JP2012185241A - Dye for color filter, coloring composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stable coloring composition which has high lightness and excellent tinctorial power and satisfies the other physical properties (color characteristic, heat resistance, light resistance, solvent resistance), and a color filter of high lightness using the same.SOLUTION: Provided is a dye for color filter, represented by the following general formula, where R-Rrepresent, individually independently, a hydrogen atom, a halogen or the like.

Description

The present invention relates to a color filter including a dye, a coloring composition, and a filter segment formed using the same, which are used for manufacturing a color filter used in a color liquid crystal display device, an organic EL display device, a color image pickup tube element, and the like. It is about.

The color liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of the light that has passed through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display by using a twisted nematic (TN) type liquid crystal. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. Therefore, liquid crystal display devices are being developed for use in televisions and personal computer monitors.

Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment of nematic liquid crystal with VA (VA)
) System, and an optically-conventional-bend (OCB) system in which the optical axes of the uniaxial retardation film are orthogonal to each other to perform optical compensation, and each of them is put into practical use.

In general, a color filter is formed in a fine strip (stripe) shape formed of a red filter layer (R), a green filter layer (G), and a blue filter layer (B) formed on the surface of a transparent substrate such as glass. The filter segments (pixels) are arranged in parallel or intersecting with each other, or the fine filter segments are arranged in a constant vertical and horizontal arrangement. The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue. Recently, in addition to a red filter layer (R), a green filter layer (G), and a blue filter layer (B), a filter segment including a yellow filter layer (Y) is also used.

On the color filter used in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. Has been. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.

One of the quality items required for the color filter is brightness. When a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights that are light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend.

Furthermore, as described above, since color liquid crystal devices have been used in televisions, personal computer monitors, etc., there is a need for higher brightness, higher contrast, wider color reproduction area, and higher reliability for color filters. It is high.

Also, C-MOS (Complementary Metal Oxide Semico
nductor: complementary metal oxide semiconductor), CCD (Charge Coupled D)
A color image pickup tube element typified by a device (charge coupled device) has a primary color filter segment of an additive mixture of a red filter layer (R), a green filter layer (G), and a blue filter layer (B) on the light receiving element. In general, color separation is performed by disposing color filters each having a color separation. Further, since high sensitivity can be obtained compared to the primary color filter, a color filter having filter segments of cyan, magenta, and yellow (CMY) corresponding to the complementary colors of red, green, and blue is often used. Complementary color filters are often used in video cameras and the like that are difficult to use an auxiliary light source such as a flash.

In recent years, color filters used in color image pickup tube elements have high transmittance,
That is, there are increasing demands for brightness and high reliability.

The color filter production method includes a dyeing method using a dye or a salt-forming dye as a colorant, a dye dispersion method, a pigment dispersion method using a pigment as a colorant, a printing method, and an electrodeposition method. Among these, the dyeing method or the dye dispersion method has a drawback that the heat resistance and light resistance are slightly inferior because the colorant is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as a colorant for the color filter, and a pigment dispersion method is often used as a manufacturing method because of the accuracy and stability of the forming method.

In the pigment dispersion method, a color resist is formed by mixing and blending a photosensitive agent or an additive into a resin in which pigment particles as a colorant are dispersed in a resin, and this color resist is applied onto a substrate by a coating device such as a spin coater. In this method, a color filter is produced by forming a coating film by the above, performing selective exposure through a mask with an aligner or a stepper, patterning by alkali development and thermosetting, and repeating this operation.

In general, the pigment particles are subjected to a micronization treatment and a pigment dispersion in which the micronized pigment is brought close to the primary particles as much as possible is used to suppress light scattering by the pigment and achieve high contrast. In addition, since the transparency of the dispersion is improved, the spectral spectrum of the dispersion has high transmittance, and high brightness is realized. By using this dispersion as a color resist, a color filter having high contrast and high brightness can be obtained.

Conventionally, an anthraquinone pigment (for example, CI Pigment Red 177) or a diketopyrrolopyrrole pigment (for example, CI Pigment Red 254) has been used as a colorant used for forming a red filter segment. It was. These pigments can be easily refined by mechanical treatment, and further, the refined pigment can be dispersed relatively easily. Therefore, these pigments are useful for improving contrast and brightness. As the formation of the red filter segment, C.I. I. Pigment Yellow 138, 139
In general, yellow pigments such as 150, 185 and the like are used in combination as a colorant.

In addition, as a colorant used for forming a green filter segment, a halogenated copper phthalocyanine pigment (for example, CI Pigment Green 36 or CI Pigment Green 7) has been conventionally used. A zinc halide phthalocyanine pigment (for example, CI Pigment Green 58) in which the central metal is replaced with zinc, which is a color material that exhibits color tone and a wide color display area and has high coloring power, has been often used ( Patent Literatures 1 to 3). These green pigments include C.I. I. Pigment yellow 138, 139, 1
It is common to use yellow pigments such as 50 and 185 in combination.

However, as described above, there is an increasing demand for higher brightness in the market, but as long as the conventionally used pigment is used in both the red filter and the green filter,
It is a situation where it is difficult to achieve further high brightness.

Further, as described above, a method for adding a yellow filter segment (pixel) to a color filter having a red filter segment, a green filter segment, and a blue filter segment has been proposed for the purpose of extending the color reproduction range of the color filter. (Patent Documents 4 and 5). Examples of the colorant used for forming the yellow filter segment include C.I. I.
Yellow pigments such as CI Pigment Yellow 138, 139, 150, and 185,
It is also necessary to increase the brightness of the yellow filter segment. Again, as long as the conventionally used pigments are used, it is difficult to achieve higher brightness.

Further, the following C.I. I. There has been a report (Patent Document 6) of improving the lightness of green, red, and yellow filter segments using Acid Yellow 5 dye, but further improvement in lightness and coloring power is required.

  C. I. Acid Yellow 5

JP-A-6-75375 Republic of Korea Open Patent Gazette 2010-0010490 JP 2004-307391 A JP 2005-196166 A JP 2004-295116 A Japanese Patent Application No. 2010-149118

An object of the present invention is to provide a pigment that has high brightness and excellent coloring power and that satisfies other physical properties (color characteristics, heat resistance, light resistance, solvent resistance), a coloring composition comprising the same, and a coloring composition that uses the same. It is to provide a color filter with high brightness.

As a result of intensive studies to solve the above problems, the present inventors have found that C.I. I. By using a dye represented by the following general formula (1) or the following general formula (2) in which one benzene ring is added to the mother skeleton of Acid Yellow 5,
It has been found that high brightness and high coloring power can be achieved by increasing the wavelength of the spectrum, and the present invention has been made based on this finding.

That is, the present invention relates to a color filter dye represented by the following general formula (1) or the following general formula (2).
General formula (1)

General formula (2)

Wherein R _{1 to} R ₂₈ are each independently a hydrogen atom, halogen atom, hydroxyl group, nitro group, substituted or unsubstituted amino group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl Group, substituted or unsubstituted aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted sulfonyl group, or Represents a substituted carbonyl group.)
Moreover, this invention relates to the coloring composition for color filters containing the pigment | dye for color filters represented by the said General formula (1) or the said General formula (2), and binder resin at least.

The present invention also relates to the color composition for a color filter as described above, further comprising a pigment.

The present invention also relates to a color filter including at least a red filter segment, a green filter segment, and a blue filter segment, wherein the at least one filter segment is formed of the color filter coloring composition described above. .

In the present invention, a color filter having high brightness and high coloring power can be obtained by using the coloring composition using the color filter dye and the resin of the present invention. Other physical properties (
A color filter having good color characteristics, heat resistance, light resistance, and solvent resistance can be obtained.

  Hereinafter, the present invention will be described in detail.

  In addition, “CI” described below means a color index (CI).

  First, the color filter dye of the present invention will be described.

In the present invention, R _{1 to} R ₂₈ in the general formula (1) and the general formula (2) are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a substituted or unsubstituted amino group, a substituted or unsubstituted group. Alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted A substituted arylthio group, a substituted sulfonyl group, or a substituted carbonyl group is represented.

