JP6950070B2 - Colored resin compositions for color filters, color material dispersions, color filters, and display devices - Google Patents

Description

The present invention relates to a colored resin composition for a color filter, a color material dispersion liquid, a color filter, and a display device.

In recent years, the market price of flat-panel image display devices has become more affordable year by year with the evolution of production technology, the demand has expanded, and the production volume has also increased. In particular, color LCD televisions have reached the mainstream of televisions. Recently, organic light emitting display devices such as organic EL displays having high visibility due to self-luminous light have also attracted attention as next-generation image display devices. In terms of the performance of these image display devices, further improvement in image quality and reduction in power consumption such as improvement in contrast and color reproducibility are strongly desired.
Color filters are used in these liquid crystal displays and organic light emitting displays. For example, in the case of a color liquid crystal display, a backlight is used as a light source, the amount of light is controlled by electrically driving the liquid crystal, and the light passes through a color filter to express colors. Therefore, color filters are indispensable for the color expression of LCD TVs, and they also play a major role in affecting the performance of displays. In the organic light emitting display device, when a color filter is used for the white light emitting organic light emitting element, a color image is formed in the same manner as in the liquid crystal display device.

As a trend in recent years, power saving of image display devices is required, and high brightness of color filters is required in order to improve the utilization efficiency of backlights. This is a major issue especially for mobile displays (mobile phones, smartphones, tablet PCs). Further, in such an image display device, further improvement in image quality such as improvement in contrast and color reproducibility is required.
Although the battery capacity has increased due to technological evolution, the amount of electricity stored in mobile devices is still finite, while the power consumption tends to increase as the screen size increases. An image display device including a color filter influences the design and performance of the mobile terminal because it is directly linked to the usable time and charging frequency of the mobile terminal.

Here, the color filter is generally formed on a transparent substrate, a colored layer formed on the transparent substrate and composed of colored patterns of the three primary colors of red, green, and blue, and on the transparent substrate so as to partition each colored pattern. It has a formed light-shielding portion.
For the colored layer of the color filter, a resin composition for forming a colored layer having a pigment or a dye as a coloring material is used. Pigments are generally superior in various resistances such as heat resistance as compared with dyes, but the brightness of manufactured color filters may be insufficient.
On the other hand, when a dye is used as a coloring material, a color filter having high brightness can be produced, but there is a problem that various resistances and contrasts are insufficient. Further, the colored resin composition used by dissolving the dye has a problem that foreign substances are easily deposited on the surface of the coating film in the drying process, and the contrast is lowered due to the fluorescence emission of the dye. Therefore, it can be used as a color filter application. There were many problems.

In recent years, in a resin composition for forming a colored layer, a color material containing a dye has been used in combination. The present inventors have described in Patent Document 1 a specific coloring material having xanthene as a basic skeleton and a blue coloring material as a coloring resin composition for a color filter capable of forming a coloring layer having excellent brightness and light resistance. Discloses a colored resin composition for a color filter, including the same.
Further, in Patent Document 2, a dye compound having a dye structure having a cation site and an anion site containing a specific structure, and the anion site and the cation site are bonded via a covalent bond and exist in the same molecule. A coloring composition containing the above is disclosed, and a dye compound having a xanthene dye structure is disclosed as a dye structure having the cation moiety. Patent Document 2 describes that the coloring composition can provide a color filter having excellent heat resistance. When the dye compound is a polymer as described in Patent Document 2, there is a problem that sufficient brightness cannot be obtained.
However, there is a demand for a colored resin composition capable of forming a colored layer in which foreign matter is less likely to be deposited on the surface of the coating film in the drying step and the brightness is improved as compared with the conventional case.

Japanese Unexamined Patent Publication No. 2014-153570 International Publication No. 2015/033814

The present invention has been made in view of the above problems, and is a colored resin composition for a color filter capable of forming a colored layer in which the generation of foreign substances is suppressed and the brightness is improved. The generation of foreign substances is suppressed and the brightness is improved. It is an object of the present invention to provide a color material dispersion liquid capable of forming a coating film, a high-brightness color filter formed by using the colored resin composition for a color filter, and a display device having the color filter.

The colored resin composition for a color filter according to the present invention contains a coloring material (A), a binder component (B), and a solvent (C), and the coloring material (A) is based on the following general formula (1). It is characterized by containing a coloring material represented by.

（一般式（１）中、Ｒ^１及びＲ^２は各々独立に、置換基を有していても良い脂肪族炭化水素基又は芳香族炭化水素基であり、Ｒ^３及びＲ^４は各々独立に、置換基を有していても良い芳香族炭化水素基又は芳香族複素環基であって、Ｒ^３及びＲ^４の芳香族炭化水素基又は芳香族複素環基はそれぞれ脂肪族炭化水素基で置換されている。Ｌ^１及びＬ^２は各々独立に、直接結合、―ＳＯ_２―、又は―ＣＯ―であり、Ｒ^５はハロゲン化脂肪族炭化水素基である。）

(In the general formula (1), R ¹ and R ² are each independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent, and R ³ and R ⁴ are independent of each other. , An aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and the aromatic hydrocarbon group or the aromatic heterocyclic group of R ³ and R ⁴ is an aliphatic hydrocarbon group, respectively. Substituted. L ¹ and L ² are independently directly bonded, -SO _2- , or -CO-, and R ⁵ is a halogenated aliphatic hydrocarbon group.)

The color material dispersion liquid according to the present invention is characterized in that the color material represented by the general formula (1) is dispersed in a solvent by a dispersant having an amine value.

The color filter according to the present invention is a color filter including at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a colored resin composition for a color filter according to the present invention. It is characterized by having a colored layer made of a cured product of.
The present invention also provides a display device having the color filter according to the present invention.

INDUSTRIAL APPLICABILITY The present invention is a colored resin composition for a color filter capable of forming a colored layer in which the generation of foreign substances is suppressed and the brightness is improved, and a coloring material dispersion liquid capable of forming a coating film in which the generation of foreign substances is suppressed and the brightness is improved. , A high-brightness color filter formed by using the colored resin composition for a color filter, and a display device having the color filter can be provided.

It is a schematic cross-sectional view which shows an example of the color filter of this invention. It is the schematic sectional drawing which shows an example of the liquid crystal display device of this invention. It is the schematic sectional drawing which shows an example of the organic light emission display device of this invention.

Hereinafter, the colored resin composition for a color filter, the color material dispersion liquid, the color filter, and the display device according to the present invention will be described in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam. Further, in the present invention, (meth) acrylic represents each of acrylic and methacrylic, and (meth) acrylate represents each of acrylate and methacrylate.

1. 1. Colored Resin Composition for Color Filters The colored resin composition for color filters according to the present invention contains a colorant (A), a binder component (B), and a solvent (C), and the colorant (A) contains the colorant (A). , It is characterized by containing a coloring material represented by the following general formula (1).

（一般式（１）中、Ｒ^１及びＲ^２は各々独立に、置換基を有していても良い脂肪族炭化水素基又は芳香族炭化水素基であり、Ｒ^３及びＲ^４は各々独立に、置換基を有していても良い芳香族炭化水素基又は芳香族複素環基であって、Ｒ^３及びＲ^４の芳香族炭化水素基又は芳香族複素環基はそれぞれ脂肪族炭化水素基で置換されている。Ｌ^１及びＬ^２は各々独立に、直接結合、―ＳＯ_２―、又は―ＣＯ―であり、Ｒ^５はハロゲン化脂肪族炭化水素基である。）

(In the general formula (1), R ¹ and R ² are each independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent, and R ³ and R ⁴ are independent of each other. , An aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and the aromatic hydrocarbon group or the aromatic heterocyclic group of R ³ and R ⁴ is an aliphatic hydrocarbon group, respectively. Substituted. L ¹ and L ² are independently directly bonded, -SO _2- , or -CO-, and R ⁵ is a halogenated aliphatic hydrocarbon group.)

