
polyoxometalate anion.
[0107] From the viewpoint of high luminance and excellent heat
resistance and light resistance, preferred is a polyoxometalate
anion containing at least one of tungsten (W) and molybdenum (Mo).
From the viewpoint of heat resistance, more preferred is a
polyoxometalate anion which contains at least tungsten and can
contain molybdenum.
[0108] As the polyoxometalate anion containing at least one of
tungsten (W) and molybdenum (Mo), for example, there may be
mentioned a tungstate ion [W.sub.10O.sub.32].sup.4- and a molybdate
ion [Mo.sub.6O.sub.19].sup.2-, which are isopolyoxometalates, and
phosphotungstate ions [PW.sub.12O.sub.40].sup.3- and
[P.sub.2W.sub.18O.sub.62].sup.6-, a silicotungstate ion
[SiW.sub.12O.sub.40].sup.4-, a phosphomolybdate ion
[PMo.sub.12O.sub.40].sup.3-, a silicomolybdate ion
[SiMO.sub.12O.sub.40].sup.4-, phosphotungstic molybdate ions
[PW.sub.12-xM.sub.xO.sub.40].sup.3- (x is an integer of 1 to 11)
and [P.sub.2W.sub.18-yMo.sub.yO.sub.62].sup.6- (y is an integer of
1 to 17) and a silicotungstic molybdate ion
[SiW.sub.12-xMo.sub.xO.sub.40].sup.4- (x is an integer of 1 to 11),
which are all heteropolyoxometalates. Of these examples, from the
viewpoint of heat resistance and availability of raw materials, the
polyoxometalate anion containing at least one of tungsten (W) and
molybdenum (Mo) is preferably a heteropolyoxometalate, more
preferably a heteropolyoxometalate containing phosphorus (P).
[0109] In the polyoxometalate anion containing at least tungsten
(W), the content ratio of the tungsten to molybdenum is not
particularly limited. Particularly from the viewpoint of excellent
heat resistance, the molar ratio of the tungsten to molybdenum is
preferably 100:0 to 85:15, more preferably 100:0 to 90:10.
[0110] In the general formula (III), as the polyoxometalate anion,
the above-mentioned polyoxometalate anions can be used alone or in
combination of two or more kinds. In the case of using a
combination of two or more kinds of the above-mentioned
polyoxometalate anions, the molar ratio of the tungsten to
molybdenum in the whole polyoxometalate anion is preferably in the
above range.
[0111] In the color material represented by the general formula
(III), the content ratio of the anion represented by the general
formula (II) to the polyoxometalate anion can be appropriately
adjusted so as to obtain a desired color tone. From the viewpoint
of heat resistance and dispersibility, the charge-based content
ratio (c:(d.times.e)) of the anion represented by the general
formula (II) to the "d"-valent polyoxometalate anion is preferably
5:95 to 40:60, more preferably 10:90 to 30:70.
[0112] In the present invention, the color material (III) is
particularly preferably a color material represented by the
following general formula (III'), from the viewpoint of excellent
heat resistance and being able to increase the temporal stability
of the below-described color resin composition.
##STR00010##
[0113] wherein A is an "a"-valent organic group in which a carbon
atom directly bound to N has no .pi. bond, and the organic group is
an aliphatic hydrocarbon group having a saturated aliphatic
hydrocarbon group at least at a terminal position directly bound to
N, or an aromatic group having the aliphatic hydrocarbon group, and
O, S, N can be contained in a carbon chain of the organic group;
each of R.sup.i to R.sup.v is independently a hydrogen atom, an
alkyl group which can have a substituent group, or an aryl group
which can have a substituent group; R.sup.ii and R.sup.iii can be
bound to form a ring structure, and/or R.sup.iv and R.sup.v can be
bound to form a ring structure; Ar.sup.1 is a divalent aromatic
group which can have a substituent group; a plurality of R.sup.is
can be the same or different; a plurality of R.sup.iis can be the
same or different; a plurality of R.sup.iiis can be the same or
different; a plurality of R.sup.ivs can be the same or different; a
plurality of R.sup.vs can be the same or different; a plurality of
Ar.sup.1s can be the same or different;
[0114] "a" is a number of 2 or more; b is a number of 1 or more;
"n" is 0 or 1, and there is no bond when "n" is 0; a plurality of
"n"s can be the same or different;
[0115] each of R.sup.1 to R.sup.4 is independently a hydrogen atom,
an alkyl group which can have a substituent group, an aryl group
which can have a substituent group, or an aralkyl group which can
have a substituent group; R.sup.1 and R.sup.2 can be bound to form
a ring structure, and/or R.sup.3 and R.sup.4 can be bound to form a
ring structure; R.sup.5 is a halogen atom, an alkyl group which can
have a substituent group, a sulfonato group (--SO.sub.3.sup.-
group) or a carboxylato group (--COO.sup.- group); m is 0 to 5;
when there are a plurality of R.sup.5s, they can be the same or
different; each of R.sup.6 and R.sup.7 is independently a hydrogen
atom, a halogen atom, or an alkyl group which can have a
substituent group;
[0116] in R.sup.1 to R.sup.5, two sulfonato groups
(--SO.sub.3.sup.- groups) are contained, or one sulfonato group
(--SO.sub.3.sup.- group) and one carboxylato group (--COO.sup.-
group) are contained;
[0117] B.sup.d- is a "d"-valent polyoxometalate anion; c and e are
positive numbers; and c:(d.times.e) is 5:95 to 50:50.
[0118] As a result of diligent research, the inventors of the
present invention have found that excellent heat resistance and a
color resin composition with excellent temporal stability can be
obtained by, in the color material represented by the general
formula (III), adjusting the charge-based content ratio of the
anion represented by the general formula (II), which is a
monovalent anion, to the "d"-valent polyoxometalate anion, within a
range of 5:95 to 50:50, that is, by adjusting
(l.times.c):(d.times.e) to be in a range of 5:95 to 50:50.
[0119] This finding will be further described with reference to
figures. FIG. 6 is a schematic view of an example of the color
material in which the cation represented by the general formula (I)
and the polyoxometalate anion form a salt. FIG. 7 is a schematic
view of an example of the color material represented by the general
formula (III'). As described above, it is presumed that the
molecular association is formed by combining the divalent or higher
cation with the divalent or higher anion. However, as shown by the
example in FIG. 6, in the case where only the cations 103
represented by the general formula (I) and the polyoxometalate
anions 105 are combined, it is presumed that the polyoxometalate
anion 106 not forming a salt or the cation 107 being represented by
the general formula (I) and not forming a salt, is present at a
terminal position of the molecular association. The polyoxometalate
anion 106 not forming a salt is highly acidic, and when it is
present at a terminal position of the molecular association, it is
presumed that the polyoxometalate anion acts on the below-described
binder component or the like and decomposes or denaturalizes it.
Therefore, it is presumed that the color material as shown by the
example in FIG. 6 is likely to increase the viscosity of the
below-described color resin composition over time, when it is
formed into the below-described color resin composition.
[0120] On the other hand, as shown by the example in FIG. 7, in the
color material 130 represented by the general formula (III'), by
combining the monovalent anion 104 represented by the general
formula (II) with the polyoxometalate anion 105 in specific
amounts, the molecular association with increased heat resistance
is formed and, at the same time, the content of the polyoxometalate
anion 105 is relatively small. Therefore, it is presumed that the
ratio of the polyoxometalate anion 106 not forming a salt
decreases, so that reaction with the binder component is inhibited.
Due to the above reasons, the color resin composition using the
color material represented by the general formula (III') is also
excellent in temporal stability.
[0121] In the present invention, the content ratio (c:(d.times.e))
of the anion represented by the general formula (II) to the
"d"-valent polyoxometalate anion is preferably 5:95 to 40:60, more
preferably 10:90 to 30:70.
[0122] The method for producing the color material (A-1) can be
appropriately selected from conventionally-known methods. For
example, the color material can be obtained by mixing the cation
represented by the general formula (I), the anion represented by
the general formula (II), and other ions used as needed, such as
polyoxometalate anion, in a solvent.
<Other Color Material>
[0123] In order to adjust color tone, the color material (A) can
further contain other color material, to the extent that does not
impair the effects of the present invention. As the other color
material, there may be mentioned known pigments and dyes, etc., and
they can be used alone or in combination of two or more kinds. As
the other color material, it is particularly preferable to use the
color material described in International Publication No. WO
2012/144521, which contains the divalent or higher cation
represented by the general formula (I) and a divalent or higher
anion. Concrete examples of the other color material and the
content of the other color material are not particularly limited,
as long as the effects of the present invention are not impaired,
and can be the same as the case of the below-described color resin
composition for color filters.
[0124] In the present invention, the average dispersed particle
diameter of the color material (A) used is not particularly
limited, as long as a desired color can be obtained when the color
material is formed into the color layer of a color filter. From the
viewpoint of increasing contrast and obtaining excellent heat
resistance and light resistance, the average dispersed particle
diameter is preferably in a range of 10 to 200 nm, more preferably
in a range of 20 to 150 nm. By setting the average dispersed
particle diameter of the color material (A) within the range, the
liquid crystal display device and organic light-emitting display
device produced by using the color resin composition for color
filters according to the present invention, can have high contrast
and high quality.
[0125] The average dispersed particle diameter of the color
material (A) in the color material dispersion liquid is the
dispersed particle diameter of the color material particles
dispersed in a dispersion medium that contains at least a solvent,
and it is measured with a laser scattering particle size
distribution analyzer. The average dispersed particle diameter can
be measured as follows with a laser scattering particle size
distribution analyzer: the color material dispersion liquid is
appropriately diluted with the solvent used for the color material
dispersion liquid to a concentration that is measurable with a
laser scattering particle size distribution analyzer (e.g.,
1,000-fold) and then measured with a laser scattering particle size
distribution analyzer (e.g., Nanotrac Particle Size Analyzer
UPA-EX150 manufactured by Nikkiso Co., Ltd.) by a dynamic light
scattering method at 23.degree. C. This average dispersed particle
diameter is a volume average particle diameter.
[0126] In the color material dispersion liquid of the present
invention, the content of the color material is not particularly
limited. From the viewpoint of dispersibility and dispersion
stability, the content of the color material is preferably in a
range of 5 to 40% by mass, more preferably 10 to 20% by mass, with
respect to the total amount of the color material dispersion
liquid.
[(B) Dispersant]
[0127] In the color material dispersion liquid of the present
invention, the color material (A-1) is dispersed in the solvent by
the dispersant (B) for use. The dispersant (B) can be selected from
those that are conventionally used as dispersants. Concrete
examples of the dispersant include surfactants such as cationic,
anionic, nonionic, amphoteric, silicone-based and fluorine-based
dispersing agents. Among surfactants, polymer surfactants (polymer
dispersants) are preferred from the viewpoint of being able to
disperse the color material homogeneously and finely.