In R _{1 to} R ₂₈ , the substituted amino group is preferably a substituted amino group having 1 to 40 carbon atoms, such as a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a propylamino group, a diamino group, Propylamino group, butylamino group, dibutylamino group, benzylamino group, dibenzylamino group, (m-tolyl) amino group, (p-tolyl)
Amino group, phenylmethylamino group, phenylamino group, diphenylamino group, di-m-
Tolylamino group, di-p-tolylamino group, di-p-pyridylamino group, di-m-pyridylamino group, phenylthiophenylamino group, diphenylthioamino group, difuranylamino group, di-p-biphenylylamino group, di (4 -Methylbiphenyl) amino group, naphthylphenylamino group, dinaphthylamino group, phenyl-p-biphenylamino group, bis [4
-(Α, α'-dimethylbenzyl) phenyl] amino group, formylamino group, acetylamino group, propionylamino group, butyrylamino group, isobutyrylamino group, benzoylamino group, isocyanate group, aziridinyl group, 2-methylazido Lysinyl group, maleimide group, acetamide group, propionamide group, butyramide group, carbamic acid methyl ester group, carbamic acid ethyl ester group, carbamic acid phenyl ester group, diglycidylamino group, bis (3-ethyloxetane-3-ylmethyl) ) Amino group and the like.

In R _{1 to} R ₂₈ , the substituted or unsubstituted alkyl group preferably has 1 carbon atom.
An alkyl group having ˜40, more preferably a substituted alkyl group having 1 to 20 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group. In addition to unsubstituted linear or branched alkyl groups such as tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, ethoxyethyl group, ethoxymethyl group, methoxymethyl group, methoxyethyl Group, 2-phenylisopropyl group, benzyl group, α-phenoxybenzyl group, α, α-dimethylbenzyl group, α, α-methylphenylbenzyl group, triphenylmethyl group, α-benzyloxybenzyl group, 3-
Methyl oxetane-3-ylmethyl group, 3-ethyloxetane-3-ylmethyl group, 2-
Isocyanatoethyl group, 2-aziridinylethyl group, 2- (tert-butylcarbodiimide) ethyl group, 2- (cyclohexylcarbodiimide) ethyl group, maleimidomethyl group, hydroxymethyl group, hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 9-hydroxynonyl group, 1-hydroxylethyl group and the like can be mentioned.

In R _{1 to} R ₂₈ , the substituted or unsubstituted cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 4 to 8 carbon atoms, such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo A heptyl group, a cyclooctyl group, an adamantyl group, etc. are mentioned.

In R _{1 to} R ₂₈ , the substituted or unsubstituted aryl group preferably has 6 carbon atoms.
A substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having ˜40, more preferably a substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having 6 to 18 carbon atoms, for example, Phenyl group, 1-naphthyl group, 2-naphthyl group, p-biphenyl group, m-biphenyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2- Fluorenyl group, 3-fluorenyl group, 9-fluorenyl group, 1-pyrenyl group, 2-pyrenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 4-methylbiphenyl group, ter Phenyl group, 4-methyl-1-naphthyl group, 4-tert-butyl-1-naphthyl group, 4-naphthyl-1-naphthyl group, 6-
Examples include phenyl-2-naphthyl group, 10-phenyl-9-anthryl group, spirofluorenyl group, 4-malemidylphenyl group, 2-benzocyclobutenyl group and the like.

In R _{1 to} R ₂₈ , the substituted or unsubstituted alkyloxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 40 carbon atoms, and more preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. Substituted alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, n-
Pentaoxy group, n-heptaoxy group, n-octyloxy group, t-octyloxy group,
Benzyloxy group, 1-adamantyloxy group, 2-adamantyloxy group, 3-methyloxetane-3-ylmethyloxy group, 3-ethyloxetane-3-ylmethyloxy group, 2-isocyanatoethyloxy group, 2-azi Lysinylethyloxy group, 2-benzocyclobutenylethyloxy group, hydroxymethyloxy group, 2-hydroxyethyloxy group, 3-hydroxypropyloxy group, 4-hydroxybutyloxy group, 5-hydroxypentyloxy group, 9 -Hydroxynonyloxy group, 2-hydroxy-2methylpropyloxy group, prop-2-nyloxy group, 1-methylprop-2-nyloxy group, bute-2
-Nyloxy group, 3-phenylprop-2-nyloxy group, prop-2-nyloxy group,
1-methylprop-2-nyloxy group, but-2-ynyloxy group, pent-2-yloxy group, 3-phenylprop-2-ynyloxy group, propynyloxy group, 2-phenylethynyl group, acrylic acid group, 1-methylacrylic group Acid group, 1,2-dimethylacrylic acid group, 1-
Examples thereof include a phenylacrylic acid group and a 4,5-dihydrooxazolylmethyloxy group.

In R _{1 to} R ₂₈ , the substituted or unsubstituted aryloxy group is preferably a substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having 6 to 40 carbon atoms, more preferably 6 carbon atoms. Substituted or unsubstituted monocyclic or condensed polycyclic aromatic groups having ˜18, for example, phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, p-biphenyloxy group, m-biphenyloxy group 2-anthryloxy group, 9-anthryloxy group, 2-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, 2-fluorenyloxy group, 3-flurane Oleenyloxy group, 9-fluorenyloxy group, 1-pyrenyloxy group, 2-pyrenyloxy group, 3-perylenyloxy group,
o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, 4-methylbiphenyloxy group, terphenyloxy group, 4-methyl-1-naphthyloxy group, 4-tert-
Butyl-1-naphthyloxy group, 4-naphthyl-1-naphthyloxy group, 6-phenyl-
A 2-naphthyloxy group, a 10-phenyl-9-anthryloxy group, a spirofluorenyloxy group, a 2-benzocyclobutenyloxy group, and the like can be given.

In R _{1 to} R ₂₈ , the substituted or unsubstituted alkylthio group is preferably a substituted or unsubstituted alkylthio group having 1 to 40 carbon atoms, more preferably a substituted or unsubstituted group having 1 to 10 carbon atoms. An alkylthio group of, for example, a methylthio group,
Ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, t-butylthio group, n-pentylthio group, n-heptylthio group, n-octylthio group, t-octylthio group, benzylthio group, 1-adamantylthio group 2-adamantylthio group, 3-methyloxetane-3-ylmethylthio group, 3-ethyloxetane-3-ylmethylthio group, 2-isocyanatoethylthio group, 2-aziridinylethylthio group, 2-benzocyclobu Tenenylethylthio group, hydroxymethylthio group, 2-hydroxyethylthio group, 3-hydroxypropylthio group, 4-hydroxybutylthio group, 5-hydroxypentylthio group, 9-hydroxynonylthio group, 2-hydroxy-2methyl Propylthio group, prope-2
-Nylthio group, 1-methylprop-2-nylthio group, but-2-enylthio group, 3-phenylprop-2-enylthio group, prop-2-nylthio group, 1-methylprop-2-nylthio group, buty- A 2-nylthio group, a pent-2-ylthio group, a 3-phenylprop-2-ylthio group, a propynylthio group, a 2-phenylethynylthio group, a 4,5-dihydrooxazolylmethylthio group, and the like can be given.

In R _{1 to} R ₂₈ , the substituted or unsubstituted arylthio group is preferably a substituted or unsubstituted monocyclic or condensed polycyclic aromatic group in which the aryl group of the arylthio group has 6 to 40 carbon atoms, Preferably, the aryl group of the arylthio group is a substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having 6 to 18 carbon atoms, such as phenylthio group, 1-naphthylthio group, 2-naphthylthio group, p-biphenyl. Thio group, m-biphenylthio group, 2-anthrylthio group, 9-anthrylthio group, 2-phenanthrylthio group, 3-
Phenanthrylthio group, 9-phenanthrylthio group, 2-fluorenylthio group, 3-fluorenylthio group, 9-fluorenylthio group, 1-pyrenylthio group, 2-pyrenylthio group,
3-perylenylthio group, o-tolylthio group, m-tolylthio group, p-tolylthio group, 4-
Methylbiphenylthio group, terphenylthio group, 4-methyl-1-naphthylthio group, 4-
tert-butyl-1-naphthylthio group, 4-naphthyl-1-naphthylthio group, 6-phenyl-2-naphthylthio group, 10-phenyl-9-anthrylthio group, spirofluorenylthio group, 2-benzocyclobutenylthio group Etc.