The colored resin composition for a color filter according to the present invention contains a coloring material represented by the above general formula (1) as a coloring material, whereby the generation of foreign substances is suppressed and a colored layer having improved brightness is formed. Can be done.
Conventionally, attempts to adopt a xanthene-based dye having xanthene as a basic skeleton in a colored layer for a color filter have been made as described in Patent Documents 1 and 2. However, the xanthene-based dyes that have been specifically used in the past are inferior in solvent solubility, and when a colored layer is formed, foreign substances that are agglomerates derived from the dye are likely to be generated. Further, it has been desired to further improve the brightness of the colored layer.
On the other hand, the coloring material represented by the above general formula (1) used in the present invention contains xanthene as a basic skeleton and also contains a specific anion portion ^{of −L 1} −N ⁻ −L ² −R ^{5. None of R 1 to} R ⁴ having only one functional group and bonded to a nitrogen atom is a hydrogen atom, and R ³ and R ⁴ are aromatic hydrocarbon groups or aromatic heterocyclic groups, and R ³ and it has a feature that an aromatic hydrocarbon or aromatic heterocyclic group of R ⁴ are each a substituted aliphatic hydrocarbon group. By using the coloring material represented by the general formula (1) having such characteristics, the colored resin composition for a color filter according to the present invention has a colored layer in which the generation of foreign substances is suppressed and the brightness is improved. Can be formed.
The action to obtain the above effect is considered as follows, although there are some unclear points. The coloring material represented by the general formula (1) has a monovalent cationic xanthene skeleton and one anionic −L ¹ −N ⁻ −L ² −R ⁵ groups, and is an intramolecular salt. Since it has only one molecule, it is easy to be electrically stabilized in one molecule. On the other hand, anionic ^-L 1 ^-N - in ^-L 2 -R ⁵ group, by bonded high electronegativity halogen in ^{R 5,} easy electron anionic sites is attracted to ^{R 5} It is presumed that the weakening of the anionic property weakens the ionic bond between the molecules. Further, in the coloring material represented by the above general formula (1), ^{none of R 1 to} R ⁴ bonded to the nitrogen atom is a hydrogen atom, and R ³ and R ⁴ are aromatic hydrocarbon groups or aromatic heterocycles. Since ^{the aromatic hydrocarbon groups or aromatic heterocyclic groups of R 3} and R ⁴ are each substituted with an aliphatic hydrocarbon group, they have low crystallinity, are difficult to aggregate, and have solvent affinity. Is estimated to be high. From these synergistic effects, it is presumed that the coloring material represented by the above general formula (1) has improved solvent solubility as compared with the conventional one, and that the generation of foreign substances is suppressed when it is used as a colored layer. ..
Further, in the coloring material represented by the above general formula (1), since the nitrogen atom bonded to the xanthene skeleton is not directly bonded to the hydrogen atom, the hydrogen atom is desorbed from the nitrogen atom and the coloring material becomes unstable. Since the nitrogen atom has an aromatic substituent such as an aromatic hydrocarbon group or an aromatic heterocyclic group, the lone electron pair of the nitrogen atom is not only the xanthene skeleton but also the aromatic. It has a highly stable molecular structure by resonating with a group hydrocarbon group or an aromatic heterocyclic group. The coloring material represented by the general formula (1) has a highly stable molecular structure as described above, and therefore has good heat resistance.
Further, in the coloring material represented by the above general formula (1), since ^{the aromatic hydrocarbon groups or aromatic heterocyclic groups of R 3} and R ⁴ are each substituted with an aliphatic hydrocarbon group, the dyes are separated from each other. Since it is hard to aggregate and has high solvent solubility, foreign matter is hard to be generated, so that the amount of transmitted light of the colored layer is not attenuated.
Further, since the color material represented by the general formula (1) has a wide range of molecular design and a wide range of adjustments such as spectral characteristics, the color material is brought closer to the target chromaticity and the brightness is further improved. Is easy.
As described above, when the coloring material represented by the general formula (1) is used, the decrease in brightness after baking in the color filter manufacturing process is suppressed because the heat resistance is good, and the dye in the color filter manufacturing process. It is presumed that the brightness of the colored layer can be improved by suppressing the aggregation of the dyes and the generation of foreign substances, and by designing the structure according to the desired chromaticity and adjusting the spectral characteristics and the like.

<Color material>
The coloring material used in the present invention includes at least a coloring material represented by the following general formula (1), and may contain other coloring materials as necessary. Each color material will be described below.
(Color material represented by the general formula (1))

（一般式（１）中の各符号は、上述の通りである。）

(Each reference numeral in the general formula (1) is as described above.)

In the general formula (1), the ^{aliphatic hydrocarbon group in R 1} and R ² may be linear, branched, or cyclic, and is not particularly limited, but for example, it has 1 or more carbon atoms and 20 carbon atoms. Examples thereof include the following linear or branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups having 5 or more and 8 or less carbon atoms (alicyclic hydrocarbon groups), and the like, and the number of carbon atoms is 10 or less. , Preferred from the viewpoint of heat resistance. As the aliphatic hydrocarbon group, a linear, branched or cyclic alkyl group which is a saturated aliphatic hydrocarbon group is preferable.
The substituent that the aliphatic hydrocarbon group may have is not particularly limited, but is, for example, a halogen atom, an aromatic hydrocarbon group, a carbamoyl group, or a monovalent ^{group represented by −CO—O—R a.} , A monovalent group represented by -O-CO-R ^a' , a monovalent group represented by -SO _2- R ^a" , a monovalent group represented by -R ^b- CO-O-R ^c , ^{-R b '-O-CO-R} c' monovalent group represented by, and ^-R b monovalent group represented by ^_"-SO 2 ^{-R _c"} and the like.
The aromatic hydrocarbon group in R ^{1 to} R ⁴ is not particularly limited, and examples thereof include an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and among them, a phenyl group. , A group having a naphthyl group or the like is preferable.
The aromatic heterocyclic group in R ³ and R ⁴ is not particularly limited, and examples thereof include an aromatic heterocyclic group having 5 to 20 carbon atoms which may have a substituent, and examples of the hetero atom include, for example, an aromatic heterocyclic group. Those containing a nitrogen atom, an oxygen atom, and a sulfur atom are preferable. Specific examples of the aromatic heterocyclic group include furan, thiophene, pyrrole, and pyridine.
The substituent which the aromatic hydrocarbon group or the aromatic heterocyclic group may have is not particularly limited, but for example, an aliphatic hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, a carbamoyl group, -CO-O. A monovalent group represented by -R ^a , a monovalent group represented by -O-CO-R ^a' , a monovalent group represented by -SO _2- R ^a" , -R ^b- CO-O- monovalent groups represented by R ^c, monovalent group represented by ^{-R b '-O-CO-R} c', monovalent group is represented by ^-R _{b ^"-SO} 2 -R ^_c" R ^a , R ^a' , R ^{a "} , R ^b , R ^b' , R ^b" , R ^c , R ^c'and R ^{c "} indicate an aliphatic hydrocarbon group. These substituents are preferably used because they do not adversely affect heat resistance and the like. It is possible to adjust the spectral characteristics by adjusting the electron attracting property and the electron donating property of these substituents. Further, the aliphatic hydrocarbon group here may be the same as the aliphatic hydrocarbon group in R ¹ and R ² .

At least one of ^{R 1} and R ² is preferably an aliphatic hydrocarbon group, and R ^{1 and R 2} are preferably an aliphatic hydrocarbon group, and among them, a linear aliphatic hydrocarbon group. Is preferable. The aliphatic hydrocarbon group preferably has 1 or more and 10 or less carbon atoms, and further, an alkyl group having 1 or more and 6 or less carbon atoms suppresses the generation of foreign substances and improves the brightness of the colored layer. It is preferable because it can be formed. A linear alkyl group having 2 or more and 6 or less carbon atoms is more preferable, and a linear alkyl group having 2 or more and 4 or less carbon atoms is more preferable, from the viewpoint of being able to form a colored layer having improved brightness. It is even more preferable that the linear alkyl group has 3 or more and 4 or less carbon atoms.
At least one of ^{R 3} and R ⁴ is preferably an aromatic hydrocarbon group, and R ^{3 and R 4 are preferably an aromatic hydrocarbon group.} The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 or more and 10 or less carbon atoms, and a phenyl group forms a colored layer in which the generation of foreign substances is suppressed and the brightness is improved. It is preferable from the possible points.
Further, both the aromatic hydrocarbon group which may have a substituent or the aromatic heterocyclic groups R ³ and R ⁴ are substituted with an aliphatic hydrocarbon group. The aliphatic hydrocarbon group substituted with the hydrogen atom of the aromatic hydrocarbon group or the aromatic heterocyclic group is preferably a linear aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 or more and 10 or less carbon atoms, and more preferably a linear alkyl group having 1 or more and 6 or less carbon atoms.
Further, ^{at least one aromatic hydrocarbon group or aromatic heterocyclic group of R 3} and R ⁴ is replaced with two or more aliphatic hydrocarbon groups per aromatic hydrocarbon group or aromatic heterocyclic group. This is preferable from the viewpoint that the generation of foreign substances is suppressed and a colored layer having improved brightness can be formed.
When any one of the aliphatic hydrocarbon groups contained in R ¹ , R ² , R ³ and R ⁴ is a linear alkyl group having 2 or more carbon atoms and further 3 or more carbon atoms, it is contained in the molecule. It tends to be easy to adjust the electron density of.
Further, when ^{any one, more preferably at least two of the aliphatic hydrocarbon groups contained in R 1} , R ² , R ³ and R ⁴ is an alkyl group having 3 or more carbon atoms, the brightness tends to be improved. There is.