[0128] Examples of polymer dispersants include: (co)polymers of
unsaturated carboxylic acid esters such as polyacrylic acid ester;
(partial) amine salts, (partial) ammonium salts and (partial)
alkylamine salts of (co)polymers of unsaturated carboxylic acids
such as polyacrylic acid; (co)polymers of hydroxyl group-containing
unsaturated carboxylic acid esters such as hydroxyl
group-containing polyacrylic acid ester, and modified products
thereof; polyurethanes; unsaturated polyamides; polysiloxanes;
long-chain polyaminoamide phosphates; polyethyleneimine derivatives
(amide and bases thereof, obtained by reaction of poly(lower
alkyleneimine) and polyester having a free carboxyl group); and
polyallylamine derivatives (reaction products obtained by reaction
of polyallylamine and one or more compounds selected from the group
consisting of the following three kinds of compounds: polyester
having a free carboxyl group, polyamide, and a co-condensate of
ester and amide (polyester amide).
[0129] Commercially-available products of such dispersants include
Disperbyk-2000 and 2001, and BYK-LPN 6919 and 21116 (all
manufactured by BYK Japan KK), AJISPER PB821 and 881 (manufactured
by Ajinomoto Co., Inc.) and so on. Of them, BYK-LPN 6919 and 21116
are preferred from the viewpoint of heat resistance, electric
reliability and dispersibility.
[0130] From the point of view that appropriate dispersion of the
color material (A-1) and excellent dispersion stability can be
achieved, the polymer dispersant is particularly preferably one or
more kinds selected from the group consisting of a polymer having
at least a constitutional unit represented by the following general
formula (IV) and urethane-based dispersants composed of compounds
having one or more urethane bonds (--NH--COO--) per molecule.
[0131] Hereinafter, the preferred dispersant will be described in
detail.
<Polymer Having at Least a Constitutional Unit Represented by
the Following General Formula (IV)>
[0132] In the present invention, a polymer having at least a
constitutional unit represented by the following general formula
(IV) can be preferably used as the dispersant (B):
##STR00011##
[0133] wherein R.sup.11 is a hydrogen atom or a methyl group; A is
a direct bond or a divalent linking group; Q is a group represented
by the following general formula (IV-a) or a nitrogen-containing
heterocyclic group which is able to form a salt and which can have
a substituent group:
##STR00012##
[0134] wherein each of R.sup.12 and R.sup.13 is independently a
hydrogen atom or a hydrocarbon group which can contain a
heteroatom, and R.sup.12 and R.sup.13 can be the same or different
from each other.
[0135] In the general formula (IV), A is a direct bond or a
divalent linking group. The direct bond means that Q is directly
bound to a carbon atom in the general formula (IV), not through a
linking group.
[0136] Examples of the divalent linking group as A include an
alkylene group having 1 to 10 carbon atoms, an arylene group, a
--CONH-- group, a --COO-- group, an ether group having 1 to 10
carbon atoms (--R'--OR''-- where each of R' and R'' is
independently an alkylene group) and combinations thereof.
[0137] From the viewpoint of dispersibility, A in the general
formula (IV) is preferably a direct bond or a divalent linking
group containing a --CONH-- group or a --COO-- group.
[0138] The above dispersants can be particularly preferably used by
allowing the constitutional unit represented by the general formula
(IV) of the dispersants to form a salt by the below-described salt
forming agent, at a desired ratio.
[0139] As the polymer having the constitutional unit represented by
the general formula (IV), block and graft copolymers having
structures disclosed in International Publication No. WO2011/108495
and Japanese Patent Application Laid-Open (JP-A) Nos. 2013-054200,
2010-237608 and 2011-75661 are particularly preferred, from the
point of view that the dispersibility and dispersion stability of
the color material and the heat resistance of the resin composition
can be increased, and a color layer with high luminance and high
contrast can be formed.
[0140] Commercially-available products of the polymers having the
constitutional unit represented by the general formula (IV) include
BYK-LPN 6919.
(Salt Forming Agent)
[0141] In the present invention, the dispersant is preferably a
polymer in which at least a part of a nitrogen site of the
constitutional unit represented by the general formula (IV) forms a
salt (hereinafter, this state may be referred to as
"salt-modified").
[0142] In the present invention, by allowing the nitrogen site of
the constitutional unit represented by the general formula (IV) to
form a salt using the salt forming agent, the dispersant strongly
adsorbs to the color material similarly forming a salt, so that the
dispersibility and dispersion stability of the color material are
increased. As the salt forming agent, acidic organophosphorus
compounds, organic sulfonic acid compounds and quaternizing agents,
which are disclosed in International Publication No. WO2011/108495
and JP-A No. 2013-054200, can be preferably used. Especially when
the salt forming agent is an acidic organophosphorus compound,
salt-forming moieties containing the acidic organophosphorus
compound of the dispersant are localized on the surface of the
color material particles, and thus the color material surface
reaches a state of being covered with phosphate. Therefore, attacks
on the dye skeleton of the color material by active oxygen
(hydrogen abstraction) are inhibited, so that the heat resistance
and light resistance of the color material containing the dye
skeleton are increased. For this reason, color deterioration by
high-temperature heating can be further inhibited by using the
polymer salt-modified by the acidic organophosphorus compound as
the dispersant, while the color material (A) having high
transmittance and being used in the present invention is in a state
of being sufficiently dispersed. Therefore, a color layer which
shows higher luminance even after the high-temperature heating step
included in the color filter production step, can be formed.
<Urethane-Based Dispersant>
[0143] The urethane-based dispersant which is preferably used as
the dispersant, is a dispersant composed of a compound having one
or more urethane bonds (--NH--COO--) per molecule.
[0144] Excellent dispersion is possible by using a small amount of
the urethane-based dispersant. By making the amount of the
dispersant small, the amount of a cure component, etc., can be
relatively large. As a result, a color layer with excellent heat
resistance can be formed.
[0145] In the present invention, the urethane-based dispersant is
preferably a reaction product of (1) polyisocyanates having two or
more isocyanate groups per molecule and (2) one or more kinds
selected from polyesters having a hydroxyl group at a single
terminal or both terminals thereof and poly(meth) acrylates having
a hydroxyl group at a single terminal or both terminals thereof.
The urethane-based dispersant is more preferably a reaction product
of (1) polyisocyanates having two or more isocyanate groups per
molecule, (2) one or more kinds selected from polyesters having a
hydroxyl group at a single terminal or both terminals thereof and
poly(meth) acrylates having a hydroxyl group at a single terminal
or both terminals thereof, and (3) a compound having an active
hydrogen and a basic or acidic group per molecule.
[0146] Examples of commercially-available dispersants include
Disperbyk-161, 162, 163, 164, 167, 168, 170, 171, 174, 182, 183,
184 and 185, and BYK-9077 (all manufactured by BYK Japan KK),
AJISPER PB711 (manufactured by Ajinomoto Co., Inc.) and EFKA-46, 47
and 48 (manufactured by EFKA CHEMICALS). Of them, Disperbyk-161,
162, 166, 170 and 174 are preferred from the viewpoint of heat
resistance, electric reliability and dispersibility.
[0147] As the dispersant (B), these dispersants can be used alone
or in combination of two or more kinds.
[0148] In the color material dispersion liquid of the present
invention, from the viewpoint of dispersibility and dispersion
stability, the content of the dispersant (B) is generally
preferably in a range of 1 to 50% by mass, more preferably in a
range of 1 to 20% by mass, with respect to the total amount of the
dispersion liquid.
[(C) Solvent]
[0149] In the present invention, the solvent (C) can be
appropriately selected from solvents which are unreactive with
components in the color material dispersion liquid or in the
below-described color resin composition and which are able to
dissolve or disperse them. Concrete examples thereof include
organic solvents such as alcohol-based solvents, ether
alcohol-based solvents, ester-based solvents, ketone-based
solvents, ether alcohol acetate-based solvents, ether-based
solvents, aprotic amide-based solvents, lactone-based solvents,
unsaturated hydrocarbon-based solvents and saturated
hydrocarbon-based solvents. Of them, ester-based solvents are
preferred from the viewpoint of solubility upon dispersion and
coating properties.
[0150] Examples of preferred ester-based solvents include methyl
methoxypropionate, ethyl ethoxypropionate, methoxy ethyl acetate,
propylene glycol monomethyl ether acetate,
3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate,
methoxybutyl acetate, ethoxy ethyl acetate, ethyl cellosolve
acetate, dipropylene glycol methyl ether acetate, propylene glycol
diacetate, 1,3-butylene glycol diacetate, cyclohexanol acetate,
1,6-hexanediol diacetate, diethylene glycol monoethyl ether
acetate, and diethylene glycol monobutyl ether acetate.
[0151] Of them, propylene glycol monomethyl ether acetate (PGMEA)
is preferably used, from the point of view that it has a low risk
to the human body and has fast heat-drying properties although it
has low volatility at around room temperature. In this case, there
is such an advantage that a special washing step is not needed when
switching from a conventional color resin composition using
PGMEA.
[0152] These solvents can be used alone or in combination of two or
more kinds.
[0153] The color material dispersion liquid of the present
invention is prepared by using the solvent (C) generally in an
amount of 50 to 95% by mass, preferably 60 to 85% by mass, with
respect to the total amount of the color material dispersion
liquid. As the solvent amount decreases, the viscosity increases
and the dispersibility decreases. As the solvent amount increases,
the color material concentration decreases and may result in a
difficulty in achieving a target chromaticity coordinate after
preparation of the color resin composition for color filters.
(Other Components)
[0154] The color material dispersion liquid of the present
invention can further contain a dispersion assisting resin and
other components as needed, as long as the effects of the present
invention are not impaired.
[0155] As the dispersion assisting resin, there may be mentioned an
alkali soluble resin for example, which will be mentioned below
under "Color resin composition for color filters". The particles of
the color material becomes less likely to contact with each other
due to steric hindrance by the alkali soluble resin, resulting in
stabilization of particle dispersion, and the particle dispersion
stabilization effect may be effective in reducing the
dispersant.
[0156] Other components include a surfactant, which is used to
increase wettability, a silane coupling agent, which is used to
increase adhesion properties, a defoaming agent, a cissing
inhibitor, an antioxidant, an aggregation inhibitor and an
ultraviolet absorber, for example.
[0157] The color material dispersion liquid of the present
invention is used as a preliminarily prepared product for preparing
the below-described color resin composition for color filters. That
is, the color material dispersion liquid is a color material
dispersion liquid which is preliminarily prepared at a stage prior
to preparing the below-described color resin composition and whose
"the mass of the color material component in the composition"/"the
mass of the solid content other than the color material component
in the composition" ratio is high. In particular, this ratio ("the
mass of the color material component in the composition"/"the mass
of the solid content other than the color material component in the
composition" ratio) is generally 1.0 or more. By mixing the color
material dispersion liquid with at least a binder component, a
color resin composition with excellent dispersibility can be
prepared.
[Method for Producing the Color Material Dispersion Liquid]
[0158] In the present invention, the method for producing the color
material dispersion liquid is needed to be a method which can
contain the color material (A), the dispersant (B), the solvent (C)
and various kinds of additional components used as needed, and
which can homogeneously disperse the color material (A-1) in the
solvent by the dispersant. The color material dispersion liquid can
be prepared by mixing them with a known mixing means.