In R _{1 to} R ₂₈ , examples of the substituted sulfonyl group include a sulfonic acid group, sulfonate, methoxysulfonyl group, phenoxysulfonyl group, dimethylaminosulfonyl group, diphenylaminosulfonyl group, ditolylaminosulfonyl group, methylsulfonyl group, ethyl A sulfonyl group, a phenylsulfonyl group, a tolylsulfonyl group, 2-butenyloxysulfonyl group, etc. are mentioned.

In R _{1 to} R ₂₈ , examples of the substituted carbonyl group include a carboxylic acid group, a carboxylate, a methoxycarbonyl group, a phenoxycarbonyl group, a dimethylaminocarbonyl group, a diphenylaminocarbonyl group, a ditolylaminocarbonyl group, a methylcarbonyl group, and ethyl. Carbonyl group, phenylcarbonyl group, tolylcarbonyl group, propenonyl group, but-2-one-
1-nonyl group, 2-methylbut-2-one-1-nonyl group, 3-phenylprop-2-one-
1-nonyl group, 2-butenyloxycarbonyl group, etc. are mentioned.

Representative examples of the color filter dyes represented by the general formulas (1) and (2) of the present invention are shown in the following Table 1, but the present invention is not limited to these representative examples.
Table 1

The compound group represented by the general formula (1) and the general formula (2) is obtained by reacting a benzoquinaldine compound and naphthalenedicarboxylic acid anhydride in benzoic acid at a high temperature as shown in the following reaction formula 1 and the following reaction formula 2. , You can get.

  Reaction formula 1

Reaction formula 2

In the compounds represented by the general formula (1) and the general formula (2), those substituted with a sulfonic acid amide, a sulfonic acid salt, a carboxylic acid amide, or a carboxylic acid salt are substituted with a sulfonic acid substitution product or a carboxylic acid substitution product. Can be obtained by amidation or salt formation. Moreover, what substituted the quaternary amine compound in the compound group represented by General formula (1) and General formula (2) can be obtained by quaternizing a tertiary amine.

The compound obtained above can be obtained by conventional isolation methods such as extraction, distillation, column purification, recrystallization,
It is isolated and purified from the reaction mixture according to conventionally known conventional methods such as reprecipitation, washing, filtration and drying.

  Next, the coloring composition for a color filter of the present invention will be described in detail.

The coloring composition composed of the color filter coloring matter of the present invention has a yellow hue itself, and can be used in combination with other pigments and dyes to give a coloring composition exhibiting green and red. In addition, it is possible to obtain a colorant having the necessary tolerance for production and excellent in color development and color reproducibility.

Moreover, although it may be used independently for yellow, in order to adjust chromaticity and to improve heat resistance, pigments and dyes may be contained as long as the effects of the present invention are not impaired.

<Pigment>
The green colorant in the case of forming a green filter segment can be contained with the green pigment and / or blue pigment described below depending on the desired hue.
(Pigment forming green filter segment)
[Green pigment]
As the green pigment, a polyhalogenated phthalocyanine pigment is preferably used. The polyhalogenated phthalocyanine pigment represents a phthalocyanine pigment having at least two or more halogen atoms. Specifically, C.I. I. Pigment Green 7, 36,
37, 58 and the like.
[Blue pigment]
As the blue pigment forming the green filter segment, it is preferable to use an aluminum phthalocyanine pigment. Aluminum phthalocyanine pigments are preferred pigments because they have higher coloring power than halogenated phthalocyanine pigments. Thereby, the addition amount of a pigment can be reduced and the film thickness of a color filter can be made small. Moreover, the point which does not contain a halogen atom is also preferable in consideration of environmental safety.

In the coloring composition for a green color filter of the present invention, particularly preferred pigments are aluminum phthalocyanine and polyhalogenated zinc phthalocyanine (CI Pigment Green 58).
[Yellow pigment]
The green colorant may further use a yellow pigment. As a yellow pigment that can be used in combination,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15
16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37
37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 7
4, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 10
6, 108, 109, 110, 113, 114, 115, 116, 117, 118, 11
9, 120, 123, 126, 127, 128, 129, 138, 139, 147, 15
0, 151, 152, 153, 154, 155, 156, 161, 162, 164, 16
6, 167, 168, 169, 170, 171, 172, 173, 174, 175, 17
6, 177, 179, 180, 181, 182, 185, 187, 188, 193, 19
4, 198, 199, 213, 214, 218, 219, 220, 221 or the like.

The use ratio of the green / blue pigment and the color filter dye of the present invention is preferably 1 to 1200 parts by weight of the color filter dye of the present invention with respect to 100 parts by weight of the pigment. More preferably 5
~ 600 parts by weight. If the addition amount of the color filter dye of the present invention is less than 1 part by weight, the reproducible chromaticity region becomes narrow, and if it exceeds 1200 parts by weight, the hue changes, which is not preferable.

In consideration of the color composition, the blending ratio of the yellow pigment and the content of the color filter dye of the present invention is 1 to 400 for the color filter dye of the present invention with respect to 100 parts by weight of the yellow pigment.
It is preferable that it is a weight part. More preferably, the color filter dye of the present invention is in the range of 5 to 300 parts by weight with respect to 100 parts by weight of the yellow pigment. These blends can be appropriately adjusted and used in consideration of the heat resistance, light resistance, and brightness of the colorant.
(Pigment forming yellow filter segment)
[Yellow pigment]
When forming a yellow filter segment, in addition to the color filter dye of the present invention,
The following yellow pigments can be used in combination.
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15
16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37
37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 7
4, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 10
6, 108, 109, 110, 113, 114, 115, 116, 117, 118, 11
9, 120, 123, 126, 127, 128, 129, 138, 139, 147, 15
0, 151, 152, 153, 154, 155, 156, 161, 162, 164, 16
6, 167, 168, 169, 170, 171, 172, 173, 174, 175, 17
6, 177, 179, 180, 181, 182, 185, 187, 188, 193, 19
4, 198, 199, 213, 214, 218, 219, 220, 221 or the like. I. Pigment Yellow 138, 139, 150, and 185 are preferably used.

The use ratio of the yellow pigment and the color filter dye of the present invention is preferably 1 to 1200 parts by weight of the color filter dye of the present invention with respect to 100 parts by weight of the yellow pigment. More preferably, 5
600 parts by weight.

In consideration of the color composition, the blending ratio of the yellow pigment and the color filter dye of the present invention is 1 to 400 parts by weight of the color filter dye of the present invention with respect to 100 parts by weight of the yellow pigment. preferable. More preferably, the color filter dye of the present invention is in the range of 5 to 300 parts by weight with respect to 100 parts by weight of the yellow pigment. These blends can be appropriately adjusted and used in consideration of the heat resistance, light resistance, and brightness of the colorant.

Particularly preferred pigments here are C.I. I. Pigment Yellow 138, 139, 150
185.
(Pigment forming red filter segment)
[Red pigment]
The red colorant in the case of forming the red filter segment can contain a red pigment described below depending on a desired dye.

Examples of red pigments include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2
48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 1
22, 146, 168, 169, 176, 177, 178, 179, 184, 185, 1
87, 200, 202, 208, 210, 242, 246, 254, 255, 264, 2
70,272,273,274,276,277,278,279,280,281,2
82, 283, 284, 285, 286, or 287 are used. Among them, C.I. I. Pigment Red 177, 179, 254 is preferably used.
[Yellow pigment, Orange pigment]
The red colorant may be used in combination with the following yellow pigment and orange pigment.

C. I. Pigment orange 43, 71, or 73, and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 1
7, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1
40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77,
81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108
109, 110, 113, 114, 115, 116, 117, 118, 119, 120
, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151
, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167
168, 169, 170, 171, 172, 173, 174, 175, 176, 177
179, 180, 181, 182, 185, 187, 188, 193, 194, 198
199, 213, 214, 218, 219, 220, 221 or the like can be used in combination.