Further, the ^{aliphatic hydrocarbon group in R 1 to} R ⁴ is preferably unsubstituted, or in the case of a branched or linear alkyl group, the substituent is preferably an aromatic hydrocarbon group, and aromatic hydrocarbon is used. The substituent of the hydrogen group or the aromatic heterocyclic group is preferably an aliphatic hydrocarbon group. In such a case, the color material represented by the general formula (1) has a reduced polarity, so that the affinity for a low-polarity solvent such as PGMEA is improved. Further, a lower polar solvent can be used even when the coloring material is dissolved in a solvent, and the use of the low polar solvent improves the stability of the colored resin composition for a color filter of the present invention. Above all, it is preferable to have only an aliphatic hydrocarbon group as a substituent of the aromatic hydrocarbon group or the aromatic heterocyclic group from the viewpoint of improving the affinity for the low polar solvent.

-L ¹ -N ^- in -L ² -R ⁵ group, ^{L 1} and ^{L 2} are each independently a direct bond, -SO ₂ -, or -CO- a but, among them, -SO ₂ -, or - It is preferably CO-, and more preferably -SO _2- because it suppresses the generation of foreign substances, has excellent heat resistance, and can form a colored layer having improved brightness.

In the −L ¹ −N ⁻ −L ² −R ⁵ groups, R ⁵ is a halogenated aliphatic hydrocarbon group, and examples of the halogen include a fluorine atom, a chlorine atom, an iodine atom and the like, and among them, a fluorine atom. Is preferable. The halogenated aliphatic hydrocarbon group of R ⁵ is preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 or more and 8 carbon atoms, and a linear or branched halogenated aliphatic hydrocarbon group having 1 or more and 5 carbon atoms. It is more preferably a branched halogenated aliphatic hydrocarbon group, and even more preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 or more and 3 or less carbon atoms. Among them, the substitution rate of halogen atoms in the aliphatic hydrocarbon group (number of halogen atoms / total number of hydrogen atoms of the aliphatic hydrocarbon group) is preferably 50% or more, more preferably 70% or more. Above all, it is preferably 100%.
The R ^5, among them it is preferable carbon number of 1 to 5 linear or branched perfluoroalkyl group.

Further, in the general formula (1), ^-L 1 ^-N having a benzene ring linked to the xanthene structure - substitution position of ^-L 2 -R ⁵ group is not particularly limited, with respect to a xanthene skeleton, ortho Alternatively, it is preferably in the para position, and the fact that ^{5 groups of −L 1} −N ⁻ −L ² −R are substituted in the ortho position with respect to the xanthene skeleton is represented by the general formula (1). It is preferable from the viewpoint of various resistances. The mechanism of action is not clear, but when the -L ^1- N ^- L ^2- R ⁵ groups are in the ortho position, they can resonate with the carbon atoms of the xanthene skeleton to which the benzene ring is bonded to form a ring structure. It is presumed that the stability of the molecule is increased, and therefore the resistance of various coloring materials is improved.

The method for producing the coloring material represented by the general formula (1) is not particularly limited, and specific examples thereof include the following methods.
The sulfofluorane compound and the corresponding amine compound are refluxed in a solvent, and the reaction solution is filtered at 60 ° C. to remove insoluble matter, and then a part of the solvent is removed and poured into 6% hydrochloric acid. Then, a large amount of water is added and the mixture is stirred at room temperature for 30 minutes, and then the wet cake is collected by filtration. By washing this wet cake with water or hot water and then drying it, a precursor of the coloring material of the above general formula (1) can be obtained. When ^{producing a coloring material of the general formula (1) in which some structures of R 1} and R ³ and R ² and R ⁴ are different and asymmetric with respect to the xanthene ring, the corresponding half amine compound is used. Is added dropwise to a highly diluted sulfofluorane compound methanol solution, and after the reaction, the remaining amine compound is added dropwise, or a 1: 1 solution of each amine compound is slowly added dropwise to the sulfofluorane compound methanol solution. By doing so, a precursor of the coloring material of the general formula (1) having a high yield and asymmetry can be obtained.
Next, trifluoromethylsulfonamide is dissolved in chloroform in the precursor of the coloring material of the general formula (1), and triethylamine is added dropwise to cause a reaction. Then, the obtained reaction solution is washed with water, and then the organic layer is separated. The coloring material of the above general formula (1) can be obtained by drying this organic layer with sodium sulfate, purifying it by column chromatography, and concentrating it under reduced pressure.
When L1 is represented by −CO−, a fluorane compound is used instead of the sulfofluorane compound, and the coloring material of the above general formula (1) can be obtained in the same manner thereafter.

Since the coloring material represented by the general formula (1) used in the present invention has high solvent solubility even in a low-polarity solvent, it is necessary for coloring layer applications without using a solvent having an alcoholic hydroxyl group. Has solvent solubility at various concentrations. The coloring material represented by the general formula (1) used in the present invention is for at least one of propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, and diethylene glycol ethyl methyl ether. , The solubility of the coloring material represented by the general formula (1) at 23 ° C. is preferably 2.0 (g / 100 g solvent) or more, and more preferably 2.5 (g / 100 g solvent) or more. preferable.

Further, the coloring material represented by the general formula (1) may be used alone or in combination of two or more.
The blending amount of the coloring material represented by the general formula (1) is not particularly limited as long as the effect of the present invention is not impaired. The coloring material represented by the general formula (1) is preferably 1 part by mass or more and 50 parts by mass or less, and preferably 1 part by mass or more and 40 parts by mass or less from the viewpoint of being matched with a desired color.

(Other color materials)
The colored resin composition for a color filter of the present invention further contains, if necessary, another coloring material different from the coloring material represented by the general formula (1) for the purpose of controlling the color tone. May be good. As the other coloring material, for example, conventionally known organic pigments, lake pigments, dyes, inorganic pigments and the like can be selected depending on the purpose, and one kind or two or more kinds can be used.
As the other coloring material, it is preferable to include a blue coloring material from the viewpoint of forming, for example, a blue coloring layer.
The blue color material used is not particularly limited, and known blue organic pigments, blue dyes, blue lake pigments and the like can be used. Here, the blue organic pigment is superior to dyes and lake pigments in various resistances such as heat resistance and light resistance, and the blue dye is soluble and therefore has higher transparency than the organic pigment. Further, the lake pigment refers to an organic pigment in which a dye soluble in water is precipitated with a lake agent (precipitant) to make it insoluble. Since the lake pigment is derived from a dye, it has a higher transmittance than a normal pigment and can meet the demand for higher brightness.

It is preferable that the coloring material (A) contains at least one of a phthalocyanine pigment and a lake pigment of a dye from the viewpoint of excellent resistance such as heat resistance of the blue colored layer.
Further, when the color material (A) contains at least one of a dye and a lake pigment of the dye, fluorescence by the color material represented by the general formula (1) can be suppressed and the contrast is improved. It is preferable because it can be used.
Further, when the coloring material (A) contains both the lake pigment and the phthalocyanine pigment of the dye in combination with the coloring material represented by the general formula (1), the heat resistance of the blue coloring layer and the like can be determined. It is preferable because it has excellent resistance, can suppress fluorescence due to the coloring material represented by the general formula (1), and can improve contrast.

Examples of the blue organic pigment include C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and the like. Of these, copper phthalocyanine-based blue pigments are preferable because they are relatively excellent in brightness.

Examples of the blue dye include methine dyes, anthraquinone dyes, azo dyes, triarylmethane dyes, phthalocyanine dyes, anthraquinone dyes and the like, among which anthraquinone dyes, phthalocyanine dyes and triarylmethane dyes. At least one selected from the group consisting of the cyanine dye and the cyanine dye is preferable from the viewpoint that a high-brightness color filter can be formed.
Above all, it is particularly preferable to use a phthalocyanine dye or an anthraquinone dye in combination because it is possible to suppress the fluorescence of the coloring material represented by the general formula (1) and improve the contrast. In particular, when at least a blue organic pigment is used as the blue color material, and when a phthalocyanine dye or an anthraquinone dye is used in combination, the effect of significantly improving the contrast is obtained.
When a blue dye is used in combination with the color material represented by the general formula (1), fluorescence can be suppressed and contrast can be improved. Therefore, the content of the blue dye is the blue dye. The total amount of the coloring material represented by the general formula (1) is preferably 1 part by mass or more and 15 parts by mass or less, and further 2 parts by mass or more and 10 parts by mass or less. preferable.

Examples of the blue lake pigment include those obtained by rake-forming the above-mentioned blue dye with a rake agent.
The rake agent is not particularly limited, and is, for example, phosphotungsten acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, 3,4,5-trihydroxybenzoic acid, ferricyanide, ferrocyanide. Etc. can be used.

Examples of the blue lake pigment include C.I. I. Pigment Blue 1, 1: 2, 2, 3, 8, 9, 10, 12, 14, 17: 1, 18, 19, 24, 24: 1, 53, 56, 56: 1, 61, 61: 1, 62, 63, 78 and the like can be mentioned.