[0159] The dispersion liquid can be prepared by the following
method: the dispersant (B) is mixed with the solvent (C) and
stirred to produce a dispersant solution; the dispersant solution
is mixed with the color material (A-1) and, as needed, other
component; and the mixture is dispersed with a known stirrer or
disperser, thereby preparing the dispersion liquid.
[0160] As the disperser used for the dispersion treatment, there
may be mentioned roller mills such as a two-roller mill and a
three-roller mill, ball mills such as a vibrating ball mill, paint
conditioners, bead mills such as a continuous disk type bead mill
and a continuous annular type bead mill, for example. In the case
of using a bead mill, a preferred dispersion condition is that the
diameter of the beads used is 0.03 to 2.00 mm, more preferably 0.10
to 1.0 mm.
[0161] In particular, a preparatory dispersion is carried out with
2 mm zirconia beads, which is a relatively large bead diameter, and
then a main dispersion is further carried out with 0.1 mm zirconia
beads, which is a relatively small bead diameter. It is preferable
to carry out filtration with a 0.5 to 5.0 .mu.m membrane filter
after the dispersion treatment.
2. Color Resin Composition for Color Filters
[0162] The color resin composition for color filters according to
the present invention includes: (A) a color material, (B) a
dispersant, (C) a solvent and (D) a binder component, wherein the
color material (A) contains a color material (A-1) in which at
least the cation represented by the general formula (I) and the
monovalent anion represented by the general formula (II) form a
salt.
[0163] In the color resin composition for color filters according
to the present invention, the above-specified color material (A-1)
is used as the color material (A) and is dispersed in the solvent
(C); therefore, a high-luminance color layer with excellent heat
resistance can be formed, with adjusting the color tone of the
color layer to a desired color tone.
[0164] The color resin composition contains the color material (A),
the dispersant (B), the solvent (C) and the binder component (D),
and it can contain other components as needed.
[0165] Hereinafter, such a color resin composition for color
filters will be described. However, the color material (A), the
dispersant (B) and the solvent (C) will not be described below,
since they can be the same as those of the above-described color
material dispersion liquid of the present invention.
[(D) Binder Component]
[0166] To provide film-forming and surface adhesion properties, the
color resin composition for color filters contains a binder
component. To provide sufficient hardness to coating films, it is
preferable that a curable binder component is contained in the
color resin composition for color filters. The curable binder
component is not particularly limited, and conventionally-known
curable binder components that are used to form color layers of
color filters can be appropriately used.
[0167] As the curable binder component, for example, there may be
used one containing a photocurable binder component that contains a
photocurable resin, the resin being polymerizable and curable by
visible light, ultraviolet or electron beam radiation, etc., or a
thermosetting binder component that contains a thermosetting resin,
the resin being polymerizable and curable by heating.
[0168] No developability is required of the curable binder
component, when it is possible to form color layers by attaching
the color resin composition for color filters selectively in a
pattern onto a substrate, such as the ink-jet method. In this case,
there may be used a known thermosetting binder component or
photosensitive binder component, appropriately, which are used to
form color layers of color filters by the ink-jet method, etc.
[0169] As the thermosetting binder, a combination of a compound
having two or more thermosetting functional groups per molecule and
a curing agent is generally used. In addition, a catalyst which can
promote a thermosetting reaction can be added. Examples of
thermosetting functional groups include an epoxy group, an oxetanyl
group, an isocyanate group and an ethylenically unsaturated bond.
As the thermosetting functional groups, epoxy groups are preferably
used. Concrete examples of the thermosetting binder component
include those mentioned in International Publication No.
WO2012/144521.
[0170] On the other hand, in the case of using a photolithography
process to form color layers, a photosensitive binder component
with alkali developability is suitably used.
[0171] Hereinafter, photosensitive binder components will be
explained. However, the curable binder component used in the
present invention is not limited to them. Besides the
below-described photosensitive binder components, a thermosetting
binder component that is polymerizable and curable by heating, such
as epoxy resin, can be further used.
[0172] Photosensitive binder components include a positive
photosensitive binder component and a negative photosensitive
binder component. Examples of positive photosensitive binder
components include those containing an alkali soluble resin and an
o-quinonediazide group-containing compound, which is a
photosensitivity-imparting component.
[0173] On the other hand, as the negative photosensitive binder
component, those containing at least an alkali soluble resin, a
polyfunctional monomer and a photoinitiator, are suitably used.
[0174] In the color resin composition for color filters, the
negative photosensitive binder component is preferred, from the
point of view that a pattern can be easily formed by a
photolithography method, using existing processes.
[0175] Hereinafter, the alkali soluble resin, the polyfunctional
monomer and the photoinitiator, which constitute the negative
photosensitive binder component, will be explained in detail.
(Alkali Soluble Resin)
[0176] In the present invention, the alkali soluble resin can be
appropriately selected, as long as it has an acidic group,
functions as a binder resin, and is soluble in developing solutions
used for pattern formation, particularly preferably in an alkali
developing solution.
[0177] In the present invention, the alkali soluble resin is
preferably a resin having a carboxyl group as the acidic group.
Concrete examples thereof include acrylic copolymers having a
carboxyl group and epoxy (meth)acrylate resins having a carboxyl
group. Of them, particularly preferred is one having a carboxyl
group and, moreover, a photopolymerizable functional group such as
an ethylenically unsaturated group in a side chain thereof. This is
because the hardness of the cured film thus formed is increased by
containing the photopolymerizable functional group. These acrylic
copolymers and epoxy (meth)acrylate resins can be used in
combination of two or more kinds.
[0178] An acrylic copolymer having a carboxyl group is obtained by
copolymerizing a carboxyl group-containing ethylenically
unsaturated monomer and an ethylenically unsaturated monomer.
[0179] The acrylic copolymer having a carboxyl group can further
contain a constitutional unit having an aromatic carbon ring. The
aromatic carbon ring functions as a component which imparts
coatability to the color resin composition for color filters.
[0180] The acrylic copolymer having a carboxyl group can further
contain a constitutional unit having an ester group. The
constitutional unit having an ester group not only functions as a
component which inhibits alkali solubility of the color resin
composition for color filters, but also functions as a component
which increases solubility in solvents and re-solubility in
solvents.
[0181] Concrete examples of the acrylic copolymer having a carboxyl
group include those described in International Publication No.
WO2012/144521. In particular, there may be mentioned copolymers
obtained from a monomer having no carboxyl group, such as methyl
(meth)acrylate and ethyl (meth)acrylate, with one or more selected
from (meth)acrylic acid and anhydrides thereof. Also, there may be
mentioned polymers obtained by introducing an ethylenically
unsaturated bond in the above copolymers by, for example, addition
of an ethylenically unsaturated compound having a reactive
functional group such as a glycidyl group or hydroxyl group. In the
present invention, however, the acrylic copolymer having a carboxyl
group is not limited to these examples.
[0182] Of these examples, the polymers obtained by introducing an
ethylenically unsaturated bond in the above copolymers by, for
example, addition of an ethylenically unsaturated compound having a
glycidyl group or hydroxyl group, are particularly preferred from
the point of view that polymerization with the below-described
polyfunctional monomer is possible upon exposure, and stable color
filters can be obtained.
[0183] The copolymerization ratio of the carboxyl group-containing
ethylenically unsaturated monomer in the carboxyl group-containing
copolymer is generally 5 to 50% by mass, preferably 10 to 40% by
mass. When the copolymerization ratio of the carboxyl
group-containing ethylenically unsaturated monomer is less than 5%
by mass, the solubility of the coating film thus obtained in alkali
developing solutions is decreased, resulting in a difficulty with
pattern formation. When the copolymerization ratio exceeds 50% by
mass, upon development with an alkali developing solution, a
pattern thus formed is likely to come off of the substrate, or
roughening of the pattern surface is likely to occur.
[0184] The molecular weight of the carboxyl group-containing
copolymer is preferably in a range of 1,000 to 500,000, more
preferably in a range of 3,000 to 200,000. When the molecular
weight is less than 1,000, there may be a remarkable decrease in
binder function after curing. When the molecular weight exceeds
500,000, upon development with an alkali developing solution,
pattern formation may be difficult.
[0185] The epoxy (meth)acrylate resin having a carboxyl group is
not particularly limited. As the resin, an epoxy (meth)acrylate
compound obtained by reaction of an acid anhydride with a reaction
product of an epoxy compound and an unsaturated group-containing
monocarboxylic acid, is suitable.
[0186] The epoxy compound, the unsaturated group-containing
monocarboxylic acid and the acid anhydride can be appropriately
selected from known ones. Concrete examples thereof include those
described in International Publication No. WO2012/144521. As each
of the epoxy compound, the unsaturated group-containing
monocarboxylic acid and the acid anhydride, those mentioned above
can be used alone or in combination of two or more kinds.
[0187] The alkali soluble resin used in the color resin composition
for color filters can be one kind of alkali soluble resin or a
combination of two or more kinds of alkali soluble resins. The
content of the alkali soluble resin is generally in a range of 10
to 1,000 parts by mass, preferably in a range of 20 to 500 parts by
mass, with respect to 100 parts by mass of the color material
contained in the color resin composition. When the content of the
alkali soluble resin is too small, sufficient alkali developability
may not be obtained. When the content is too large, the ratio of
the color material is relatively small, so that sufficient color
density may not be obtained.
(Polyfunctional Monomer)
[0188] The polyfunctional monomer used in the color resin
composition for color filters is not particularly limited, as long
as it is polymerizable with the below-described photoinitiator. As
the polyfunctional monomer, a compound having two or more
ethylenically unsaturated double bonds is generally used.
Preferably, the polyfunctional monomer is a polyfunctional
(meth)acrylate having two or more acryloyl or methacryloyl
groups.
[0189] Such a polyfunctional (meth)acrylate can be appropriately
selected from conventionally known ones. Concrete examples thereof
include those mentioned in International Publication No.
WO2012/144521.
[0190] These polyfunctional (meth)acrylates can be used alone or in
combination of two or more kinds. When excellent photocurability
(high sensitivity) is required of the color resin composition the
present invention, the polyfunctional monomer is preferably one
having three (trifunctional) or more polymerizable double bonds.
Preferred are poly(meth) acrylates of trivalent or higher
polyalcohols and dicarboxylic acid-modified products thereof.
Concrete examples thereof include trimethylolpropane
tri(meth)acrylate, pentaerythritol tri(meth)acrylate and succinic
acid-modified products of pentaerythritol tri(meth)acrylate,
pentaerythritol tetra(meth)acrylate, dipentaerythritol
tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and
succinic acid-modified products of dipentaerythritol
penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.
[0191] The content of the polyfunctional monomer used in the color
resin composition for color filters is not particularly limited. It
is generally about 5 to 500 parts by mass, preferably in a range of
20 to 300 parts by mass, with respect to 100 parts by mass of the
alkali soluble resin. When the content of the polyfunctional
monomer is smaller than the range, photocuring may not proceed
sufficiently and the color resin composition exposed to light may
be dissolved. When the content of the polyfunctional monomer is
larger than the range, there may be a decrease in alkali
developability.