The usage ratio of the red pigment and the color filter dye of the present invention is preferably 1 to 800 parts by weight of the color filter dye of the present invention with respect to 100 parts by weight of the red pigment. More preferably 5-4
00 parts by weight. If the addition amount of the color filter dye of the present invention is less than 1 part by weight, the reproducible chromaticity region becomes narrow, and if it exceeds 800 parts by weight, the hue changes, which is not preferable.

In consideration of the color composition, the mixing ratio of the red pigment and the color filter dye of the present invention is 1 to 400 parts by weight of the color filter dye of the present invention with respect to 100 parts by weight of the red pigment. preferable. More preferably, the color filter dye of the present invention is in the range of 5 to 300 parts by weight with respect to 100 parts by weight of the red pigment.

Particularly preferred pigments here are C.I. I. Pigment Red 177,254.
(Miniaturization of pigment)
As the pigment that may be added to the coloring composition for a color filter of the present invention, a pigment refined by a treatment such as a salt milling treatment can be used. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less.

The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, for 100 or more pigment particles, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. At this time, the pigment particles were sampled on a grid mesh to prepare a sample for TEM observation.

Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the total weight of the pigment from the viewpoint of both processing efficiency and production efficiency.

The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2
-Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy -2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like are used. The water-soluble organic solvent is 100 parts by weight based on the total weight of the pigment.
5 to 1000 parts by weight is preferably used, and 50 to 500 parts by weight is most preferably used.

When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. It is preferable that the usage-amount of resin is 5-200 weight part with respect to 100 weight part of the total weight of a pigment.
<Binder resin>
The binder resin is a colorant such as a pigment or a dye, particularly one that disperses the color filter dye of the present invention, or a dye that dyes and penetrates the color filter dye of the present invention,
A thermoplastic resin, a thermosetting resin, etc. are mentioned.

The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. Also,
Furthermore, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used for the purpose of improving photosensitivity and improving solvent resistance.

In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for an alkali development resist for color filters, no coating film foreign matter is generated after the colorant is applied. The stability of the colorant is preferably improved. When a linear resin that does not have an ethylenically unsaturated double bond in the side chain is used, the colorant is not easily trapped in the resin and the colorant mixture, and has a degree of freedom. The colorant component tends to agglomerate and precipitate,
By using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain,
Because the colorant is easily trapped in the resin and colorant mixture, it is difficult for the dye to elute and the colorant component does not aggregate or precipitate in the solvent resistance test. When the resin film is formed, the colorant molecule is fixed by the three-dimensional crosslinking of the resin,
It is presumed that even if the solvent is removed in the subsequent development process, the colorant component is less likely to aggregate and precipitate.

In order for the weight average molecular weight (Mw) of the binder resin to disperse the colorant preferably,
The range of 10,000 to 100,000 is preferable, and more preferably 10,000 to 80,
000 range. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

When the binder resin is used as a photosensitive color composition for a color filter, from the viewpoint of dispersibility, permeability, developability, and heat resistance of the pigment and the color filter dye of the present invention, a colorant adsorbing group and development The balance of the carboxyl group that acts as an alkali-soluble group at the time, the aliphatic group that acts as an affinity group for the colorant carrier and the solvent, and the aromatic group, dispersibility, penetrability, development of the pigment and the color filter dye of the present invention The resin having an acid value of 20 to 300 mgKOH / g is preferable. Acid value is 20mgKOH /
If it is less than g, the solubility with respect to a developing solution is bad, and it is difficult to form a fine pattern. 30
If it exceeds 0 mgKOH / g, no fine pattern remains.

The binder resin is preferably used in an amount of 30 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 500 parts by weight or less.
(Thermoplastic resin)
Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resin,
Examples include polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Among them, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (a) and (b).

[Method (a)]
As the method (a), for example, an unsaturated ethylenic monomer having an epoxy group and another 1
The carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond is added to the side chain epoxy group of the copolymer obtained by copolymerizing with more than one type of monomer, There is a method of reacting a produced hydroxyl group with a polybasic acid anhydride to introduce an unsaturated ethylenic double bond and a carboxyl group.

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 2-glycidoxyethyl (meth).
An acrylate, 3,4 epoxy butyl (meth) acrylate, and 3,4 epoxy cyclohexyl (meth) acrylate are mentioned, These may be used independently or may use 2 or more types together. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)
Acrylate is preferred.

As unsaturated monobasic acids, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro,
Examples thereof include monocarboxylic acids such as cyano-substituted products, and these may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like.
More than one type may be used together. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

As a method similar to the method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (b)]
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3
-Hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate may be mentioned. The above may be used together. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.
(Thermosetting resin)
Examples of the thermosetting resin used for the binder resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.
<Organic solvent>
In the coloring composition for a color filter of the present invention, a coloring agent is sufficiently dispersed and permeated in a coloring agent carrier, and is applied on a substrate such as a glass substrate so that a dry film thickness is 0.2 to 5 μm. A solvent can be included to facilitate the formation of the filter segment.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5
-Trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3
-Butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-
Heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o- Chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, se
c-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol Monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, die Lenglycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene Propylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, Tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate Propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like.

Among them, since the color filter dye and pigment of the present invention have good dispersion and dissolution, L-lactic acid, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. It is preferable to use aromatic alcohols such as glycol acetates and benzyl alcohol, and ketones such as cyclohexanone.
In particular, propylene glycol monomethyl ether acetate is more preferable from the viewpoint of health and safety and low viscosity.

These organic solvents can be used individually by 1 type or in mixture of 2 or more types. When it is set as 2 or more types of mixed solvents, it is preferable that said preferable organic solvent is contained 65 to 95 weight% in 100 weight part of the whole organic solvent. In particular, propylene glycol monomethyl ether acetate is preferably the main component, and is 65 to 100 in all organic solvents.
It is preferable that it is contained by weight.

Moreover, since the organic solvent can adjust a coloring composition to an appropriate viscosity and can form the filter segment of the target uniform film thickness, it is 800-40 with respect to 100 weight part of the total weight of a coloring agent.
It is preferably used in an amount of 00 parts by weight.
<Method for producing colored composition>
The color composition for color filter of the present invention preferably comprises a colorant containing the color filter pigment of the present invention in a colorant carrier comprising the resin and, if necessary, a solvent, preferably a dispersion aid such as a pigment derivative. Along with the agent, it can be produced by finely dispersing using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. Further, when the color filter dye of the present invention is highly soluble, specifically, it is highly soluble in the solvent to be used. And need not be manufactured.

The coloring composition for color filters of the present invention can also be produced by mixing pigments, the coloring matter for color filters of the present invention, and other colorants separately dispersed in a colorant carrier.
(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.
In the present invention, the color filter dye of the present invention can also serve as a dispersion aid for the pigment used in combination.

Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-156
No. 20, JP-B 59-40172, JP-B 63-17102, JP-B 5
-9469 etc. can be used, These can be used individually or in mixture of 2 or more types.

The blending amount of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, and most preferably 35 parts by weight or less with respect to 100 parts by weight of the colorant.

The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to stabilize dispersion in the colorant carrier. It works. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

As a commercially available resin-type dispersant, Disperbyk-1 manufactured by Big Chemie Japan Co., Ltd.
01, 103, 107, 108, 110, 111, 116, 130, 140, 154, 1
61, 162, 163, 164, 165, 166, 170, 171, 174, 180, 1
81, 182, 183, 184, 185, 190, 2000, 2001, 2020, 20
25, 2050, 2070, 2095, 2150, 2155 or Anti-Terra
-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13 from Lubrizol Japan, Lactimon, Lactimon-WS, or Bykumen
650, 13940, 16000, 17000, 18000, 20000, 21000,
24000, 26000, 27000, 28000, 31845, 32000, 3250
0, 32550, 33500, 32600, 34750, 35100, 36600, 38
500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 40 manufactured by Ciba Japan
15, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 44
01, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 43
30, 4340, 450, 451, 453, 4540, 4550, 4560, 4800,
5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 1
50, 1501, 1502, 1503, etc., Ajinomoto Fine Techno Co., Ltd. Addispar PA
111, PB711, PB821, PB822, PB824, and the like.

Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

The coloring composition for a color filter of the present invention can be used as a photosensitive coloring composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.
<Photopolymerizable monomer>
Photopolymerizable monomers that can be used in the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce transparent resins, and these may be used alone or in combination of two or more. Can do. The compounding amount of the monomer is 5 to 4 with respect to 100 parts by weight of the colorant.
The amount is preferably 00 parts by weight, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate,
Triethylene glycol di (meth) acrylate, tripropylene glycol di (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,
6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A
Diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate,
Dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate, and other acrylic and methacrylate esters , (Meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. However, it is not necessarily limited to these.
<Photopolymerization initiator>
In the coloring composition for a color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator or the like is added to add a solvent developing type or an alkali developing type coloring. It can be adjusted in the form of a resist material. The blending amount when using the photopolymerization initiator is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the total amount of the colorant, and 10 to 150 parts by weight from the viewpoint of photocurability and developability. It is more preferable.

As photopolymerization initiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl)
2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethyl Amino) -2-[(4-methylphenyl) methyl] -1- [
Acetophenone compounds such as 4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin methyl ether Benzoin compounds such as benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal;
Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4
Benzophenone compounds such as '-methyldiphenyl sulfide or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2
-Chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2
Thioxanthone compounds such as 2,4-diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6
-Bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6
-Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine,
2- (4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4
A triazine compound such as trichloromethyl- (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O -(Acetyl) -N- (1-phenyl-2-oxo-2- (4 '
Oxime ester compounds such as -methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, or 2
Phosphine compounds such as 1,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds;
Alternatively, titanocene compounds and the like are used.

These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 5 to 200% by weight based on the total amount of the colorant in the color filter coloring composition (100% by weight), and 10 from the viewpoint of photocurability and developability. More preferably, it is -150 weight%.
<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer. Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives,
Polymethine dyes such as ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives,
Indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalillo Porphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler ketone derivatives, α- Acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, , 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′ or 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4, , 4′-diethylaminobenzophenone and the like.

More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

Two or more kinds of sensitizers may be used in any ratio as required. The compounding amount when using the sensitizer is 3 to 6 with respect to 100 parts by weight of the total weight of the photopolymerization initiator contained in the colored composition.
The amount is preferably 0 part by weight, and more preferably 5 to 50 parts by weight from the viewpoint of photocurability and developability.
<Amine compound>
Moreover, the coloring composition for color filters of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.
<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coloring composition for a color filter of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-3 manufactured by Big Chemie
10, BYK-370 and the like. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the leveling agent is usually 0.003 to 0 in a total of 100% by weight of the coloring composition.
. It is preferable to use 5% by weight.

Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130.
, FZ-2166, FZ-2191, FZ-2203, FZ-2207,
It is not limited to these.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine,
Examples thereof include sodium stearate, sodium lauryl sulfate, monoethanolamine of a styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.

Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.
<Curing agent, curing accelerator>
Moreover, in order to assist the hardening of a thermosetting resin in the coloring composition for color filters of this invention,
If necessary, it may contain a curing agent, a curing accelerator, and the like. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4
-Methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.) Imidazole derivatives bicyclic amidine compounds and salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2) -Phenylimidazole,
1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (For example, 2,4-
Diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino -6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.
<Other additive components>
The coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the colorant.

Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β
-Epoxy silanes such as (3,4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyl Trimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxy Silanes, aminosilanes such as N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, etc. Silane coupling agent Is mentioned. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of the colorant in the coloring composition.
<Removal of coarse particles>
The colored composition for a color filter of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.
<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. Further, in addition to the three color filter segments, a yellow filter segment may be provided.

Preferably, at least one green filter segment is formed using the coloring composition for a color filter of the present invention.

The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a resin. Examples of the blue coloring composition include C.I. I. Pigment Blue 1
1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16
, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 6
1, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76,
78,
A blue pigment such as 79 is used.

In addition, C.I. I. Pigment Violet 1, 1: 1, 2, 2:
2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 2
Purple pigments such as 9, 31, 32, 37, 39, 42, 44, 47, 49, and 50 can be used in combination.

As the transparent substrate constituting the color filter, a glass plate such as soda lime glass, low alkali borosilicate glass or non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or the like is used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.
<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

The filter segment formation by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as a printing ink,
Low cost and excellent mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender pigment.

When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In addition,
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition due to oxygen. UV exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the color filter coloring composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” means “parts by weight”.

The weight average molecular weight (Mw) of the acrylic resin is TSKgel column (manufactured by Tosoh Corporation).
Is a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (HLC-8120GPC, manufactured by Tosoh Corporation) equipped with an RI detector using THF as a developing solvent.

First, the color filter dye of the present invention, acrylic resin solution (binder resin component) used in Examples and Comparative Examples, C.I. I. A description will be given of a coloring composition, a fine pigment, a pigment dispersion, and a method for synthesizing and manufacturing a blue resist material using an acid yellow 5 dye.
<Synthesis Method of Color Filter Dye>
Synthesis example 1
Synthesis Method of Compound 1 The following benzoquinaldine compound 1 (30 parts), naphthalenedicarboxylic anhydride 1 (40
Part) and benzoic acid (75 parts) were heated and stirred at 200 ° C. for 7 hours. After cooling, methanol (1
00 parts) was added and stirred for 1 h. The precipitated solid was collected by suction filtration. The solid was further placed in methanol (200 parts), stirred for 1 hour, and then collected by suction filtration. Compound 1 was obtained by drying overnight in a vacuum dryer (40 ° C.). (50.9 parts) was obtained. TOF-MS (autoflex II manufactured by Bruker Daltonics) m / z = 373 (MS theoretical value: 373).
Benzoquinaldine compound 1

Naphthalene dicarboxylic anhydride 1

Synthesis Examples 2 to 70
In the synthesis example 1 described above, the compounds shown in Table 2 were synthesized by changing the benzoquinaldine compound 1 and naphthalenedicarboxylic anhydride 1 used to benzoquinaldine compounds and naphthalenedicarboxylic anhydrides corresponding to the respective compounds.
Regarding the structure of the color filter dye of the present invention obtained in Synthesis Examples 1 to 70, TOF-M
S spectrum (manufactured by Bruker Daltonics, autoflex II)
, Measurement mode: positive or negative mode). Table 2 shows the structure of the benzoquinaldine compound and naphthalenedicarboxylic anhydride used, the theoretical value of the synthesized compound, and the measurement result of the actual measurement MS spectrum. The compound numbers are the same as those described in Table 1 in this specification.

  Table 2

Synthesis Example 71
Compound 92 Synthesis Method Compound 76 (3.3 parts), thionyl chloride (2 parts) and dehydrated DMF (30 parts), which are color filter dyes of the present invention, are placed in a 100 ml flask, and the mixture is heated at 80 ° C. for 8 hours under nitrogen. Stir with heating. After standing to cool, the remaining thionyl chloride is removed with an evaporator, and the amine compound 2
-Ethylhexylamine (2.9 parts) was added, and the mixture was heated and stirred at 80 ° C for 7 hours under nitrogen. After allowing to cool, the mixture was poured into ice water and stirred for 1 hour, and the precipitated solid was collected. Put solid in methanol (100 ml) and stir for 1 h. The solid was collected by suction filtration. The compound 92 was obtained by drying overnight in a vacuum dryer (40 ° C.). (3.3 parts) was obtained. TOF-MS (autoflex II manufactured by Bruker Daltonics) m / z = 565 (MS theoretical value: 565).

Synthesis Examples 72-80
In the above synthesis example 71, the compounds shown in Table 3 were synthesized by changing the color filter dye and amine compound of the present invention used to the color filter dye and amine compound of the present invention corresponding to each compound.
Regarding the structure of the color filter dye of the present invention obtained in Synthesis Examples 71 to 80, TOF-
Identification was made by MS spectrum (autoflex II, Bruker Daltonics, measurement mode: positive or negative mode). Table 3 shows the structures of the color filter dye and amine compound used, the theoretical values of the synthesized compounds, and the measured mass spectrum. The compound numbers are shown in Table 1 in this specification.
It is the same as described in.