The blue dye and the blue lake pigment are not particularly limited, but among them, a triarylmethane-based coloring material containing triarylmethane as a basic skeleton is preferable from the viewpoint of improving the brightness and contrast of the colored layer.
Examples of the triarylmethane-based blue color material include triarylmethane-based dyes having a triarylmethane skeleton as described in, for example, International Publication No. 2012/039416 and International Publication No. 2012/039417. And triarylmethane-based lake pigments and the like.

Further, as the triarylmethane-based lake pigment, those represented by the following general formula (2) are also preferably used from the viewpoint of achieving high brightness of the colored layer.

（一般式（２）中、Ａは、Ｎと直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基、又は当該脂肪族炭化水素基を有する芳香族基を表し、炭素鎖中にＯ、Ｓ、Ｎが含まれていてもよい。Ｂ^ｃ−はｃ価のアニオンを表す。Ｒ^ＸＩ〜Ｒ^ＸＶは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、Ｒ^ＸＩＩとＲ^ＸＩＩＩ、Ｒ^ＸＩＶとＲ^ＸＶが結合して環構造を形成してもよい。Ａｒ^１は置換基を有していてもよい２価の芳香族基を表す。複数あるＲ^ＸＩ〜Ｒ^ＸＶ及びＡｒ^１はそれぞれ同一であっても異なっていてもよい。
ａ及びｃは２以上の整数、ｂ及びｄは１以上の整数を表す。ｅは０又は１であり、ｅが０のとき結合は存在しない。複数あるｅは同一であっても異なっていてもよい。）

(In the general formula (2), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group is at least saturated aliphatic hydrocarbon at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and O, S, and N may be contained in the carbon chain. B ^c− is a c-valent anion. ^{R XI to} R ^XV each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ^XII , R ^XIII , and ^RXIV . good .Ar ¹ be R ^XV combine to form a ring structure represents a divalent aromatic group which may have a substituent. plural ^R XI ^{to R XV} and Ar ¹ each identical It may or may not be different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )

A in the general formula (2) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group is at least a saturated fat at the terminal directly bonded to N. Represents an aliphatic hydrocarbon group having a group hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group, and contains O (oxygen atom), S (sulfur atom), and N (nitrogen atom) in the carbon chain. It may be. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as color tone and transmittance of the cationic color-developing site are not affected by the linking group A and other color-developing sites, and are not affected by the monomer. Similar colors can be retained.
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N is linear, branched or cyclic unless the carbon atom at the terminal directly bonded to N has a π bond. Any of the above, the carbon atom other than the terminal may have an unsaturated bond, or may have a substituent, and O, S, and N are contained in the carbon chain. May be good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group and the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
Further, in A, the aromatic group having an aliphatic hydrocarbon group is a monocyclic or polycyclic aromatic group having at least an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N. It may be mentioned and may have a substituent, and may be a heterocycle containing O, S, N.
Among them, from the viewpoint of skeletal robustness, A preferably contains a cyclic aliphatic hydrocarbon group or aromatic group.
As the cyclic aliphatic hydrocarbon group, the alicyclic hydrocarbon group Aribashi is particularly preferable from the viewpoint of skeletal robustness. The alicyclic hydrocarbon group with a bridge refers to a polycyclic aliphatic hydrocarbon group having a bridging structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane and adamantane. Among the alicyclic hydrocarbon groups with bridges, norbornane is preferable. Examples of the aromatic group include a group containing a benzene ring and a naphthalene ring, and among them, a group containing a benzene ring is preferable. For example, when A is a divalent organic group, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms or an aromatic group in which two alkylene groups having 1 to 20 carbon atoms such as a xylylene group are substituted. And so on.

The valence a in A is the number of color-developing cation sites constituting the cation, and a is an integer of 2 or more. In this lake pigment, since the cation valence a is 2 or more, it is excellent in heat resistance, and it is particularly preferable that the cation valence a is 3 or more. The upper limit of a is not particularly limited, but from the viewpoint of ease of production, a is preferably 4 or less, and more preferably 3 or less.

^{Specific examples of Ar 1} and R ^{XI to} R ^{XV in} the general formula (2) include those described in the pamphlet of International Publication No. 2012/144520.

In the lake pigment represented by the general formula (2), the anion portion (B ^c− ) is not particularly limited and may be an organic anion or an inorganic anion. Here, the organic anion represents an anion containing at least one carbon atom. The inorganic anion represents an anion that does not contain a carbon atom. ^{In the present invention, Bc−} is preferably an inorganic anion from the viewpoint of high brightness and excellent heat resistance.
Specific examples of the organic anion and the inorganic anion include those described in Pamphlet No. 2012/144520.
Among them, an anion of an inorganic acid containing at least one of tungsten (W) and molybdenum (Mo) is preferable from the viewpoint of high brightness and excellent heat resistance.

In the general formula (2), b represents the number of cations, d represents the number of anions in the molecular assembly, and b and d represent integers of 1 or more. When b is 2 or more, a plurality of cations in the molecular assembly may be used alone or in combination of two or more. When d is 2 or more, a plurality of anions in the molecular assembly may be used alone or in combination of two or more, and organic anions and inorganic anions may be used in combination. ..

E in the general formula (2) is an integer of 0 or 1. e = 0 represents the triarylmethane skeleton and e = 1 represents the xanthene skeleton. A plurality of e may be the same or different. In the lake pigment represented by the general formula (2) used in the present invention, those containing at least a triarylmethane skeleton are preferably used.
The lake pigment represented by the general formula (2) can be prepared by referring to, for example, International Publication No. 2012/144520 Pamphlet.

When a blue color material is used in combination with the color material represented by the general formula (1), the blending amount thereof is not particularly limited as long as the effect of the present invention is not impaired. The color material represented by the general formula (1) is preferably 30 parts by mass or more and 99 parts by mass or less, and more preferably 50 parts by mass or more and 98 parts by mass or less with respect to 100 parts by mass of the material. , 60 parts by mass or more and 95 parts by mass or less is particularly preferable. Within this range, the color tone of the blue colored layer can be controlled without impairing the effect of the present invention.

Further, examples of the organic pigment used as another color material, which is different from the color material represented by the general formula (1) and the blue color material, include C.I. I. Pigment Violet 19, 23, 29, 32, 36, 38 and the like.

Examples of lake pigments used as other coloring materials include C.I. I. Pigment Violet 1, 2, 3, 3: 1, 3: 3, 4, 5, 5: 1, 6: 1, 7: 1, 9, 12, 20, 26, 27, 39 and the like.

Examples of dyes used as other coloring materials include red dyes such as xanthene dyes, azo dyes, perinone dyes, and dipyrromethene dyes.

When the other coloring material is used, the blending amount thereof is not particularly limited as long as the effect of the present invention is not impaired. For example, the coloring material represented by the general formula (1) and the blue coloring material are used. The other coloring material is preferably 0.5 parts by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, based on 100 parts by mass of the total mass of the above. It is particularly preferable that the amount is not less than 30 parts by mass. Within this range, the color tone can be controlled without impairing the effect of the present invention.

The total content of the coloring material is preferably 3% by mass to 65% by mass, more preferably 4% by mass to 60% by mass, based on the total solid content of the colored resin composition for the color filter. When it is at least the above lower limit value, the colored layer when the colored resin composition for a color filter is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm) has a sufficient color density. Further, if it is not more than the above upper limit value, it is possible to obtain a colored layer having excellent storage stability, sufficient hardness, and adhesion to a substrate. In particular, when forming a colored layer having a high colorant concentration, the total content of the colored material is 15% by mass to 65% by mass, more preferably 25, based on the total solid content of the colored resin composition for the color filter. It is preferable to mix in a ratio of mass% to 60% by mass.
In the present invention, the solid content includes all substances other than the above-mentioned solvent, and also includes a polyfunctional monomer dissolved in the solvent and the like.

<Binder component>
The colored resin composition for a color filter of the present invention contains a binder component in order to impart film forming property and adhesion to the surface to be coated. It is preferable to contain a curable binder component in order to impart sufficient hardness to the coating film. The curable binder component is not particularly limited, and a curable binder component used for forming a colored layer of a conventionally known color filter can be appropriately used.
Examples of the curable binder component include a photocurable binder component containing a photocurable resin that can be polymerized and cured by visible light, ultraviolet rays, electron beams, etc., and a thermosetting resin that can be polymerized and cured by heating. Those containing a thermosetting binder component containing the same can be used.

When a photolithography step is used to form the colored layer, a photosensitive binder component having alkali developability is preferably used. A thermosetting binder component may be further used as the photosensitive binder component.
Examples of the photosensitive binder component include a positive type photosensitive binder component and a negative type photosensitive binder component. Examples of the positive photosensitive binder component include a system containing an alkali-soluble resin and an o-quinonediazide group-containing compound as a photosensitive-imparting component.