(Photoinitiator)
[0192] The photoinitiator used in the color resin composition for
color filters is not particularly limited. As the photoinitiator,
conventionally-known various kinds of photoinitiators can be used
alone or in combination of two or more kinds. Concrete examples
thereof include those mentioned in International Publication No.
WO2012/144521.
[0193] The content of the photoinitiator used in the color resin
composition for color filters is generally about 0.01 to 100 parts
by mass, preferably 5 to 60 parts by mass, with respect to 100
parts by mass of the polyfunctional monomer.
[0194] When the content is smaller than the range, sufficient
polymerization reaction may not be caused, so that the hardness of
the color layer may not be sufficient. When the content is larger
than the range, the content of the color material and so on in the
solid content of the color resin composition is relatively small,
so that sufficient color density may not be obtained.
<Optionally-Added Compounds>
[0195] As needed, the color resin composition for color filters can
further contain other color material or various kinds of
additives.
(Other Color Material)
[0196] Other color material can be added as needed, in order to
adjust color tone. For example, it can be selected from
conventionally-known pigments and dyes, according to the purpose,
and such pigments and dyes can be used alone or in combination of
two or more kinds.
[0197] As the other color material, it is particularly preferable
to use the color material described in International Publication
No. WO 2012/144521, which contains the divalent or higher cation
represented by the general formula (I) and a divalent or higher
anion.
[0198] Concrete examples of the other color material include
pigments such as C. I. Pigment Violet 1, C. I. Pigment Violet 2, C.
I. Pigment Violet 3, C. I. Pigment Violet 19, C. I. Pigment Violet
23, C. I. Pigment Blue 1, C. I. Pigment Blue 15, C. I. Pigment Blue
15:3, C. I. Pigment Blue 15:4, C. I. Pigment Blue 15:6, C. I.
Pigment Blue 60, C. I. Pigment Red 81, C. I. Pigment Red 82, and
dyes such as Acid Red.
[0199] In the case of using the other color material, the content
is not particularly limited. Especially in the case of using the
color material described in International Publication No. WO
2012/144521 as the other material, which contains the divalent or
higher cation represented by the general formula (I) and a divalent
or higher anion, the color material can be preferably used in a
desired amount.
[0200] The content of the other color material is preferably 40
parts by mass or less, more preferably 20 parts by mass or less,
with respect to 100 parts by mass of the total amount of the color
materials. This is because when the content is in this range, color
tone can be adjusted without impairing the properties of the color
material (A-1), such as high transmittance, heat resistance and
light resistance.
(Antioxidant)
[0201] From the viewpoint of heat resistance and light resistance,
it is preferable that the color resin composition for color filters
further contains an antioxidant. The antioxidant can be
appropriately selected from conventionally-known ones. Concrete
examples of the antioxidant include a hindered phenol-based
antioxidant, an amine-based antioxidant, a phosphorus-based
antioxidant, a sulfur-based antioxidant and a hydrazine-based
antioxidant. From the viewpoint of heat resistance, it is
preferable to use a hindered phenol-based antioxidant.
[0202] The hindered phenol-based antioxidant means an antioxidant
that contains at least one phenol structure in which at least one
of the 2- and 6-positions of the hydroxyl group is substituted with
a substituent group having 4 or more carbon atoms.
[0203] In the case of using the antioxidant, the amount is not
particularly limited, as long as it is in a range that does not
impair the effects of the present invention. The amount of the
antioxidant used is preferably 0.1 to 5.0 parts by mass, more
preferably 0.5 to 4.0 parts by mass, with respect to the total
solid content 100 parts by mass of the color resin composition.
When the amount of the antioxidant used is equal to or more than
the lower limit, excellent heat resistance is obtained. When the
amount is equal to or less than the upper limit, the color resin
composition can be a highly-sensitive photosensitive resin
composition.
(Other Additives)
[0204] Examples of additives include, besides the above-mentioned
antioxidant, a polymerization terminator, a chain transfer agent, a
leveling agent, a plasticizer, a surfactant, a defoaming agent, a
silane coupling agent, an ultraviolet absorber and an adhesion
enhancing agent.
[0205] Concrete examples of the surfactant and the plasticizer
include those mentioned in International Publication No.
WO2012/144521.
<The Content of Each Component in the Color Resin
Composition>
[0206] The total content of the color material (A) is preferably 3
to 65% by mass, more preferably 4 to 55% by mass, with respect to
the total solid content of the color resin composition. When the
total content is equal to or more than the lower limit, the color
layer obtained by applying the color resin composition for color
filters to a predetermined thickness (generally 1.0 to 5.0 .mu.m)
has sufficient color density. When the total content is equal to or
less than the upper limit, excellent dispersibility and dispersion
stability can be obtained, and a color layer with sufficient
hardness and adhesion to the substrate can be obtained. In the
present invention, "solid content" includes all the above-described
components other than the solvent, and it also includes the
polyfunctional monomer in a liquid form.
[0207] Also, the content of the dispersant (B) is not particularly
limited, as long as it is able to homogeneously disperse the color
material (A). For example, the dispersant content is 3 to 40 parts
by mass, with respect to the total solid content of the color resin
composition. More preferably, the content is 5 to 35 parts by mass,
particularly preferably 5 to 25 parts by mass, with respect to the
total solid content of the color resin composition. When the
content is equal to or more than the lower limit, the color
material (A) has excellent dispersibility and dispersion stability,
and it has excellent storage stability. When the content is equal
to or less than the upper limit, excellent developing properties
can be obtained.
[0208] The total amount of the binder component (D) is 10 to 92% by
mass, preferably 15 to 87% by mass, with respect to the total solid
content of the color resin composition. When the total amount is
equal to or more than the lower limit, a color layer with
sufficient hardness and adhesion to the substrate can be obtained.
When the total amount is equal to or less than the upper limit,
excellent developing properties can be obtained, and generation of
fine wrinkles can be inhibited, which is due to heat shrinkage.
[0209] The content of the solvent (C) can be appropriately
determined in a range which can form a color layer with accuracy.
In general, the content is preferably in a range of 55 to 95% by
mass, particularly preferably in a range of 65 to 88% by mass, with
respect to the total amount of the color resin composition
including the solvent. When the content of the solvent is in the
range, excellent coatability can be provided to the color resin
composition.
<Method for Producing the Color Resin Composition for Color
Filters>
[0210] The method for producing the color resin composition for
color filters is not particularly limited, as long as it is a
method in which the color material (A), the dispersant (B), the
solvent (C), the binder component (D) and various kinds of
additional components that are added as needed are contained, and
the color material (A) can be homogeneously dispersed in the
solvent (C) by the dispersant (B). The color resin composition can
be prepared by mixing them using a known mixing means.
[0211] Examples of the method for preparing the color resin
composition include the following:
[0212] (1) a method of mixing the color material dispersion liquid
of the present invention with the binder component (D) and various
kinds of additional components used as needed;
[0213] (2) a method of adding the color material (A), the
dispersant (B), the binder component (D) and various kinds of
additional components used as needed to the solvent (C) at the same
time and mixing them; and
[0214] (3) a method of adding the dispersant (B), the binder
component (D) and various kinds of additional components used as
needed to the solvent (C), mixing them, adding the color material
(A) thereto and then mixing them.
[0215] Of these methods, the method (1) is preferred, from the
viewpoint of effectively preventing the aggregation of the color
material and homogeneously dispersing the color material.
3. Color Filter
[0216] The color filter according to the present invention includes
at least a transparent substrate and color layers disposed on the
substrate, wherein at least one of the color layers contains a
color material (A-1) in which at least a cation represented by the
following general formula (I) and a monovalent anion represented by
the following general formula (II) form a salt:
##STR00013##
(symbols in the general formulae (I) and (II) are as described
above.)
[0217] Such a color filter of the present invention will be
explained, with reference to figures. FIG. 1 is a schematic
sectional view of an example of the color filter of the present
invention. FIG. 1 shows that a color filter 10 of the present
invention contains a transparent substrate 1, a light shielding
part 2 and a color layer 3.
(Color Layer)
[0218] At least one of the color layers used in the color filter of
the present invention is a color layer that contains the color
material (A-1) in which at least the cation represented by the
general formula (I) and the monovalent anion represented by the
general formula (II) form a salt.
[0219] It is generally formed on an opening of the light shielding
part on the below-described transparent substrate and is generally
composed of color patterns in three or more colors.
[0220] The arrangement of the color layers is not particularly
limited and can be a general arrangement such as a stripe type, a
mosaic type, a triangle type or a four-pixel arrangement type. The
width, area, etc., of the color layer can be determined
appropriately.
[0221] The thickness of the color layer is appropriately controlled
by controlling the applying method, the solid content
concentration, viscosity, etc., of the color resin composition for
color filters. In general, the thickness is preferably in a range
of 1 to 5 .mu.m.
[0222] For example, when the color resin composition for color
filters is a photosensitive resin composition, the color layer can
be formed by the following method. It is preferable that the color
layer which is used in the color filter of the present invention
and contains the color material (A-1) in which at least the cation
represented by the general formula (I) and the monovalent anion
represented by the general formula (II) form a salt, is formed
using the above-described color resin composition for color
filters, which contains: the color material (A), the dispersant
(B), the solvent (C) and the binder component (D), wherein the
color material (A) contains the color material (A-1) in which at
least the cation represented by the general formula (I) and the
monovalent anion represented by the general formula (II) form a
salt. It is also preferable that the color layer is a cured product
of the color resin composition for color filters.
[0223] First, the color resin composition for color filters is
applied onto the below-described transparent substrate by a coating
method such as a spray coating method, a dip coating method, a bar
coating method, a roll coating method or a spin coating method to
form a wet coating film.
[0224] Then, the wet coating film is dried with a hot plate, an
oven, etc. The dried film is subjected to exposure through a mask
with a given pattern to cause a photopolymerization reaction of the
alkali soluble resin, the polyfunctional monomer, etc., thereby
obtaining a photosensitive coating film. Examples of light sources
and lights that can be used for the exposure include a low pressure
mercury lamp, a high pressure mercury lamp and a metal halide lamp,
and ultraviolet rays and electron beams. The exposure amount is
appropriately controlled, according to the used light source and
the thickness of the coating film.
[0225] The film can be heated to promote polymerization reaction
after the exposure. The heating condition is appropriately
determined, depending on the content ratio of the components used
in the color resin composition of the present invention, the
thickness of the coating film, etc.
[0226] Next, the thus-obtained film is developed with a developing
solution to dissolve and remove unexposed portions, thereby forming
a coating film in a desired pattern. As the developing solution, a
solution obtained by dissolving alkali in water or aqueous solvent,
is generally used. An appropriate amount of surfactant, etc., can
be added to the alkali solution. The developing method can be
selected from general developing methods.