  Table 3

Synthesis Example 81
Compound 113 Synthesis Method Compound 103 (1.0 part) and acetone (30 parts), which are color filter pigments of the present invention, were placed in a 100 ml flask and stirred in an ice bath. Iodomethane (0.28 parts) dissolved in acetone (10 parts) was added dropwise so as to keep the temperature at 5 ° C. or lower. After stirring for 5 hours, the mixture was returned to room temperature and stirred for 2 hours. The precipitated solid was collected by suction filtration. Vacuum dryer (40 ° C)
And dried overnight to give compound 113. (0.796 parts) was obtained. TOF-MS (autoflex II manufactured by Bruker Daltonics) m / z = 581 (MS theoretical value: 581).

Synthesis examples 82 to 83
In the synthesis example 81 described above, the compounds shown in Table 4 were synthesized by changing the color filter dye and iodomethane of the present invention used to the color filter dye and halide of the present invention corresponding to each compound.
Regarding the structure of the color filter dye of the present invention obtained in Synthesis Examples 81 to 83, TOF-
Identification was made by MS spectrum (autoflex II, Bruker Daltonics, measurement mode: positive or negative mode). Table 4 shows the structures of the color filter dyes and amine compounds used, the theoretical values of the synthesized compounds, and the measured mass spectra. The compound numbers are shown in Table 1 in this specification.
It is the same as described in.

  Table 4

Synthesis Example 84
Compound 119 Synthesis Method Compound 76 (1.5 parts) and water (50 parts), which are coloring agents for color filters of the present invention, were placed in a 300 ml beaker and stirred. Arcard 2HT-75 (manufactured by Lion Corporation, 3.2 parts) dissolved in water (110 parts) was added and stirred at 80 ° C. for 1 hour. The precipitated solid was collected by suction filtration. The collected solid was put into a 300 ml beaker, water (200 parts) was added, and the mixture was stirred at 80 ° C. for 30 minutes. The precipitated solid was collected by suction filtration and dried overnight in a vacuum dryer (60 ° C.) to obtain Compound 119. (2.36 parts) was obtained. TOF-MS (autoflex II manufactured by Bruker Daltonics) m / z = 579 (positive), 452 (negative) (MS theoretical value: 57
9 (positive), 452 (negative)).

Synthesis Examples 85-88
In the synthesis example 84 described above, the compounds shown in Table 5 were synthesized by changing the color filter dye of the present invention used to the color filter dye of the present invention corresponding to each compound.
Regarding the structure of the color filter dye of the present invention obtained in Synthesis Examples 84 to 88, TOF-
Identification was made by MS spectrum (autoflex II, Bruker Daltonics, measurement mode: positive or negative mode). Table 5 shows the structure of the color filter dye of the present invention used, the theoretical value of the synthesized compound, and the measured mass spectrum. The compound numbers are the same as those described in Table 1 in this specification.

  Table 5

<Method for producing acrylic resin solutions 1 to 4>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 2,2'-
A mixture of 0.4 parts of azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Acrylic resin solution 1 was prepared by addition.
(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 2
-A mixture of 8.5 parts of hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction is continued for another 3 hours,
A copolymer resin solution was obtained.

Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours.

About 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content.
Acrylic resin solution 2 was prepared by adding cyclohexanone to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. The weight average molecular weight (Mw) was 18000.
(Preparation of acrylic resin solution 3)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of glycerol monomethacrylate, and 2,2′-azobisisobutyronitrile.
33 parts of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution.

Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, after cooling to room temperature, 6.5 parts of 2-methacryloyloxyl ethyl isocyanate, 7 parts of a mixture of 0.08 parts dibutyltin laurate and 26 parts cyclohexanone
The solution was added dropwise at 0 ° C. over 3 hours.

About 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content.
Acrylic resin solution 3 was prepared by adding cyclohexanone to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. The weight average molecular weight (Mw) was 19000.
(Preparation of acrylic resin solution 4)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group), 0.3% of triethylamine were subsequently added.
5 parts were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.

After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, an acrylic resin solution 4 was prepared. The weight average molecular weight (Mw) is 190.
00.
<C. I. Acid Yellow 5 Series Dye Production Method>
C. I. The acid yellow 5 dye (A-1) was adjusted as follows.
(Preparation of acid dye A)
For acid dye A, acid dyes manufactured by BASF, Acid Yellow 5 Liquid
The solvent component therein was distilled off under reduced pressure, washed with ethanol, dried and pulverized to form a powder, and an acid dye A having n of 1 in the structure described above was obtained.
(Preparation of resin 1 having a cationic group)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2′-azobis (2,4-dimethylvaleronitrile) ) 6.5 parts, and methyl ethyl ketone 25.1
After the parts were made uniform, they were charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content, and the weight average molecular weight (Mw) was 6830, and then cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 having a resin component having a cationic group of 47% by weight was obtained. The resulting resin has an ammonium salt value of 34 mg KOH.
/ G.

Here, the weight average molecular weight (Mw) of the resin having a cationic group was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. Also,
The ammonium salt value of the resin having a cationic group in the side chain is a value converted to the equivalent of potassium hydroxide after being obtained by titration with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator. Represents the ammonium salt value of the solid content.
(Preparation of CI Acid Yellow 5-Type Dye (A-1))
The acid dye A is added to 2000 parts of water with 51 parts of the resin 1 having a cationic group, sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 10 parts of an aqueous solution prepared in 90 parts of water is prepared and added dropwise to the above resin solution little by little. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, the reaction solution was dropped onto the filter paper, and it was judged that the target product was obtained with the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the solid remaining on the filter paper is dried by removing moisture with a dryer, and 32 parts of C.I. I. Acid yellow 5 series dye (A-1) was obtained. At this time, C.I. I.
The content of the effective pigment component derived from the acidic dye A in Acid Yellow 5 series dye (A-1) was 32% by weight.
(Preparation of coloring composition (A-2) using CI Acid Yellow 5 series dye)
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a colored composition (A-2).
C. I. Acid Yellow 5 series dye (A-1): 11.0 parts acrylic resin solution 1: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts <Production method of refined pigment>
(Miniaturization of color filter dyes)
Compound 1, 200 parts synthesized in Synthesis Example 1, 1400 parts sodium chloride, and 360 parts diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C.
For 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of a fine color filter dye (DQ-1) was obtained. The average primary particle diameter of the obtained dye was 90 nm.

Refinement was carried out in the same manner as in the above method except that Compound 1 of the above method was changed to the other color filter pigment of the present invention to obtain refined pigments (DQ-1 to 88). Table 6 shows the average primary particle diameters of the used color filter dyes of the present invention and the resulting refined dyes.

(Preparation of blue fine pigment 1)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Ink Manufacturing Co., Ltd.) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. did. Next, this kneaded product is put into 8 liters of warm water and heated to 80 ° C.
The mixture was stirred for 2 hours with heating to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight to obtain 190 parts of blue fine pigment 1. The average primary particle diameter of the obtained pigment was 79 nm.
(Preparation of purple fine pigment 1)
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (Toyo Ink Manufacturing Co., Ltd. “LIONOGEN VIOLET RL”) 200 parts, sodium chloride 140
0 parts and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of purple fine pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 28 nm.
(Preparation of blue fine pigment 2)
A glass 4-necked flask was charged with 60.0 parts of phthalonitrile, 300 parts of 1-chloronaphthalene, and 15.6 parts of aluminum chloride, and stirred under reflux for 6 hours. Thereafter, heating was stopped, the mixture was allowed to cool to about 200 ° C., filtered while hot, and washed by sprinkling with 600 parts of hot toluene and 300 parts of acetone. The obtained wet cake was dispersed in 250 parts of toluene and stirred and refluxed for 3 hours. The mixture was again filtered while hot, washed by sprinkling with 600 parts of hot toluene and 300 parts of acetone, dispersed in 1500 parts of ion-exchanged water, and heated and stirred at 60 to 70 ° C. for 60 minutes. Filtration, washing with water and vacuum drying at 50 ° C. gave a blue solid aluminum phthalocyanine pigment (AlPc—Cl) having the desired structure. 30 parts of the obtained pigment were gradually dissolved in 1200 parts of concentrated sulfuric acid while keeping the temperature at about 5 ° C., and stirred at this temperature for 1 hour. This is ice water 600
The mixture was added to 0 part with stirring so that the temperature did not exceed 5 ° C., and further stirred for 1 hour after the end of the addition. After filtration and washing with water, it was redispersed in 6500 parts of ion exchange water and filtered again. After washing with water, the wet cake was redispersed in 2500 parts of 4% aqueous ammonia and stirred under reflux for 6 hours. After filtration, the cake was washed with ion-exchanged water and then vacuum-dried at 50 ° C. to obtain a blue solid aluminum phthalocyanine pigment (AlPc—OH) having the desired structure.