On the other hand, as the negative photosensitive binder component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is preferably used.
In the colored resin composition for a color filter according to the present invention, a negative photosensitive binder component is preferable because a pattern can be easily formed by using an existing process by a photolithography method.
Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator constituting the negative photosensitive binder component will be specifically described.

(Alkali-soluble resin)
The alkali-soluble resin in the present invention has an acidic group, acts as a binder resin, and is appropriately selected and used as long as it is soluble in a developing solution used for pattern formation, particularly preferably an alkaline developing solution. be able to.
In the present invention, the acid value of the alkali-soluble resin is not particularly limited. From the viewpoint of improving the stability over time such as dispersion stability and improving the heat resistance of the colored layer obtained from the resin composition, a resin having an acid value of 30 mgKOH / g or more and 300 mgKOH / g or less is used as the alkali-soluble resin. Is preferable.
In the present invention, the acid value represents the mass (mg) of KOH required to neutralize 1 g of solid content, and refers to the value obtained by the potentiometric titration method according to JIS K 0070.

The preferred alkali-soluble resin in the present invention is a resin having a carboxy group as an acidic group, specifically, an acrylic copolymer having a carboxy group, an epoxy (meth) acrylate resin having a carboxy group, and a carboxy group. Polyamideimide resin and the like can be mentioned. Among these, those having a carboxy group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain are particularly preferable. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. Further, the alkali-soluble resin selected from the group consisting of the acrylic copolymer having a carboxy group, the epoxy acrylate resin having a carboxy group, and the polyamide-imide resin having a carboxy group may be one kind. Two or more kinds may be mixed and used.

The acrylic copolymer having a carboxy group is obtained by copolymerizing a carboxy group-containing ethylenically unsaturated monomer and another ethylenically unsaturated monomer.

Specific examples of the acrylic copolymer having a carboxy group include those described in JP2013-029832, and specifically, for example, methyl (meth) acrylate and ethyl (meth). ) An example thereof is a copolymer composed of a monomer having no carboxy group such as acrylate and one or more selected from (meth) acrylic acid and its anhydride. Further, examples thereof include polymers in which an ethylenically unsaturated bond is introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above copolymer, but the present invention is limited thereto. It is not something that is done.

The monomer having no carboxy group preferably has a hydrocarbon ring. By including a bulky hydrocarbon ring in the colored layer, the solvent resistance and heat resistance of the obtained colored layer are enhanced.
Examples of such a hydrocarbon ring include an aliphatic hydrocarbon ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, and a combination thereof. May have a substituent such as an alkyl group, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group, a hydroxyl group, a nitro group, an amino group or a halogen atom.
The hydrocarbon ring may be contained as a monovalent group or may be contained as a divalent or higher valent group.

Specific examples of hydrocarbon rings include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), and adamantan. Rings: Aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycycles such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilben, and cardo structures (9,9-diarylfluorene), etc. Can be mentioned.

When the hydrocarbon ring contains an aliphatic hydrocarbon ring, it is preferable because the heat resistance and adhesion of the colored layer are improved and the brightness of the obtained colored layer is improved.

The alkali-soluble resin preferably has a crosslinked cyclic hydrocarbon ring, which is an aliphatic hydrocarbon ring having a structure in which two or more rings share two or more atoms.
Specific examples of the crosslinked cyclic hydrocarbon ring include norbornane, isobornane, adamantane, tricyclo [5.2.1.0 (2,6)] decane, and tricyclo [5.2.1.0 (2,6)]. Decene, tricyclopentene, tricyclopentane, tricyclopentadiene, dicyclopentadiene; examples thereof include groups in which some of these groups are substituted with substituents.
Examples of the substituent include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a halogen atom and the like.

The lower limit of the number of carbon atoms of the crosslinked ring-type hydrocarbon ring is preferably 5 or more, and particularly preferably 7 or more, from the viewpoint of compatibility with other materials and solubility in an alkaline developer. The upper limit is preferably 12 or less, and particularly preferably 10 or less.

The copolymerization ratio of the carboxy group-containing ethylenically unsaturated monomer in the carboxy group-containing copolymer is usually 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass. In this case, if the copolymerization ratio of the carboxy group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the obtained coating film in an alkaline developer is lowered, and pattern formation becomes difficult. Further, when the copolymerization ratio exceeds 50% by mass, the formed pattern tends to fall off from the substrate and the film on the surface of the pattern tends to be roughened during development with an alkaline developer.

The acid value of the carboxy group-containing copolymer is preferably 30 mgKOH / g or more and 200 mgKOH / g or less, more preferably 50 mgKOH / g or more and 150 mgKOH / g or less, and 60 mgKOH / g or more and 120 mgmgKOH / g or less. It is even more preferable to have.
The weight average molecular weight of the carboxy group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 4,000 to 25,000. If it is less than 1,000, the binder function after curing is remarkably lowered, and if it exceeds 50,000, it may be difficult to form a pattern during development with an alkaline developer. The weight average molecular weight referred to here is obtained as a standard polystyrene-equivalent value by gel permeation chromatography (GPC).

The epoxy (meth) acrylate resin having a carboxy group is not particularly limited, but is an epoxy (meth) obtained by reacting a reaction product of an epoxy compound with an unsaturated group-containing monocarboxylic acid with an acid anhydride. Epoxy compounds are suitable.
The acid value of the epoxy (meth) acrylate resin having a carboxy group is preferably 30 mgKOH / g or more and 200 mgKOH / g or less, more preferably 50 mgKOH / g or more and 150 mgKOH / g or less, and more preferably 60 mgKOH / g or more. It is even more preferably 120 mgmgKOH / g or less.
The epoxy compound for preparing the epoxy (meth) acrylate resin having a carboxy group, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known ones and used.

The epoxy compound is not particularly limited, but is bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, aliphatic epoxy compound, or Examples thereof include epoxy compounds such as bisphenol fluorene type epoxy compounds. These may be used alone or in combination of two or more.

Examples of the unsaturated group-containing monocarboxylic acid include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, and (meth) acrylic acid dimer. These unsaturated group-containing monocarboxylic acids may be used alone or in combination of two or more.

Examples of acid anhydrides include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, and endobicyclo- [2,2,1 ] -A polyvalent carboxylic acid anhydride derivative such as hepto-5-ene-2,3-dicarboxylic acid anhydride can be mentioned. These may be used alone or in combination of two or more.

Among the epoxy (meth) acrylate resins having a carboxy group, those containing a structure (cardo structure) in which two phenyl groups are bonded to the C-9 position of fluorene in the molecule have improved brightness and. It is preferable because the curability of the colored layer is improved and the residual film ratio of the colored layer is increased.

The exact mechanism of the epoxy (meth) acrylate resin having a carboxy group containing a cardo structure is unknown, but it is considered to be highly sensitive to radicals because the fluorene skeleton contains a π-conjugated system, which will be described later. By combining with an oxime ester-based photopolymerization initiator, required performances such as sensitivity, developability, and development adhesion can be improved. Further, since the epoxy (meth) acrylate resin having a carboxy group containing the cardo structure has high solvent resolubility, it is possible to design a colored resin composition having no agglutination even at a high color concentration. preferable.

The epoxy (meth) acrylate resin having a carboxy group containing a cardo structure is, for example, an epoxy compound of a bisphenol fluorene compound to obtain an epoxy compound of a bisphenol fluorene compound, which is reacted with (meth) acrylic acid to form an epoxy (meth) acrylate. It can be obtained by reacting this epoxy (meth) acrylate with a polyvalent carboxylic acid or an acid anhydride thereof. Examples of the epoxy (meth) acrylate resin having a carboxy group containing a cardo structure include a polymerizable compound represented by the general formula (1) described in JP-A-2007-197720 and JP-A-2006-308698. Preferable examples thereof include a reaction product (polycondensate product) of an epoxy (meth) acrylate having a fluorene skeleton and a polybasic acid described in Japanese Patent Publication No.

The polyamide-imide resin having a carboxy group is not particularly limited, but is preferably 90 mgKOH / g or more, more preferably 110 mgKOH / g or more, and even more preferably 110 mgKOH / g or more from the viewpoint of developability. It is preferably 130 mgKOH / g or more. On the other hand, the acid value of the polyamide-imide resin having a carboxy group is preferably 300 KOH mg / g or less, and more preferably 250 KOH mg / g or less, from the viewpoint of suppressing water stains and excellent stability of the colored resin composition. preferable.

As the polyamide-imide resin having a carboxy group, it is possible to form a colored layer having improved brightness and contrast, and it is easy to obtain a colored resin composition for a color filter having good developability and suppressing the occurrence of water stain after development. From the point of view, it is preferable that the polyamide-imide resin has a repeating unit represented by the following general formula (A).