[0227] After the developing treatment, generally, the developing
solution is rinsed off, followed by drying of the cured coating
film of the color resin composition, thereby forming a color layer.
A heating treatment can be carried out after the developing
treatment to sufficiently cure the coating film. The heating
condition is not particularly limited and is appropriately
determined depending on the intended use of the coating film.
(Light Shielding Part)
[0228] In the color filter of the present invention, the light
shielding part is formed in pattern on the below-described
transparent substrate, and it can be the same as those used in
general color filters.
[0229] The pattern shape of the light shielding part is not
particularly limited, and examples thereof include a stripe-shaped
pattern, a matrix-shaped pattern, etc. As the light shielding part,
for example, there may be mentioned one produced by dispersing or
dissolving a black pigment in a binder resin, and thin metal layers
of chromium, chromium oxide, etc. When the light shielding part is
such a thin metal layer, the layer can be a stack of two layers of
one CrO.sub.x layer (x is an arbitrary number) and one Cr layer, or
can be a stack of three layers of one CrO.sub.x layer (x is an
arbitrary number), one CrN.sub.y layer (y is an arbitrary number)
and one Cr layer, the stack of three layers having a further
reduced reflectance.
[0230] When the light shielding part is one produced by dispersing
or dissolving a black color material in a binder resin, the method
for producing the light shielding part is not particularly limited
and is only required to be a method which can pattern the light
shielding part. For example, there may be mentioned a
photolithography method using a color resin composition for the
light shielding part, a printing method using the same, an ink-jet
method using the same, etc.
[0231] When the light shielding part is a thin metal layer, the
thickness is about 0.2 to 0.4 .mu.m. When the light shielding part
is formed from the black color material dispersed or dissolved in
the binder resin, the thickness is about 0.5 to 2 .mu.m.
(Transparent Substrate)
[0232] The transparent substrate of the color filter of the present
invention is not particularly limited, as long as it is a substrate
that is transparent to visible light. It can be selected from
general transparent substrates used in color filters. Concrete
examples thereof include inflexible transparent rigid materials
such as silica glass plate, non-alkali glass plate and synthetic
silica plate, and transparent flexible materials with flexibility
and flexible properties such as transparent resin film, optical
resin plate and flexible glass.
[0233] The thickness of the transparent substrate is not
particularly limited. Depending on the intended use of the color
filter of the present invention, one having a thickness of about
100 .mu.m to 1 mm can be used, for example.
[0234] In addition to the transparent substrate, the light
shielding part and the color layer, the color filter of the present
invention can also contain an overcoat layer and a transparent
electrode layer, for example. Moreover, an orientation layer and a
columnar spacer can be formed in the color layer.
5. Liquid Crystal Display Device
[0235] The liquid crystal display device of the present invention
contains the above-described color filter of the present invention,
a counter substrate, and a liquid crystal layer disposed between
the color filter and the counter substrate.
[0236] Such a liquid crystal display device of the present
invention will be explained with reference to a figure. FIG. 2 is a
schematic view of an example of the liquid crystal display device
of the present invention. As shown in FIG. 2, a liquid crystal
display device 40, which is the liquid crystal display device of
the present invention, contains a color filter 10, a counter
substrate 20 containing a TFT array substrate, etc., and a liquid
crystal layer 30 formed between the color filter 10 and the counter
substrate 20.
[0237] The liquid crystal display device of the present invention
is not limited to the configuration shown in FIG. 2. It can be a
configuration which is generally known as a liquid crystal display
device containing a color filter.
[0238] The method for driving the liquid crystal display device of
the present invention is not particularly limited and can be
selected from driving methods which are generally used in liquid
crystal display devices. Examples of such driving methods include a
TN method, an IPS method, an OCB method and an MVA method. In the
present invention, any of these methods can be suitably used.
[0239] The counter substrate can be appropriately selected,
depending on the driving method, etc., of the liquid crystal
display device of the present invention.
[0240] Also, the liquid crystal constituting the liquid crystal
layer can be selected from various liquid crystals with varying
dielectric anisotropies and mixtures thereof, depending on the
driving method, etc., of the liquid crystal display device of the
present invention.
[0241] The method for forming the liquid crystal layer can be
selected from methods which are generally used to produce liquid
crystal cells. Examples thereof include a vacuum injection method
and a liquid crystal dripping method.
[0242] In the vacuum injection method, for example, a liquid
crystal cell is produced in advance, using a color filter and a
counter substrate; liquid crystal is heated to become isotropic
liquid; the liquid crystal is injected into the liquid crystal
cell, in the form of isotropic liquid, using the capillary effect;
the liquid crystal cell is encapsulated with an adhesive agent,
thereby forming a liquid crystal layer; then, the encapsulated
liquid crystal can be oriented by gradually cooling the liquid
crystal cell to room temperature.
[0243] In the liquid crystal dripping method, for example, a
sealing agent is applied to the periphery of the color filter; the
color filter is heated to the temperature at which the liquid
crystal is in an isotropic phase; the liquid crystal is dripped
with a dispenser or the like, in the form of isotropic liquid; the
color filter and the counter substrate are stacked under reduced
pressure and attached to each other via the applied sealing agent,
thereby forming a liquid crystal layer; then, the encapsulated
liquid crystal can be oriented by gradually cooling the liquid
crystal cell to room temperature.
6. Organic Light-Emitting Display Device
[0244] The organic light-emitting display device of the present
invention contains the above-described color filter of the present
invention and an organic light-emitting material.
[0245] Such an organic light-emitting display device of the present
invention will be explained with reference to a figure. FIG. 3 is a
schematic view of an example of the organic light-emitting display
device of the present invention. As shown in FIG. 3, an organic
light-emitting display device 100, which is the organic
light-emitting display device of the present invention, contains a
color filter 10 and an organic light-emitting material 80. An
organic protection layer 50 and/or an inorganic oxide layer 60 can
be disposed between the color filter 10 and the organic
light-emitting material 80.
[0246] As the method for stacking the components of the organic
light-emitting material 80, for example, there may be mentioned a
method of stacking a transparent positive electrode 71, a positive
hole injection layer 72, a positive hole transport layer 73, a
light-emitting layer 74, an electron injection layer 75 and a
negative electrode 76 in this sequence on the color filter, a
method of attaching the organic light-emitting material 80 formed
on a different substrate onto the inorganic oxide layer 60. In the
organic light-emitting material 80, the transparent positive
electrode 71, the positive hole injection layer 72, the positive
hole transport layer 73, the light-emitting layer 74, the electron
injection layer 75, the negative electrode 76 and other components
can be selected from conventionally-known materials and used. The
organic light-emitting display device 100 produced as above is
applicable to passive or active drive organic EL displays, for
example.
[0247] The organic light-emitting display device of the present
invention is not limited to the configuration shown in FIG. 3. It
can have any one of configurations which are generally known as
those of organic light-emitting display devices containing a color
filter.
EXAMPLES
[0248] Hereinafter, the present invention will be described in
detail, by way of examples. The present invention is not limited by
these examples.
Synthesis Example 1
Synthesis of Dimeric Triarylmethane Dye
[0249] With reference to the method for producing intermediates 3
and 4 described in International Publication No. WO2012/144521,
15.9 g of a dimeric triarylmethane dye represented by the following
chemical formula (1) was obtained (yield 70%).
[0250] The compound thus obtained was confirmed to be a target
compound from the following analysis results:
[0251] MS(ESI) (m/z): 511(+), divalent
[0252] Elemental analysis values: CHN measurement values (78.13%,
7.48%, 7.78%); theoretical values (78.06%, 7.75%, 7.69%)
##STR00014##
Synthesis Example 2
Synthesis of Co-Lake Color Material A1
[0253] First, 5 g (4.58 mmol) of the dimeric triarylmethane dye
obtained in Synthesis Example 1, which is a basic dye, was added to
300 ml of water and dissolved at 90.degree. C. to prepare a basic
dye aqueous solution. Then, 0.620 g (0.916 mmol) of Acid Red 289
(AR289, manufactured by Tokyo Chemical Industry Co., Ltd.), which
is an acidic dye, and 9.39 g (2.75 mmol) of phosphotungstic acid
n-hydrate H.sub.3[PW.sub.12O.sub.40].nH.sub.2O (n=30) (manufactured
by Nippon Inorganic Colour & Chemical Co., Ltd.), which is a
polyoxometalate, were added to 100 mL of water, and the mixture was
stirred at 90.degree. C., thereby preparing an aqueous solution.
The aqueous solution thus prepared was added to the basic dye
aqueous solution in a dropwise manner for 15 minutes at 90.degree.
C., and the mixture was stirred at 90.degree. C. for 1 hour. A
precipitate thus produced was obtained by filtration and washed
with water. A cake thus obtained was dried to obtain 12.96 g of a
co-lake color material A1 represented by the following chemical
formula (2) (yield 98%). The co-lake color material A1 corresponds
to the color material (A-1) used in the present invention.
##STR00015##
Synthesis Examples 3 to 10
[0254] Co-lake color materials A2 to A4, blue lake color materials
A1 to A3, and violet lake color materials A1 and A2 were obtained
in the same manner as Synthesis Example 2, except that the basic
dye, acidic dye and polyoxometalate were changed as shown in Table
1. The co-lake color materials A2 to A4 and the violet lake color
material A1 correspond to the color material (A-1) used in the
present invention.
[0255] In Table 1, the value of each component represents the mass
(g) and is expressed as the amount of substance (mmol) in
parentheses.
[0256] Also, c:(d.times.e) represents {negative charge derived from
acidic dye component:negative charge derived from polyoxometalate}
in each color material and is 10:90 for the co-lake color material
A1, 10:90 for the co-lake color material A2, 30:70 for the co-lake
color material A3, and 20:80 for the co-lake color material A4.
TABLE-US-00001 TABLE 1 Basic dye Polyoxometalate Dimeric Acidic dye
Phosphotungstic Phosphomolybdic Synthesis Color triarylmethane
Basic Acid Acid acid n-hydrate acid n-hydrate W:Mo Yield Example
material dye Blue 7 Red 289 Red 52 (n = 30) (n = 30) ratio (%)
Synthesis Co-lake 5.00 0.620 -- 9.39 -- 100:0 98 Example 2 color
(4.58 mmol) (0.916 mmol) (2.75 mmol) material A1 Synthesis Co-lake
5.00 -- 0.620 -- 9.21 0.130 98:2 97 Example 3 color (4.58 mmol)
(0.916 mmol) (2.69 mmol) (0.055 mmol) material A2 Synthesis Co-lake
5.00 -- 1.86 -- 7.31 -- 100:0 96 Example 4 color (4.58 mmol) (2.78
mmol) (2.14 mmol) material A3 Synthesis Co-lake 5.00 -- -- 1.06
8.35 -- 100:0 95 Example 5 color (4.58 mmol) (1.83 mmol) (2.44
mmol) material A4 Synthesis Blue lake 5.00 -- -- -- 10.44 -- 100:0
99 Example 6 color (4.58 mmol) (3.05 mmol) material A1 Synthesis
Blue lake 5.00 -- -- -- 10.23 0.144 98:2 98 Example 7 color (4.58
mmol) (2.99 mmol) (0.061 mmol) material A2 Synthesis Blue lake --
5.00 -- -- 11.09 -- 100:0 94 Example 8 color (9.72 mmol) (3.24
mmol) material A3 Synthesis Violet lake 5.00 -- 6.20 -- -- -- -- 81
Example 9 color (4.58 mmol) (9.15 mmol) material A1 Synthesis
Violet lake -- 5.00 6.58 -- -- -- -- 80 Example 10 color (9.72
mmol) (9.72 mmol) material A2
Synthesis Example 11
Synthesis of Red Lake Color Material A1
[0257] First, 5 g (10.44 mmol) of Rhodamine 6G (manufactured by
Taoka Chemical Co., Ltd.), which is a basic dye, was added to 300
ml of water and dissolved at 90.degree. C. to prepare a basic dye
aqueous solution. Then, 11.90 g (3.48 mmol) of phosphotungstic acid
n-hydrate H.sub.3[PW.sub.12O.sub.40].nH.sub.2O (n=30) (manufactured
by Nippon Inorganic Colour & Chemical Co., Ltd.), which is a
polyoxometalate, was added to 100 mL of water, and the mixture was
stirred at 90.degree. C., thereby preparing an aqueous solution.