50 parts of this (AlPc-OH) pigment, 150 parts of sodium chloride, and 25 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.).
Kneaded for hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. A blue fine pigment 2 was obtained. The average primary particle diameter of the obtained pigment was 28 nm.
(Preparation of green fine pigment 1)
Phthalocyanine green pigment C.I. I. Pigment Green 58 ("FAS" manufactured by DIC Corporation
TGEN GREEN A110 ") was used as a commercial product. The average primary particle diameter of the green fine pigment 1 was 22 nm.
(Preparation of green fine pigment 2)
Phthalocyanine green pigment C.I. I. Pigment Green 36 (Toyo Ink Manufacturing Co., Ltd.
Lionol Green 6YK) was used as it was on the market. The average primary particle diameter of the green fine pigment 2 was 63 nm.
(Preparation of yellow fine pigment 1)
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 (“Irgafore Yellow 2R-CF” manufactured by Ciba Japan), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. did. Next, this kneaded product was put into 5 liters of warm water and 70 ° C.
The mixture was stirred for 1 hour with heating to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight to obtain 490 parts of a yellow fine pigment 1. The average primary particle diameter of the obtained pigment was 92 nm.
(Preparation of yellow fine pigment 2)
Nickel complex yellow pigment C.I. I. Pigment Yellow 150 ("E" manufactured by LANXESS
-4GN ") 200 parts, sodium chloride 1400 parts, and diethylene glycol 360
The parts were placed in a stainless gallon kneader (Inoue Seisakusho) and kneaded at 120 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of yellow fine pigment 2 were obtained. The obtained pigment had a volume average primary particle size of 67 nm.
(Preparation of yellow fine pigment 3)
Nickel complex yellow pigment C.I. I. 270 parts of Pigment Yellow 138 (trade name Paliotor Yellow K0961HD, manufactured by BASF), 1350 parts of sodium chloride, and 500 parts of diethylene glycol were charged into a stainless 1 gallon kneader (Inoue Seisakusho) and kneaded at 120 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 250 parts of yellow fine pigment 3
Got. The average primary particle diameter of the obtained pigment was 36 nm.
(Preparation of red fine pigment 1)
Anthraquinone red pigment C.I. I. Pigment Red 177 (Ciba Japan “chromophthaled red A2B”) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho), 8
The mixture was kneaded at 0 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red fine pigment 1 were obtained. The average primary particle diameter of the obtained pigment was 54 nm.
<Method for producing colored composition>
(Preparation of colored composition (DP-1))
After stirring and mixing the following mixture uniformly, Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm.
Was dispersed for 5 hours, and filtered through a 5.0 μm filter to prepare a colored composition (DP-1).
Blue fine pigment 1 (CI Pigment Blue 15: 6): 11.0 parts acrylic resin solution 1: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin-type dispersant (Ciba Japan) "EFKA4300" manufactured by the company): 1.0 part Hereinafter, the colored composition (DP) except that the blue fine pigment was changed to the fine pigment shown in Table 7
A colored composition (DP-2 to 9)) was produced in the same manner as in -1).

<Method for producing blue resist material>
(Preparation of blue resist material B-1)
After stirring and mixing the following mixture uniformly, it is filtered through a 1.0 μm filter,
Blue resist material B-1 was obtained.
Pigment dispersion (DP-1): 48.0 parts Pigment dispersion (DP-2): 12.0 parts Acrylic resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (Shin-Nakamura Chemical Co., Ltd.) "NK ester ATMPT"
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.): 1.2 parts sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts ethylene glycol monomethyl ether acetate: 23.2 parts
[Examples 1 to 94]
<Method for producing colored composition>
(Preparation of colored composition (DP-10))
After stirring and mixing the following mixture uniformly, Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm.
Was dispersed for 5 hours, and then filtered through a 5.0 μm filter to prepare a colored composition (DP-10).
Fine Dye DQ-1: 11.0 parts acrylic resin solution 1: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts resin type dispersant (“EFKA4300” manufactured by Ciba Japan): 0 parts Hereinafter, the colored composition is the same as the colored composition (DP-10) except that the refined dye DQ-1 and the acrylic resin solution 1 are changed to the refined dye and the acrylic resin solution shown in Table 8. The thing (DP-11-103) was produced.

[Examples 95 to 186, Comparative Examples 1 to 6]
(Example 1; Preparation of resist material G-1)
After stirring and mixing the following mixture uniformly, it is filtered through a 1.0 μm filter,
An alkali developing resist material (G-1) was obtained.
Colored composition (DP-6): 6.0 parts Colored composition (DP-10): 54.0 parts Acrylic resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (Shin Nakamura Chemical Co., Ltd.) "NK ester ATMPT"
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts propylene glycol monomethyl ether acetate (PGMAC): 23 .2 parts (Examples 96 to 186, Comparative Examples 1 to 6; Resist materials G-2 to 94, R-1 to 2, Y-1 to
Preparation of 2)
Hereinafter, except that the kind and the blending amount of the coloring composition are changed as shown in Table 9, the resist material G-
In the same manner as in Example 1, alkaline development resist materials G-2 to 94, R-1 to 2, and Y-1 to 2 were obtained.

(Examples 187 to 192; resist material G-95 to 100))
Resist material G replacing the colored composition (DP-10) of Example 95 with DP-98, 99, 100
Alkali-developable resist materials G-95, 96, and 97 were obtained in the same manner as -1.
Further, the color-developing composition (DP-57) of Example 142 was replaced with DP-101, 102, 103 to obtain alkali developing resist materials G-98, 99, 100 in the same manner as the resist material G-48.
(Evaluation of resist material)
Each test of the color characteristics (brightness, coloring power), foreign matter, heat resistance, and light resistance of the obtained resist materials G-1 to 90, R-1 to 2, and Y-1 to 2 is performed by the following methods. went. Table 10 shows the results of the test.
(Color characteristics (lightness, coloring power))
In a C light source on a glass substrate, the resist materials G-1 to 100 are x = 0.264, y = 0.
. A resist material was applied to a thickness of 600, and the substrate was heated at 230 ° C. for 20 minutes. The resist material R-1 and 2 were coated with a resist material so that x = 0.340 and y = 0.640, and the substrate was heated at 230 ° C. for 20 minutes. Resist materials Y-1 and 2 have x = 0.4
A resist material is applied to a film thickness such that 40, y = 0.506.
Heated for 0 minutes. Thereafter, the brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). In addition, as an index of coloring power, the film thickness was measured with a stylus type surface shape measuring instrument ("Dektak 6M" manufactured by ULVAC). The relative film thickness was determined with G-93 being 1 for the green resist material, R-2 being 1 for the red resist material, and Y-2 being 1 for the yellow resist material. The smaller the relative film thickness, the better the coloring power.
(Coating foreign material test method)
A resist material was applied on the transparent substrate so that the dried coating film became about 2.5 μm, and the whole surface was exposed to ultraviolet light, and then heated in an oven at 230 ° C. for 20 minutes and allowed to cool to obtain an evaluation substrate. The evaluation was performed by observing the surface using a metal microscope “BX60” manufactured by Olympus System. The magnification is 500 times, and the number of particles that can be confirmed in any five visual fields through transmission is counted. In the following evaluation results, ◎ and ○ are good, Δ is a level that does not cause a problem in use although there are many foreign matters, and × indicates coating unevenness due to the foreign matters.
◎: Less than 5 ○: 5 or more, less than 20 △: 20 or more, less than 100 ×: 100 or more (Method of coating film heat resistance test)
A resist material is applied on a transparent substrate so that the dry coating thickness is about 2.5 μm, and after UV exposure through a mask having a predetermined pattern, an alkali developer is sprayed to remove uncured parts. Thus, a desired pattern was formed. Then, after heating in an oven at 230 ° C. for 20 minutes and allowing to cool, the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source is microspectrophotometric. Measurement was performed using a meter (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). After that, as a heat resistance test, it was heated in an oven at 250 ° C. for 1 hour, and the chromaticity 2 with a C light source (L * (2)
, A * (2), b * (2)).