（一般式（Ａ）において、Ｒａはそれぞれ独立に、２価の脂肪族ジイソシアネート類の残基を表し、Ｒｂは、下記一般式（Ｂ１）、（Ｂ２）又は（Ｂ３）で表される構造単位であり、Ｒｃは、下記一般式（Ｃ１）、（Ｃ２）、（Ｃ３）、（Ｃ４）、（Ｃ５）、（Ｃ６）、（Ｃ７）、（Ｃ８）、（Ｃ９）、又は（Ｃ１０）で表される構造単位である。ポリアミドイミド樹脂中に存在する複数のＲａ、Ｒｂ及びＲｃは、それぞれ同一であっても異なっていても良い。Ｒｂの少なくとも１つは下記一般式（Ｂ１）又は（Ｂ２）で表される構造単位であり、Ｒｃ及び樹脂末端の少なくとも１つにおいて酸性基を含む。ｎは繰り返し単位数を表し、１以上である。）

(In the general formula (A), Ra independently represents a residue of divalent aliphatic diisocyanates, and Rb is a structural unit represented by the following general formula (B1), (B2) or (B3). Rc is represented by the following general formulas (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9), or (C10). The structural unit represented. The plurality of Ra, Rb and Rc present in the polyamideimide resin may be the same or different. At least one of Rb is the following general formula (B1) or ( It is a structural unit represented by B2) and contains an acidic group at at least one of Rc and the resin terminal. N represents the number of repeating units and is 1 or more.)

（一般式（Ｂ１）、（Ｂ２）、（Ｂ３）、（Ｃ１）、（Ｃ２）、（Ｃ３）、（Ｃ４）、（Ｃ５）、（Ｃ６）、（Ｃ７）、（Ｃ８）、（Ｃ９）、及び（Ｃ１０）において、Ｒｄはそれぞれ独立に、炭素数６〜２０の置換基を有しても良い芳香族若しくは脂肪族トリカルボン酸残基又はテトラカルボン酸残基である。Ｒｅはそれぞれ独立に、アルコール化合物から水酸基を除いた残基を表す。）

(General formulas (B1), (B2), (B3), (C1), (C2), (C3), (C4), (C5), (C6), (C7), (C8), (C9) In (C10), Rd is an aromatic or aliphatic tricarboxylic acid residue or a tetracarboxylic acid residue which may have a substituent having 6 to 20 carbon atoms, respectively. Re is independently. , Represents a residue obtained by removing a hydroxyl group from an alcohol compound.)

Residues of aliphatic diisocyanates in the repeating unit represented by the general formula (A), aromatic or aliphatic tricarboxylic acid residues or tetracarboxylic acid residues which may have a substituent having 6 to 20 carbon atoms. Etc. may be introduced by appropriately selecting an aliphatic diisocyanate or an aromatic or aliphatic tricarboxylic acid or tetracarboxylic acid which may have a substituent having 6 to 20 carbon atoms. The polyamide-imide resin having the repeating unit represented by the general formula (A) can be prepared, for example, by referring to International Publication No. 2015/008744.

The alkali-soluble resin used in the colored resin composition for a color filter of the present invention may be used alone or in combination of two or more, and the content thereof is a colored resin for a color filter. It is usually in the range of 10 parts by mass to 1000 parts by mass, preferably in the range of 20 parts by mass to 500 parts by mass with respect to 100 parts by mass of the coloring material contained in the composition. When the content of the alkali-soluble resin is at least the above lower limit, sufficient alkali developability can be easily obtained, and when the content of the alkali-soluble resin is at least the above upper limit, the proportion of the coloring material is relatively relative. It does not become too low, and it is easy to obtain a sufficient coloring density.

(Polyfunctional monomer)
The polyfunctional monomer used in the colored resin composition for a color filter may be any as long as it can be polymerized by the photoinitiator, and is not particularly limited, and usually, a compound having two or more ethylenically unsaturated double bonds is used. It is preferably used, and particularly preferably a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups.
As such a polyfunctional (meth) acrylate, it may be appropriately selected and used from conventionally known ones. Specific examples include those described in Japanese Patent Application Laid-Open No. 2013-029832.

One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination. Further, when the colored resin composition for a color filter of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional monomer has three or more polymerizable double bonds (trifunctional). Poly (meth) acrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid-modified products are preferable, and specifically, trimethylpropantri (meth) acrylate and pentaerythritol tri (meth) are preferable. ) Acrylate, succinic acid-modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate The succinic acid modified product of the above, dipentaerythritol hexa (meth) acrylate and the like are preferable.

The content of the polyfunctional monomer used in the colored resin composition for a color filter is not particularly limited, but the polyfunctional monomer is preferably 5% by mass to 60% by mass with respect to the total solid content of the colored resin composition for a color filter. It is in the range of mass%, more preferably 10 mass% to 40 mass%. When the content of the polyfunctional monomer is at least the above lower limit value, photocuring proceeds sufficiently, elution of the exposed portion during development can be suppressed, and when the content of the polyfunctional monomer is at least the above upper limit value, alkaline development is performed. The sex is sufficient.

(Light initiator)
The initiator used in the colored resin composition for a color filter of the present invention is not particularly limited, and one or a combination of two or more of various conventionally known initiators can be used.
Examples of the initiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone and the like. Can be done. Specific examples of the initiator include aromatic ketones such as benzophenone, 4,4'-bisdiethylaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, and benzoin such as ethylbenzoin. , 2- (o-Chlorophenyl) -4,5-phenylimidazole dimer and other biimidazoles, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazol and other halos Methyloxaziazole compounds, halomethyl-S-triazine compounds such as 2- (4-butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-Diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,1-hydroxy-cyclohexyl-phenylketone, benzyl, benzoyl benzoic acid, methyl benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, p-dimethylaminobenzoic acid Isoamyl, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenylsulfide, 1-hydroxy-cyclohexyl -Phenylketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [ 4- (Methylthio) phenyl] -2- (4-morpholinyl) -1-propanol and the like can be mentioned.
Among them, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1- Butanone, 4,4'-bis (diethylamino) benzophenone, and diethylthioxanthone are preferably used. Furthermore, it is sensitive to combine an α-aminoacetophenone-based initiator such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one with a thioxanthone-based initiator such as diethylthioxanthone. It is preferable because it suppresses adjustment and water stains and improves development resistance.
When the α-aminoacetophenone-based initiator and the thioxanthone-based initiator are used, the total content thereof is preferably 5% by mass to 15% by mass with respect to the total solid content of the colored resin composition. When the amount of the initiator is 15% by mass or less, the sublimated product in the manufacturing process is reduced, which is preferable. When the amount of the initiator is 5% by mass or more, development resistance such as water stain is improved.

In the present invention, the initiator preferably contains an oxime ester-based photoinitiator. The coloring material represented by the general formula (1) used in the present invention tends to have lower sensitivity than the conventionally used pigments exhibiting blue to purple, but an oxime ester-based photoinitiator is used. This makes it possible to improve the sensitivity. Further, by using the oxime ester-based photoinitiator, it is easy to suppress the variation in the line width in the plane when forming the fine line pattern. Further, by using the oxime ester-based photoinitiator, the residual film ratio tends to be improved and the effect of suppressing the occurrence of water stains tends to be enhanced. In addition, water stain means that when a component that enhances alkali developability is used, traces of water stain are generated after alkaline development and rinsing with pure water. Since such water stains disappear after post-baking, there is no problem as a product, but there is a problem that it is detected as unevenness abnormality in the appearance inspection of the patterning surface after development, and it is not possible to distinguish between a normal product and an abnormal product. Occurs. Therefore, if the inspection sensitivity of the inspection device is lowered in the visual inspection, the yield of the final color filter product is lowered as a result, which causes a problem.
The oxime ester-based photoinitiator preferably has an aromatic ring, and has a condensed ring containing an aromatic ring, from the viewpoint of reducing contamination of the colored resin composition for a color filter by decomposition products and contamination of the apparatus. It is more preferable to have a fused ring containing a benzene ring and a hetero ring.
Examples of the oxime ester-based photoinitiator include 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime), Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Application Laid-Open No. 2001-233842, Japanese Patent Application Laid-Open No. 2010-527339, Japanese Patent Application Laid-Open No. 2010-527338, It can be appropriately selected from the oxime ester-based photoinitiators described in JP-A-2013-041153 and the like. Commercially available products include Irgacure OXE-01, ADEKA ARKULS NCI-930 with diphenylsulfide skeleton, TR-PBG-345, TR-PBG-304 with carbazole skeleton, TR-PBG-365 with fluorene skeleton, and diphenylsulfide skeleton. TR-PBG-3057 (all manufactured by Joshu Powerful Electronics New Materials Co., Ltd.) and the like may be used. In particular, it is preferable to use an oxime ester-based photoinitiator having a diphenylsulfide skeleton or a fluorene skeleton from the viewpoint of brightness. Further, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.
Further, it is preferable to use two or more kinds of oxime ester-based photoinitiators in combination because the brightness and the residual film ratio are easily improved and the effect of suppressing the occurrence of water stains is high. In particular, the combined use of two types of oxime ester-based photoinitiators having a diphenyl sulfide skeleton or the combined use of an oxime ester-based photoinitiator having a diphenyl sulfide skeleton and an oxime ester-based photoinitiator having a fluorene skeleton has high brightness and heat resistance. It is preferable because of its high property. Further, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton in combination with an oxime ester-based photoinitiator having a fluorene skeleton or an oxime ester-based photoinitiator having a diphenyl sulfide in terms of excellent sensitivity and brightness.