The aqueous solution thus prepared was added to the basic dye
aqueous solution in a dropwise manner for 15 minutes at 90.degree.
C., and the mixture was stirred at 90.degree. C. for 1 hour. A
precipitate thus produced was obtained by filtration and washed
with water. A cake thus prepared was dried to obtain 13.25 g of a
red lake color material A1 represented by the following chemical
formula (3) (yield 96%):
##STR00016##
Synthesis Example 12
Synthesis of Binder Resin A
[0258] First, 130 parts by mass of diethylene glycol ethyl methyl
ether (EMDG), which is a solvent, was put in a reactor equipped
with a cooling tube, an addition funnel, a nitrogen inlet, a
mechanical stirrer and a digital thermometer. After the temperature
of the solvent was increased to 110.degree. C. under a nitrogen
atmosphere, a mixture of 32 parts by mass of methyl methacrylate,
22 parts by mass of cyclohexyl methacrylate, 24 parts by mass of
methacrylic acid, and 2 parts by mass of
.alpha.,.alpha.'-azobisisobutyronitrile (AIBN), which is an
initiator, and 4.5 parts by mass of n-dodecyl mercaptan, which is a
chain transfer agent, were continuously added to the solvent in a
dropwise manner for 1.5 hours each.
[0259] Then, with maintaining the synthesis temperature, the
reaction was continued. Two hours after the completion of the
addition of the mixture in a dropwise manner, 0.05 part by mass of
p-methoxyphenol, which is a polymerization terminator, was added
thereto.
[0260] Next, with injecting air into the mixture, 22 parts by mass
of glycidyl methacrylate was added to the mixture. After the
temperature of the mixture was increased to 110.degree. C., 0.2
part by mass of triethylamine was added thereto, and an addition
reaction was caused at 110.degree. C. for 15 hours in the mixture,
thereby obtaining the binder resin A (solid content 44% by
mass).
[0261] The binder resin A thus obtained had a mass average
molecular weight Mw of 8,500 and an acid value of 85 mgKOH/g. The
mass average molecular weight Mw was calculated by gel permeation
chromatography (GPC) using polystyrene as a standard material and
THF as an eluent. The acid value was measured according to
JIS-K0070.
Synthesis Example 13
Synthesis of Organic Phosphonate Ester Compound 1
[0262] First, 142.61 parts by mass of diethylene glycol ethyl
methyl ether (EMDG), 50.00 parts by mass of phenylphosphonic acid
(product name: PPA; manufactured by: Nissan Chemical Industries,
Ltd.) and 0.10 part by mass of p-methoxyphenol were put in a
reactor equipped with a cooling tube, an addition funnel, a
nitrogen inlet, a mechanical stirrer and a digital thermometer.
With stirring the mixture under a nitrogen atmosphere, the
temperature of the mixture was increased to 120.degree. C. Then,
44.96 parts by mass of glycidyl methacrylate (GMA) was added to the
mixture in a dropwise manner for 30 minutes. The mixture was then
heated and stirred for 2 hours, thereby obtaining a 40.0% by mass
solution of the organic phosphonate ester compound 1, in which half
the divalent acidic groups of the PPA were esterified with the
epoxy groups of the GMA. The progress of the esterification
reaction was confirmed by an acid value measurement. The
composition ratio of the product thus obtained was confirmed by a
.sup.31P-NMR measurement. The acid value was 190 mgKOH/g. The
composition ratio was as follows: the organic phosphonate monoester
compound was 55% by mass; the organic phosphonate diester compound
was 23% by mass; and the PPA was 22% by mass.
Synthesis Example 14
Preparation of Phosphate-Modified Dispersant Solution A
[0263] In a 100 mL recovery flask, 30.07 parts by mass of PGMEA and
10.15 parts by mass (active solid content 6.09 parts by mass) of a
block copolymer containing tertiary amino groups (a block copolymer
having a constitutional unit represented by the general formula
(IV) and a constitutional unit represented by the general formula
(V)) (product name: BYK-LPN 6919; manufactured by: BYK-Chemie GmbH)
(amine value 120 mgKOH/g, solid content 60% by mass) were
dissolved. Then, 9.78 parts by mass (active solid content 3.91
parts by mass) (1.0 molar equivalent with respect to the tertiary
amino groups of the block copolymer) of the organic phosphonate
ester compound 1 of Synthesis Example 13 was added to the mixture.
The mixture was stirred at 40.degree. C. for 30 minutes, thereby
preparing the phosphate-modified dispersant solution A (solid
content 20% by mass). At this time, the amino groups of the block
copolymer included those forming salts by an acid-base reaction
with the acidic groups of the organic phosphonate ester compound
1.
Synthesis Example 15
Preparation of Phosphate-Modified Dispersant Solution B
[0264] In a 100 mL recovery flask, 34.30 parts by mass of PGMEA and
14.26 parts by mass (active solid content 8.55 parts by mass) of
BYK-LPN 6919 were dissolved. Then, 1.45 parts by mass (0.5 molar
equivalent with respect to the tertiary amino groups of the block
copolymer) of phenylphosphonic acid (product name: PPA;
manufactured by: Nissan Chemical Industries, Ltd.) was added to the
mixture. The mixture was stirred at 40.degree. C. for 30 minutes,
thereby preparing the phosphate-modified dispersant solution B
(solid content 20% by mass). At this time, the amino groups of the
block copolymer included those forming salts by an acid-base
reaction with the acidic groups of the PPA.
Synthesis Example 16
Production of Graft Polymer A
<Production of Macromonomer A>
[0265] First, 80.0 parts by mass of propylene glycol monomethyl
ether acetate (PGMEA) was put in a reactor equipped with a cooling
tube, an addition funnel, a nitrogen inlet, a mechanical stirrer
and a digital thermometer. With stirring under a nitrogen flow, the
temperature of the PGMEA was increased to 90.degree. C. Then, a
mixed solution of 50.0 parts by mass of methyl methacrylate, 15.0
parts by mass of n-butyl methacrylate, 15.0 parts by mass of benzyl
methacrylate, 20.0 parts by mass of 2-ethoxyethyl methacrylate, 4.0
parts by mass of mercaptoethanol, 30 parts by mass of PGMEA, and
1.0 part by mass of .alpha.,.alpha.'-azobisisobutyronitrile (AIBN)
was added to the PGMEA in a dropwise manner for 1.5 hours, and the
mixture was reacted for 3 hours. Next, the nitrogen flow was
stopped, and the reaction solution was cooled to 80.degree. C.
Then, 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko
K. K.), 0.125 part by mass of dibutyltin dilaurate, 0.125 part by
mass of p-methoxyphenol, and 10 parts by mass of PGMEA were added
to the reaction solution, and the reaction solution was stirred for
3 hours, thereby obtaining a 49.5% by mass solution of the
macromonomer A. The macromonomer A thus obtained was confirmed by
gel permeation chromatography (GPC) in a condition of
N-methylpyrrolidone, addition of 0.01 mol/L lithium
bromide/polystyrene standard. As a result, the macromonomer A had a
mass average molecular weight (Mw) of 4,040, a number average
molecular weight (Mn) of 1,930 and a molecular weight distribution
(Mw/Mn) of 2.09.
<Synthesis of Graft Copolymer A>
[0266] First, 80.0 parts by mass of PGMEA was put in a reactor
equipped with a cooling tube, an addition funnel, a nitrogen inlet,
a mechanical stirrer and a digital thermometer. With stirring under
a nitrogen flow, the temperature of the PGMEA was increased to
85.degree. C. Then, a mixed solution of 67.33 parts by mass (active
solid content 33.33 parts by mass) of the macromonomer A solution,
16.67 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMA),
1.24 parts by mass of n-dodecyl mercaptan, 20.0 parts by mass of
PGMEA, and 0.5 part by mass of AIBN, was added in a dropwise manner
for 1.5 hours. The mixture was then heated and stirred for 3 hours.
A mixed solution of 0.10 part by mass of AIBN and 10.0 parts by
mass of PGMEA was added thereto in a dropwise manner for 10
minutes. The mixture was further heated at the same temperature for
1 hour, thereby obtaining a 26.0% by mass solution of the graft
copolymer A. As a result of GPC measurement, the thus-obtained
graft copolymer A had a mass average molecular weight (Mw) of
11,510, a number average molecular weight (Mn) of 4,730, and a
molecular weight distribution (Mw/Mn) of 2.43.
Synthesis Example 17
Preparation of Phosphate-Modified Dispersant Solution C
[0267] In a 100 mL recovery flask, 16.77 parts by mass of PGMEA and
23.50 parts by mass (active solid content 6.11 parts by mass) of
the graft copolymer A of Synthesis Example 16 (a graft copolymer
having a constitutional unit represented by the general formula
(IV) and a constitutional unit represented by the general formula
(VI)) were dissolved. Then, 9.72 parts by mass (active solid
content 3.89 parts by mass) (1.0 molar equivalent with respect to
the tertiary amino groups of the graft copolymer) of the organic
phosphonate ester compound 1 of Synthesis Example 13 was added to
the mixture. The mixture was stirred at 40.degree. C. for 30
minutes, thereby preparing the phosphate-modified dispersant
solution C (solid content 20% by mass). At this time, the amino
groups of the graft copolymer included those forming salts by an
acid-base reaction with the acidic groups of the organic
phosphonate ester compound 1.
Production Example 1
Preparation of Color Material Dispersion Liquid A
[0268] First, 13.0 parts by mass of the co-lake color material A1
prepared in Synthesis Example 2, which is a color material, 22.75
parts by mass (active solid content 4.55 parts by mass) of the
phosphate-modified dispersant solution A prepared in Synthesis
Example 14, 13.30 parts by mass (active solid content 5.85 parts by
mass) of the binder resin A of Synthesis Example 12, and 50.95
parts by mass of PGMEA were mixed. Using a paint shaker
(manufactured by Asada Iron Works Co., Ltd.), the mixture was
subjected to a pre-dispersion for 1 hour with 2 mm zirconia beads
and then a main dispersion for 4 hours with 0.1 mm zirconia beads,
thereby obtain the color material dispersion liquid A.