Using the measured color difference value, the color difference ΔEab * was calculated by the following formula, and the heat resistance of the coating film was evaluated in the following four stages. Moreover, if evaluation is more than (circle), it is a level which is satisfactory practically.
ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
A: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 5.0 ×: ΔEab * is 5.0 or more

(Method of coating light resistance test)
A test substrate is prepared in the same procedure as the coating heat resistance test, and the chromaticity is 1 (L * (1), a *) with a C light source.
(1), b * (1)) were measured using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). Thereafter, the substrate was tested for light resistance ("SUNTEST" manufactured by TOYOSEIKI).
CPS + ") and left for 500 hours. After removing the substrate, the chromaticity 2 (L
* (2), a * (2), b * (2)) are measured, the color difference ΔEab * is calculated in the same manner as the coating heat resistance test, and the light resistance of the coating film is determined according to the same criteria as heat resistance. evaluated.

The resist materials (G-1 to 90) of Examples 95 to 184 are the resist materials (G-9 of Comparative Example 1).
Compared with 1), the coloring power was also high (relative film thickness was small). Moreover, Comparative Examples 2-4
As compared with the resist materials (G-92 to 94), the brightness (Y) was high and the coloring power was high (relative film thickness was small).
The resist material (R-1) of Example 185 is compared with the resist material (R-2) of Comparative Example 5,
The results were high brightness (Y) and high tinting strength (relative film thickness was small).
The resist material (Y-1) of Example 186 is compared with the resist material (Y-2) of Comparative Example 6,
The results were high brightness (Y) and high tinting strength (relative film thickness was small).
Furthermore, the resist materials (G-1 to 90, R-1, and Y-1) of Examples 95 to 186 have practically no problem in other physical properties (coating foreign matter, light resistance, heat resistance). there were.
Solvent resistance of the obtained resist materials G-1 and 48, color characteristics of the coating film of G-95 to 100 (lightness,
Color strength), foreign matter, heat resistance, light resistance, and solvent resistance were tested. In the solvent resistance test, the following methods, color characteristics (brightness, coloring power), foreign matter, heat resistance, and light resistance were performed by the above methods. Table 1 shows the results.
It is shown in 1.
(Method of coating solvent resistance test)
A test substrate is prepared in the same procedure as the heat resistance test, and the chromaticity is 1 with the C light source (L * (1), a * (1)
, B * (1)) was measured using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. After removing the substrate, measure chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source, and calculate the color difference ΔEab * in the same manner as the coating film heat resistance test. Then, the solvent resistance of the coating film was evaluated according to the same criteria as the heat resistance.

The resist materials (G-95 to 97) of Examples 187 to 189 are the same as the resist materials of Example 95 (G-95 to 97).
G-1) showed the same brightness (Y) and coloring power. In addition, the resist materials (G-98 to 100) of Examples 190 to 192 have the same lightness (Y) as the resist material (G-48) of Example 142.
, Showed coloring power.
Further, the resist materials (G-95 to 100) of Examples 187 to 192 were at a level causing no practical problem in other physical properties (coating foreign matter, light resistance, heat resistance).

In the resist materials (G-1, 48) of Examples 95 and 142, the solvent resistance is at a level that causes no problem in practical use, but the resist materials (G-95) of Examples 187 to 192 in which the acrylic resin solution is changed. ~ 100), further improvement was confirmed.
[Example 193]
(Color filter (CF-1))
A black matrix is patterned on a glass substrate, and a red resist material (R-1) is applied on the substrate with a spin coater to a film thickness such that x = 0.640, y = 0.340. A colored coating was formed. The film was irradiated with ultraviolet rays of 300 mJ / cm @ 2 using a super high pressure mercury lamp through a photomask. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. In the same manner, the green resist material (G-1) is formed to a thickness such that x = 0.264 and y = 0.600, and x = 0.150 using the blue resist material (B-1). Each was applied to a film thickness such that y = 0.060, and a green filter segment and a blue filter segment were formed to obtain a color filter (CF-1).
(Production of liquid crystal display device)
A transparent ITO electrode layer was formed on the obtained RGB color filter, and a polyimide alignment layer was formed thereon. A color display device was produced on the other surface of this glass substrate in combination with a three-wavelength CCFL light source of a polarizing plate. Formed. On the other hand, a TFT array and a pixel electrode were formed on one surface of another (second) glass substrate, and a polarizing plate was formed on the other surface. The two glass substrates prepared in this way are arranged facing each other so that the electrode layers face each other, and are aligned using spacer beads while keeping the distance between the two substrates constant, and an opening for injecting a liquid crystal composition The periphery was sealed with a sealant so as to leave After injecting the liquid crystal composition from the opening, the opening was sealed. The liquid crystal display device thus fabricated was used as a backlight unit with three wavelengths C
A color display device was fabricated in combination with a CFL light source.
[Examples 194 to 197, Comparative Examples 7 and 8]
(Color filter (CF-2 to 7))
Hereinafter, the color filters (CF-2˜) of Examples 194 to 197 and Comparative Examples 7 and 8 were combined with the resist material shown in Table 12 and the three-wavelength CCFL light source by the same method as the production of the color filter (CF-1). 7) and a color display device were produced.

Thereafter, in the obtained color display device, a light source is emitted to display a color image, and the brightness of each color filter segment portion is measured with a microspectrophotometer (“OSP-SP2 manufactured by Olympus Optical Co., Ltd.).
00 "). The results are shown in Table 12.

When Examples 193 to 195 are compared with Comparative Example 7, the color filter formed by the color filter coloring composition of the present invention has at least one filter segment (compared to a conventionally used filter segment containing a pigment). In the color filter (CF-2, 3) containing the coloring composition for a color filter of the present invention, the brightness is improved. As a result, the brightness of white display is increased and the performance as a color filter is confirmed to be improved. It was.

Further, it was confirmed that the brightness of the color filter (CF-1) formed from the coloring composition for color filter of the present invention was improved for both green and red, and as a result, the brightness of white display was increased.

Further, when Examples 196 and 197 are compared with Comparative Example 8, the color filter formed by the color filter coloring composition containing the color filter dye of the present invention is a filter segment containing a conventionally used pigment. In comparison, the brightness of the color filter (CF-6) containing at least one filter segment (yellow) containing the color filter dye of the present invention is improved, and as a result, the brightness of white display is increased and the performance as a color filter is improved. Was confirmed.
Furthermore, when green, red and yellow all contain the color filter dye of the present invention (CF
-5) It was confirmed that the brightness was further improved, and as a result, the brightness of white display was increased.

From the above results, by using the color filter pigment and coloring composition of the present invention, it is possible to increase the brightness and coloring power of the color filter, and it can be suitably used without any other physical properties.

Claims (4)

A color filter dye represented by the following general formula (1) or the following general formula (2).
General formula (1)

General formula (2)

Wherein R _{1 to} R ₂₈ are each independently a hydrogen atom, halogen atom, hydroxyl group, nitro group, substituted or unsubstituted amino group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl Group, substituted or unsubstituted aryl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted sulfonyl group, or Represents a substituted carbonyl group.) A color filter coloring composition comprising at least a color filter dye represented by the general formula (1) or the general formula (2) and a binder resin. The coloring composition for a green color filter according to claim 2, further comprising a pigment. A color filter comprising at least a red filter segment, a green filter segment, and a blue filter segment, wherein at least one filter segment is formed by the color filter coloring composition according to claim 2 or 3.