Further, it is preferable to use an oxime ester-based photoinitiator in combination with a photoinitiator having a tertiary amine structure from the viewpoint of suppressing water stains and improving sensitivity. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure which is an oxygen quencher in the molecule, the radicals generated from the initiator are not easily deactivated by oxygen, and the sensitivity can be improved. be. Examples of commercially available photoinitiators having a tertiary amine structure include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (for example, Irgacure 907, manufactured by BASF). 2-Benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (eg, Irgacure 369, manufactured by BASF), 4,4'-bis (diethylamino) benzophenone (eg, Hycure ABP, etc.) (Made by Kawaguchi Yakuhin).
Further, it is preferable to combine the oxime ester-based photoinitiator with the thioxanthone-based initiator from the viewpoints of adjusting the sensitivity, suppressing water stains, and improving the development resistance. It is preferable to combine an initiator in that the brightness and the residual film ratio are improved, the sensitivity can be easily adjusted, the effect of suppressing the occurrence of water stains is high, and the development resistance is improved.
Compared with the red and green coloring compositions, the blue and purple coloring compositions are less likely to transmit ultraviolet rays, and there is a tendency for the problem of insufficient curing mainly in the deep part of the coating film to occur. In particular, when the coloring material represented by the general formula (1) used in the present invention which exhibits purple color is used, insufficient curing is likely to occur. Therefore, the curability of the coating film by combining with thioxanthone having a sensitizing effect Is improved.

The content of the photoinitiator used in the colored resin composition for a color filter of the present invention is usually about 0.01 parts by mass to 100 parts by mass, preferably about 5 parts by mass with respect to 100 parts by mass of the polyfunctional monomer. It is 60 parts by mass. When this content is at least the above lower limit value, photocuring is sufficiently advanced and the exposed portion is suppressed from being eluted during development, while when it is at least the above upper limit value, the yellowing of the obtained colored layer is weakened and the brightness is increased. It is possible to suppress the decrease.
Further, the total content of two or more kinds of oxime ester-based photoinitiators as the photoinitiator used in the color filter colored resin composition of the present invention is based on the total solid content of the color filter colored resin composition. It is preferably in the range of 0.1% by mass to 12.0% by mass, more preferably 1.0% by mass to 8.0% by mass, from the viewpoint of sufficiently exerting the combined effect of these photoinitiators. ..

The total content of the binder component used in the colored resin composition for a color filter of the present invention is preferably 35% by mass to 97% by mass, preferably 40% by mass, based on the total solid content of the colored resin composition for a color filter. It is more preferable to blend in a ratio of% to 96% by mass. When it is at least the above lower limit value, a colored layer having excellent hardness and adhesion to the substrate can be obtained. Further, when it is not more than the above upper limit value, the developability is excellent and the generation of minute wrinkles due to heat shrinkage is suppressed.

<Solvent>
The solvent contained in the colored resin composition for a color filter of the present invention may be an organic solvent that does not react with each component in the colored resin composition for a color filter and can dissolve or disperse them, and is particularly limited. It is not something that is done.
The coloring material represented by the general formula (1) may be used by being dissolved in a solvent, or may be used by being dispersed.

Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, i-propyl alcohol and methoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate and methoxypropion. Ester solvents such as methyl acid, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, n-butyl butyrate, clohexanol acetate; acetone, Ketone solvents such as methyl ethyl ketone, cyclohexanone, 2-heptanone; glycol ether acetate such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate Solvents: Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA); Diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl Glycol ether solvents such as ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether; N, N-dimethyl Aprotonic amide solvents such as formamide, N, N-dimethylacetamide, N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated carbides such as benzene, toluene, xylene and naphthalene. Hydrogen-based solvents; saturated hydrocarbon-based solvents such as N-heptane, N-hexane, and N-octane; organic solvents such as aromatic hydrocarbons such as toluene and xylene can be mentioned. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferably used in terms of the solubility of other components. Among them, the solvents used in the present invention include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, and 3-methoxybutyl. It is preferable to contain at least one selected from the group consisting of acetate from the viewpoint of solubility of other components and application suitability.

Further, from the viewpoint of developability, solvent resolubility and the like, it is also preferable to use a mixed solvent containing two or more kinds of solvents.

When a mixed solvent is used, the above-mentioned glycol ether acetate is used as the first solvent for reasons such as high safety; moderate volatility; good dispersibility due to moderate solubility; etc. It is preferable to use a system solvent. Among them, 2-methoxyethyl acetate or propylene glycol monomethyl ether acetate having a boiling point (meaning the boiling point at atmospheric pressure; the same applies hereinafter) of less than 150 ° C. is more preferable, and propylene glycol monomethyl ether acetate (PGMEA) is particularly preferable. preferable.

Examples of the second solvent (solvent other than the first solvent) include a solvent having a boiling point of 150 ° C. or higher, a solvent having an alcoholic hydroxyl group, and the like.
The second solvent may be used alone or in combination of two or more.

When the first solvent is a solvent having a boiling point of less than 150 ° C., if a solvent having a boiling point of 150 ° C. or higher is used as the second solvent, uneven drying is less likely to occur, foreign matter is less likely to be generated, and solvent resolubility is likely to be improved. ..
Examples of solvents having a boiling point of 150 ° C. or higher include diethylene glycol ethyl methyl ether (boiling point 179 ° C.), 3-methoxy-3-methyl-1-butyl acetate (boiling point 188 ° C.), diethylene glycol ethyl methyl ether (boiling point 179 ° C.), 3. -Methoxybutyl acetate (boiling point 172 ° C.) and the like can be mentioned. As the solvent having a boiling point of 150 ° C. or higher as the second solvent, at least one of a glycol ether acetate solvent and a glycol ether solvent is more preferable from the viewpoint of suppressing bumping during drying under reduced pressure.

When a mixed solvent is used, the content of the solvent having a boiling point of 150 ° C. or higher is preferably 40% by mass or less, more preferably 30% by mass or less in the total solvent. Further, 3% by mass or more is preferable, 5% by mass or more is more preferable, and 10% by mass or more is further preferable.
Within the above range, uneven drying is unlikely to occur, and the drying time does not become too long, resulting in good productivity.

The boiling point of the above-mentioned "solvent having a boiling point of 150 ° C. or higher" is preferably 240 ° C. or lower, and particularly preferably 200 ° C. or lower, from the viewpoint that the drying time does not become too long.

Further, when a solvent having an alcoholic hydroxyl group is used as the second solvent, the solvent resolubility tends to be further improved.
Examples of the solvent having an alcoholic hydroxyl group include the alcohol-based solvent, the carbitol-based solvent, and the glycol ether-based solvent. Specific examples thereof include propylene glycol monomethyl ether (boiling point: 121 ° C.) and 3-methoxy-. Examples thereof include 3-methyl-1-butanol (boiling point of 174 ° C.) and diacetone alcohol (boiling point of 166 ° C.).
When a mixed solvent is used, the content of the solvent having an alcoholic hydroxyl group is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less in the total solvent. Further, 0.1% by mass or more is preferable, 0.3% by mass or more is more preferable, and 1% by mass or more is further preferable.

Since the coloring material represented by the general formula (1) used in the present invention has high solvent solubility even in a low-polarity solvent, a solvent having an alcoholic hydroxyl group is used as the main solvent (50% by mass or more of the total solvent). ), It has solvent solubility at the concentration required for colored layer applications. The coloring material represented by the general formula (1) used in the present invention is dissolved in at least one of a glycol ether solvent and a glycol ether acetate solvent having no alcoholic hydroxyl group to form a colored resin composition. It is also possible to adjust things.

Further, in the colored resin composition for a color filter of the present invention, when the coloring material represented by the general formula (1) is dissolved and used, the solubility of the coloring material at 23 ° C. is 2.0 (g / g / g /. A solvent (100 g solvent) or more is preferably used. The coloring material represented by the general formula (1) used in the present invention can be dissolved in a lower polar solvent than the conventional one as described above. Further, the coloring material represented by the general formula (1) has a higher solubility in the solvent used for dissolving the conventional xanthene dye than the conventional xanthene dye, so that the amount of the solvent used is high. Workability is improved, such as reducing the amount of

In the colored resin composition for a color filter according to the present invention, the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. It is usually preferably in the range of 55% by mass to 95% by mass, and above all, in the range of 65% by mass to 88% by mass with respect to the total amount of the colored resin composition for a color filter containing the solvent. Is more preferable. When the content of the solvent is within the above range, the coatability can be made excellent.