Production Examples 2 to 11
Preparation of Color Material Dispersion Liquids B to K
[0269] The color material dispersion liquids B to K were prepared
in the same manner as Production Example 1, except that the color
material and the dispersion time were changed as shown in Table
2.
TABLE-US-00002 TABLE 2 Production Color material Color material
content (part by mass) Dispersion Example dispersion liquid Blue
color material Violet color material time (hr) Production Color
material Co-lake color material A1 13 -- -- 4 Example 1 dispersion
liquid A Production Color material Co-lake color material A2 13 --
-- 4 Example 2 dispersion liquid B Production Color material
Co-lake color material A3 13 -- -- 4 Example 3 dispersion liquid C
Production Color material Blue lake color material A1 13 -- -- 4
Example 4 dispersion liquid D Production Color material Blue lake
color material A2 13 -- -- 4 Example 5 dispersion liquid E
Production Color material Blue lake color material A3 13 -- -- 4
Example 6 dispersion liquid F Production Color material Copper
phthalocyanine 13 -- -- 4 Example 7 dispersion liquid G pigment
Production Color material -- -- Violet lake color material 13 3
Example 8 dispersion liquid H A1 Production Color material -- --
Violet lake color material 13 3 Example 9 dispersion liquid I A2
Production Color material Blue lake color material A1 11.7
Dioxazine pigment 1.3 4 Example 10 dispersion liquid J Production
Color material Copper phthalocyanine 9.75 Dioxazine pigment 3.25 4
Example 11 dispersion liquid K pigment
[0270] In Table 2, [0271] Dioxazine pigment: C. I. Pigment Violet
23 (primary particle diameter 60 nm) [0272] Copper phthalocyanine
pigment: C. I. Pigment Blue 15:6 (primary particle diameter 40
nm)
Example 1
[0273] First, 28.57 parts by mass of the color material dispersion
liquid H obtained in Production Example 8, 28.29 parts by mass of
the following binder composition A, 43.14 parts by mass of PGMEA,
0.04 part by mass of surfactant R08MH (manufactured by DIC) and 0.4
part by mass of silane coupling agent KBM503 (manufactured by
Shin-Etsu Silicones) were mixed. The mixture thus obtained was
subjected to pressure filtration, thereby obtaining a color resin
composition A.
<Binder Composition a (Solid Content 40% by Mass)>
[0274] Alkali soluble resin (the binder resin A of Synthesis
Example 4, solid content 44% by mass): 18.18 parts by mass [0275]
Pentafunctional to hexafunctional acrylate monomer (product name:
ARONIX M403; manufactured by TOAGOSEI Co., Ltd.): 8.00 parts by
mass [0276] Photopolymerization initiator:
2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropane-1-one (product
name: Irgacure 907; manufactured by: BASF): 3.00 parts by mass
[0277] Photosensitizer: 2,4diethylthioxanthone (product name:
KAYACURE DETX-S; manufactured by: Nippon Kayaku Co., Ltd.): 1.00
part by mass [0278] Solvent: propylene glycol monomethyl ether
acetate (PGMEA): 19.82 parts by mass
Examples 2 to 8
[0279] Color resin compositions C, E, F, I, J, K and L were
obtained in the same manner as Example 1, except that the color
material dispersion liquid was changed as shown in Table 3.
Comparative Examples 1 to 6
[0280] Color resin compositions B, D, G, H, M and N were obtained
in the same manner as Example 1, except that the color material
dispersion liquid was changed as shown in Table 3.
TABLE-US-00003 TABLE 3 Example Color resin composition Dispersion
liquid content (part by mass) Example 1 Color resin composition A
-- -- Color material 28.57 dispersion liquid H Comparative Color
resin composition B -- -- Color material 28.57 Example 1 dispersion
liquid I Example 2 Color resin composition C Color material 20.00
Color material 8.57 dispersion liquid G dispersion liquid H
Comparative Color resin composition D Color material 20.00 Color
material 8.57 Example 2 dispersion liquid G dispersion liquid I
Example 3 Color resin composition E Color material 28.57 -- --
dispersion liquid C Example 4 Color resin composition F Color
material 20.00 Color material 8.57 dispersion liquid D dispersion
liquid H Comparative Color resin composition G Color material 20.00
Color material 8.57 Example 3 dispersion liquid D dispersion liquid
I Comparative Color resin composition H Color material 20.00 Color
material 8.57 Example 4 dispersion liquid F dispersion liquid I
Example 5 Color resin composition I Color material 28.57 -- --
dispersion liquid A Example 6 Color resin composition J Color
material 25.71 Color material 2.86 dispersion liquid D dispersion
liquid H Example 7 Color resin composition K Color material 28.57
-- -- dispersion liquid B Example 8 Color resin composition L Color
material 25.71 Color material 2.86 dispersion liquid E dispersion
liquid H Comparative Color resin composition M Color material 28.57
-- -- Example 5 dispersion liquid J Comparative Color resin
composition N Color material 28.57 -- -- Example 6 dispersion
liquid K
Comparative Example 7
[0281] First, 20.00 parts by mass of the color material dispersion
liquid H obtained in Production Example 8, 1.70 parts by mass of a
10% by mass methanol solution of AR289, 30.52 parts by mass of the
binder composition A, 47.78 parts by mass of PGMEA, 0.04 part by
mass of surfactant R08MH (manufactured by DIC) and 0.4 part by mass
of silane coupling agent KBM503 (manufactured by Shin-Etsu
Silicones) were mixed. The mixture thus obtained was subjected to
pressure filtration, thereby obtaining a color resin composition
O.
(Evaluation)
<Optical Performance Evaluation, Heat Resistance
Evaluation>
[0282] Each of the blue color resin compositions obtained in
Examples and Comparative Examples was applied onto a glass
substrate having a thickness of 0.7 mm ("OA-10G" manufactured by
Nippon Electric Glass Co., Ltd.) using a spin coater, heat-dried on
a hot plate at 80.degree. C. for 3 minutes, and then irradiated
with ultraviolet light at 40 mJ/cm.sup.2 using a ultrahigh-pressure
mercury lamp, thereby obtaining a cured film (blue color layer).
The color substrate was subjected to post-baking (it may be
referred to as "PB" in Tables) in a clean oven at 230.degree. C.
for 60 minutes. The chromaticity (x, y), luminance (Y) and color
coordinates (L, a, b) of the thus-obtained color layer before and
after the post-baking, were measured using microscopic
spectrophotometer "OSP-SP200" manufactured by Olympus Corporation.
The contrast was measured using contrast measuring device "CT-1B"
manufactured by Tsubosaka Electric Co., Ltd.
[0283] Given that the color coordinates before the post-baking are
determined as L.sub.1, a.sub.1, b.sub.1 and the color coordinates
after the post-baking are determined as L.sub.2, a.sub.2, b.sub.2,
the chromaticity (.DELTA.Eab) is calculated by the following
formula and used as an indicator of heat resistance. At this time,
when the value of .DELTA.Eab is 10 or less, the color resin
composition is determined to be particularly suitable for practical
use. When the value of .DELTA.Eab is more than 20, the color resin
composition is determined to be unsuitable for practical use.
.DELTA.Eab={(L.sub.2-L.sub.1).sup.2+(a.sub.2-a.sub.1).sup.2+(b.sub.2-b.s-
ub.1).sup.2}.sup.1/2
[0284] Evaluation results are shown in Tables 4 to 7.
TABLE-US-00004 TABLE 4 Optical performance Color resin (230.degree.
C., 60 min, after PB) Example composition Color material x y Y C/R
.DELTA.Eab Example 1 Color resin Violet lake color 0.1612 0.0300
2.07 2,678 14.5 composition A material A1 Comparative Color resin
Violet lake color 0.1663 0.0300 1.91 713 22.8 Example 1 composition
B material A2
TABLE-US-00005 TABLE 5 Optical performance Color resin (230.degree.
C., 60 min, after PB) Example composition Color material x y Y C/R
.DELTA.Eab Example 2 Color resin Copper phthalocyanine Violet lake
color 0.1466 0.0570 5.10 2,486 12.5 composition C pigment material
A1 Comparative Color resin Copper phthalocyanine Violet lake color
0.1469 0.0570 4.94 1,455 13.0 Example 2 composition D pigment
material A2
TABLE-US-00006 TABLE 6 Optical performance Color resin (230.degree.
C., 60 min, after PB) Example composition Color material x y Y C/R
.DELTA.Eab Example 3 Color resin Co-lake color material A3 0.1514
0.0570 5.99 3,662 6.6 composition E Example 4 Color resin Blue lake
color Violet lake color 0.1528 0.0570 5.85 3,914 8.8 composition F
material A1 material A1 Comparative Color resin Blue lake color
Violet lake color 0.1538 0.0570 5.66 2,260 9.5 Example 3
composition G material A1 material A2 Comparative Color resin Blue
lake color Violet lake color 0.1617 0.0570 5.09 1,319 34.0 Example
4 composition H material A3 material A2
TABLE-US-00007 TABLE 7 Optical performance Color resin (230.degree.
C., 60 min, after PB) Example composition Color material x y Y C/R
.DELTA.Eab Example 5 Color resin Co-lake color material A1 0.1462
0.0820 9.71 4,048 7.6 composition I Example 6 Color resin Blue lake
color Violet lake color 0.1470 0.0820 9.56 4,945 8.5 composition J
material A1 material A1 Example 7 Color resin Co-lake color
material A2 0.1469 0.0820 9.49 4,739 7.9 composition K Example 8
Color resin Blue lake color Violet lake color 0.1478 0.0820 9.34
4,806 9.2 composition L material A2 material A1 Comparative Color
resin Blue lake color Dioxazine pigment 0.1466 0.0820 9.12 3,600
8.9 Example 5 composition M material A1 Comparative Color resin
Copper Dioxazine pigment 0.1464 0.0820 8.72 3,090 3.1 Example 6
composition N phthalocyanine pigment Comparative Color resin Blue
lake color AR289 Not evaluated due to precipitation Example 7
composition O material A1
[Results]
[0285] From the results in Table 4, the color layer formed with the
blue color resin composition of Example 1, which contains the
violet lake color material A1 in which the cation represented by
the general formula (I) and the monovalent anion represented by the
general formula (II) form a salt, can be evaluated as a
high-luminance color material with high heat resistance, because
the color layer is smaller in .DELTA.Eab and higher in luminance
than Comparative Example 1 using the color material in which Basic
Blue 7 and the monovalent anion represented by the general formula
(II) form a salt.
[0286] This advantage is also clear from the following: as is shown
by a comparison between Example 2 and Comparative Example 2 in
Table 5, this advantage is maintained in the case of being combined
with the copper phthalocyanine pigment, and as is shown by a
comparison between Example 4 and Comparative Example 3 in Table 6,
this advantage is also maintained in the case of being combined
with the blue lake color material. From these results, it is clear
that the color material in which the cation represented by the
general formula (I) and the monovalent anion represented by the
general formula (II) form a salt, is excellent as a color material
for adjusting the color of the blue color material.
[0287] Next, from a comparison between Example 6 and Comparative
Example 5 in Table 7, Example 6 using the violet lake color
material A1 in which the cation represented by the general formula
(I) and the monovalent anion represented by the general formula
(II) form a salt, is remarkably higher in luminance after the
post-baking and is better in heat resistance than Comparative
Example 5 using the dioxazine pigment. As is shown by Comparative
Example 6, the dioxazine pigment is excellent in heat resistance
when combined with other pigment. However, when the dioxazine was
combined with the dimeric triarylmethane dye, the heat resistance
decreased (Comparative Example 5). From these results, it is clear
that in the case of combining the color material in which the
cation represented by the general formula (I) and the monovalent
anion represented by the general formula (II) form a salt, with the
dimeric triarylmethane dye, the effects of high luminance after the
post-baking and excellent heat resistance become remarkable.
[0288] The color resin composition O of Comparative Example 7 could
not be evaluated since particles (which are considered to be AR289)
were heavily precipitated after the color resin composition was
applied using the spin coater and heat-dried on the hot plate at
80.degree. C. for 3 minutes.
[0289] In addition, considering all the results in detail, it is
clear from comparisons between Example 3 and Example 4, between
Example 5 and Example 6, and between Example 7 and Example 8, that
the color layer using the color material represented by the general
formula (III), which was obtained by laking the dimeric
triarylmethane dye, AR289 and the heteropolyoxometalate at the same
time, is particularly small in .DELTA.Eab and high in luminance.
This is considered to result from the following: the heat
resistance of the dyes were further increased by that the dimeric
triarylmethane dye, AR289 and the heteropolyoxometalate were laked
in such a manner that AR289 was incorporated in the color material
having a three-dimensional crosslinking structure composed of the
dimeric triarylmethane dye and the heteropolyoxometalate.
Production Example 12
Preparation of Color Material Dispersion Liquid L
[0290] First, 13.0 parts by mass of the co-lake color material A1
prepared in Synthesis Example 2, which is a color material, 22.75
parts by mass (active solid content 4.55 parts by mass) of the
phosphate-modified dispersant solution B prepared in Synthesis
Example 15, 13.30 parts by mass (active solid content 5.85 parts by
mass) of the binder resin A of Synthesis Example 12, and 50.95
parts by mass of PGMEA were mixed. Then, using a paint shaker
(manufactured by Asada Iron Works Co., Ltd.), the mixture was
subjected to a pre-dispersion for 1 hour with 2 mm zirconia beads
and then a main dispersion for 4 hours with 0.1 mm zirconia beads,
thereby obtaining the color material dispersion liquid L.
Production Example 13
Preparation of Color Material Dispersion Liquid M
[0291] The color material dispersion liquid M was obtained in the
same manner as Production Example 12, except that the
phosphate-modified dispersant solution C was used in place of the
phosphate-modified dispersant solution B.
Production Example 14
Preparation of Color Material Dispersion Liquid N
[0292] The color material dispersion liquid N was obtained in the
same manner as Production Example 12, except that 15.17 parts by
mass of Disperbyk-161 (a urethane-based dispersant manufactured by
BYK-Chemie GmbH, solid content 30% by mass) was used in place of
the phosphate-modified dispersant solution B, and the amount of the
PGMEA was changed to 58.54 parts by mass.
Production Example 15
Preparation of Color Material Dispersion Liquid O
[0293] The color material dispersion liquid O was obtained in the
same manner as Production Example 12, except that 11.38 parts by
mass of BYK-LPN 21116 (a block copolymer manufactured by BYK-Chemie
GmbH, solid content 40% by mass) was used in place of the
phosphate-modified dispersant solution B, and the amount of the
PGMEA was changed to 62.33 parts by mass.
Production Example 16
Preparation of Color Material Dispersion Liquid P
[0294] The color material dispersion liquid P was obtained in the
same manner as Production Example 12, except that the co-lake color
material A4 of Synthesis Example 5 was used in place of the co-lake
color material A1.
Production Example 17
Preparation of Color Material Dispersion Liquid Q
[0295] The color material dispersion liquid Q was obtained in the
same manner as Production Example 12, except that 11.7 parts by
mass of the blue lake color material A1 of Synthesis Example 6 and
1.3 parts by mass of the red lake color material A1 of Synthesis
Example 11 were used in place of the co-lake color material A1.
Production Example 18
Preparation of Color Material Dispersion Liquid R
[0296] The color material dispersion liquid R was obtained in the
same manner as Production Example 12, except that the blue lake
color material A1 of Synthesis Example 6 was used in place of the
co-lake color material A1.
Production Example 19
Preparation of Color Material Dispersion Liquid S
[0297] The color material dispersion liquid S was obtained in the
same manner as Production Example 12, except that the blue lake
color material A3 of Synthesis Example 8 was used in place of the
co-lake color material A1.
Example 9
[0298] A color resin composition I-2 was obtained in the same
manner as Example 1, except that the color material dispersion
liquid L of Production Example 12 was used in place of the color
material dispersion liquid H.
Example 10
[0299] A color resin composition I-3 was obtained in the same
manner as Example 9, except that the color material dispersion
liquid M of Production Example 13 was used in place of the color
material dispersion liquid L.
Example 11
[0300] A color resin composition I-4 was obtained in the same
manner as Example 9, except that the color material dispersion
liquid N of Production Example 14 was used in place of the color
material dispersion liquid L.
Example 12
[0301] A color resin composition I-5 was obtained in the same
manner as Example 9, except that the color material dispersion
liquid O of Production Example 15 was used in place of the color
material dispersion liquid L.
Example 13
[0302] A color resin composition P was obtained in the same manner
as Example 9, except that the color material dispersion liquid P of
Production Example 16 was used in place of the color material
dispersion liquid L.
Comparative Example 8
[0303] A color resin composition Q was obtained in the same manner
as Example 9, except that the color material dispersion liquid Q of
Production Example 17 was used in place of the color material
dispersion liquid L.
Comparative Example 9
[0304] A color resin composition R was obtained in the same manner
as Example 9, except that the color material dispersion liquid R of
Production Example 18 was used in place of the color material
dispersion liquid L.
Comparative Example 10
[0305] A color resin composition S was obtained in the same manner
as Example 9, except that the color material dispersion liquid S of
Production Example 19 was used in place of the color material
dispersion liquid L.
(Evaluation)
<Optical Performance Evaluation, Heat Resistance
Evaluation>
[0306] The color resin compositions of Examples 9 to 14 and 5, and
those of Comparative Examples 8 to 11 and 5 were evaluated for
optical performance and heat resistance, in the same manner as
above. The results are shown in Table 8.
<Temporal Stability Evaluation>
[0307] The color resin compositions of Examples 9 to 14 and
Comparative Examples 8 to 11 were measured for shear viscosity
(mPasec) at a shear rate of 60 rpm, using "Rheometer MCR301"
manufactured by Anton Paar. For evaluation, each color resin
composition was measured for the viscosity just after the
preparation and the viscosity after 7 days of storage at room
temperature. The results are shown in Table 8.
TABLE-US-00008 TABLE 8 Optical performance Viscosity Color resin
(230.degree. C., 60 min, after PB) After 7 Example composition
Color material x y Y C/R .DELTA.Eab Initial days Example 5 Color
resin Co-lake color material A1 0.1462 0.0820 9.71 4,048 7.6 2.63
2.65 composition I Example 9 Color resin Co-lake color material A1
0.1462 0.0820 9.77 4,120 6.8 2.68 2.65 composition I-2 Example 10
Color resin Co-lake color material A1 0.1460 0.0820 9.77 4,230 5.8
2.65 2.69 composition I-3 Example 11 Color resin Co-lake color
material A1 0.1455 0.0820 9.76 3,967 4.3 2.85 2.81 composition I-4
Example 12 Color resin Co-lake color material A1 0.1467 0.0820 9.58
4,061 11.9 2.71 2.66 composition I-5 Example 13 Color resin Co-lake
color material A4 0.1445 0.0820 9.84 2,819 3.9 2.67 2.68
composition P Comparative Color resin Blue lake Dioxazine 0.1466
0.0820 9.12 3,600 8.9 2.69 5.04 Example 5 composition M color
pigment material A1 Comparative Color resin Blue lake Red lake
0.1480 0.0820 9.43 4,526 11.9 2.79 6.54 Example 8 composition Q
color color material A1 material A1 Comparative Color resin Blue
lake color material A1 0.1398 0.0820 9.33 4,890 7.5 2.70 5.19
Example 9 composition R Comparative Color resin Blue lake color
material A3 0.1514 0.1464 16.83 4,718 65.6 2.64 2.65 Example 10
composition S
CONCLUSION
[0308] As is shown by the results in Table 8, the color resin
compositions containing the blue lake color material A1, such as
Comparative Examples 5, 8 and 9, showed an increase in viscosity
over time. Meanwhile, it is clear that the color resin compositions
of Examples 5 and 9 to 13, which were prepared using the co-lake
color material A1 or A4 represented by the general formula (III'),
are excellent in temporal stability and high in luminance after the
post-baking. The color resin composition of Comparative Example 10
was excellent in temporal stability; however, it was very poor in
heat resistance, so that the color was severely deteriorated after
the post-baking and could not compared in the standard color.
[0309] For the substrate to which the color resin composition Q of
Comparative Example 8 was applied, it was found that at the time of
post-baking, a red dye, which is considered to be derived from the
red lake color material A1, attaches to and contaminate the
environment. This is considered to be because the red lake color
material A1 was sublimated by heat.
REFERENCE SIGNS LIST
[0310] 1. Transparent substrate [0311] 2. Light shielding part
[0312] 3. Color layer [0313] 10. Color filter [0314] 20. Counter
substrate [0315] 30. Liquid crystal layer [0316] 40. Liquid crystal
display device [0317] 50. Organic protection layer [0318] 60.
Inorganic oxide layer [0319] 71. Transparent positive electrode
[0320] 72. Positive hole injection layer [0321] 73. Positive hole
transport layer [0322] 74. Light-emitting layer [0323] 75. Electron
injection layer [0324] 76. Negative electrode [0325] 80. Organic
light-emitting material [0326] 100. Organic light-emitting display
device [0327] 101. Color-forming moiety [0328] 102. Linking group A
[0329] 103. Cation represented by the general formula (I) [0330]
104. Monovalent anion represented by the general formula (II)
[0331] 105. Polyoxometalate anion [0332] 106. Polyoxometalate anion
not forming a salt [0333] 107. Cation being represented by the
general formula (I) and not forming a salt [0334] 110. Color
material (A-1) [0335] 120. Color material represented by the
general formula (III) [0336] 130. Color material represented by the
general formula (III')
* * * * *