In addition, the colored resin composition for a color filter according to the present invention may contain a dispersant and other optional additive components, if necessary. The colored resin composition for a color filter according to the present invention may be prepared by dissolving the coloring material in the solvent, or may be used together with a dispersant described later.

<Dispersant>
As the dispersant, a known dispersant can be appropriately selected and used. For example, a cationic, anionic, nonionic, amphoteric, silicone-based, or fluorine-based surfactant can be used. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable because it can be dispersed uniformly and finely.

Examples of the polymer dispersant include polymer dispersants such as modified polyurethane, modified polyacrylate, modified polyester, and modified polyamide. Specifically, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (partial) amine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid, (partial) ammonium. Salts and (partial) alkylamine salts; (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters having an amino group, (partial) acid modified products of the amino group of the polymer; hydroxyl group-containing polyacrylic acid (Co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as esters and their modifications; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; poly (lower alkyleneimine) and free Examples thereof include amides obtained by reaction with carboxy group-containing polyesters and salts thereof.

Further, as the dispersant used in the present invention, a dispersant having an amine value is preferable from the viewpoint that the coloring material can be preferably dispersed and the dispersion stability is good, and in particular, a dispersant having an amine value of 5 mgKOH / g or more and 200 mgKOH is preferable. It is preferably less than / g, and more preferably 40 mgKOH / g or more and 120 mgKOH / g or less. In the present invention, the amine value represents the mass (mg) of potassium hydroxide (KOH) equivalent to the amount of hydrochloric acid required to neutralize 1 g of solid content, and is measured by the method described in JIS K7237. be able to.

As the dispersant having an amine value, a polymer dispersant is preferable, a polymer dispersant containing a nitrogen atom in the main chain or a side chain is more preferable, and a polymer dispersant having an amine or an ammonium salt is further preferable. When a polymer dispersant having an amine or ammonium salt is used, the amine or ammonium salt is preferably present at the side chain or the resin terminal.
Examples of the polymer dispersant having an amine or ammonium salt include (partial) amine salts, (partial) ammonium salts and (partial) alkylamine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid; Examples thereof include polyurethanes; unsaturated polyamides; polyethyleneimine derivatives; polyallylamine derivatives and the like.

Commercially available products used as dispersants in the present invention include, for example, EFKA-4046, EFKA-4047, EFKA polymer 10, EFKA polymer 400, EFKA polymer 401, EFKA polymer 4300, EFKA polymer 4310, EFKA polymer 4320, EFKA polymer. 4330 (above, manufactured by BASF Japan Ltd.), Disperbyk111, Disperbyk161, Disperbyk165, Disperbyk167, Disperbyk182, Disperbyk2000, Disperbyk2001, Disperbyk2001, BYK-LPN6919, BYK-LPN6919, BYK-LPN6919 (The above is manufactured by Lubrizol), Azisper (registered trademark) PB821, PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like.

Further, as the dispersant used to disperse the coloring material represented by the general formula (1), a polymer dispersant composed of a polymer containing a repeating unit having a tertiary amine has good dispersibility. It is preferable because it is possible to realize excellent brightness, suppress the generation of foreign substances when forming the colored layer, have excellent resolubility in a solvent, and can form a colored layer having excellent heat resistance.

(Polymer containing a repeating unit having a tertiary amine)
The repeating unit having a tertiary amine is a site having an affinity with the coloring material represented by the general formula (1). In particular, the tertiary amine of the repeating unit and the ^{5 groups of −L 1} −N ⁻ −L ² −R of the coloring material are stabilized by acid-base interaction. A polymer dispersant consisting of a polymer containing a repeating unit having a tertiary amine usually contains a repeating unit that serves as a site having an affinity for a solvent.
Examples of the polymer containing a repeating unit having a tertiary amine include (a) a block copolymer having a block portion composed of a repeating unit having a tertiary amine and a block portion having a solvent affinity, and (b) 3 A graft copolymer containing a repeating unit having a secondary amine and a repeating unit having a polymer chain having solvent affinity is preferably used. In the graft copolymer, the repeating unit having a tertiary amine may be contained in the polymer chain corresponding to the branch portion, and has a solvent affinity with the repeating unit having a polymer chain containing the repeating unit having a tertiary amine. It may be a graft copolymer containing a repeating unit having a polymer chain having.

The repeating unit having a tertiary amine may have a tertiary amine, and the tertiary amine may be contained in the side chain of the block polymer or may form a main chain.
Above all, it is preferable that it is a repeating unit having a tertiary amine in the side chain, and above all, it has a structure represented by the following general formula (I) because the main chain skeleton is hard to be thermally decomposed and has high heat resistance. However, it is more preferable.

（一般式（Ｉ）中、Ｒ^１１は、水素原子又はメチル基、Ｑは、直接結合又は２価の連結基、Ｒ^１２は、炭素数１〜８のアルキレン基、−［ＣＨ（Ｒ^１５）−ＣＨ（Ｒ^１６）−Ｏ］_ｘ−ＣＨ（Ｒ^１５）−ＣＨ（Ｒ^１６）−又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−（ＣＨ_２）_ｙ−で示される２価の有機基、Ｒ^１３及びＲ^１４は、それぞれ独立に、置換されていてもよい鎖状又は環状の炭化水素基を表すか、Ｒ^１３及びＲ^１４が互いに結合して環状構造を形成する。Ｒ^１５及びＲ^１６は、それぞれ独立に水素原子又はメチル基である。
ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。）

(In the general formula (I), R ¹¹ is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, R ¹² is an alkylene group having 1 to 8 carbon atoms, and-[CH (R ¹⁵ )). −CH (R ¹⁶ ) −O] _x −CH (R ¹⁵ ) −CH (R ¹⁶ ) − or − [(CH ₂ ) _y −O] _z − (CH ₂ ) _y − , ^{R 13} and ^{R 14} each independently represent a optionally substituted linear or cyclic hydrocarbon ^{group, R 13} and ^{R 14} form a ring structure by bonding with each other ^{.R 15} and R ¹⁶ is an independent hydrogen atom or methyl group, respectively.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

Examples of the divalent linking group Q of the general formula (I) include an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, an -COO- group, and an ether group having 1 to 10 carbon atoms (-. R'-OR "-: R'and R" are independently alkylene groups) and combinations thereof. Among them, Q is a -COO- group or -CONH- because of the heat resistance of the obtained polymer, the solubility in propylene glycol monomethyl ether acetate (PGMEA) preferably used as a solvent, and the relatively inexpensive material. It is preferably a group.

The divalent organic group R ¹² of the general formula (I) is an alkylene group having 1 to 8 carbon atoms, − [CH (R ¹⁵ ) −CH (R ¹⁶ ) −O] _x −CH (R ¹⁵ ) −CH. (R ¹⁶ )-or-[(CH ₂ ) _y- O] _z- (CH ₂ ) _y- . The alkylene group having 1 to 8 carbon atoms may be linear or branched, and is, for example, a methylene group, an ethylene group, a propylene group, various butylene groups, various hexylene groups and the like.
R ¹⁵ and R ¹⁶ are independently hydrogen atoms or methyl groups, respectively.
The R ¹² is preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility, and more preferably R ¹² is a methylene group, an ethylene group, a propylene group or a butylene group, and the methylene group and ethylene. Groups are more preferred.

Examples of the optionally substituted chain or cyclic hydrocarbon group in R ¹³ and R ¹⁴ include an alkyl group, an aralkyl group, an aryl group and the like.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group and the like. 1 to 18 are preferable, and among them, a methyl group or an ethyl group is more preferable.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The number of carbon atoms of the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xsilyl group and the like. The number of carbon atoms of the aryl group is preferably 6 to 24, more preferably 6 to 12. The preferable number of carbon atoms does not include the number of carbon atoms of the substituent.
Further, the hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom and a bromine atom.

^{Examples of the cyclic structure formed by bonding R 13} and R ¹⁴ of the general formula (I) to each other include a nitrogen-containing heterocyclic monocycle having a 5- to 7-membered ring or a fused ring formed by condensing two of them. Be done. The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a saturated ring.

Examples of the repeating unit represented by the general formula (I) include alkyl group-substituted aminos such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. Examples thereof include group-containing (meth) acrylates, alkyl group-substituted amino group-containing (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide. Of these, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.

In the block portion composed of the repeating unit having the tertiary amine, it is preferable that three or more structural units represented by the general formula (I) are contained. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is preferable to contain 3 to 100 pieces, more preferably 3 to 50 pieces, and further preferably 3 to 30 pieces.

Both a block portion composed of a repeating unit having a tertiary amine (hereinafter, may be referred to as A block) and a block portion having a solvent affinity (hereinafter, may be referred to as B block). The block portion having solvent affinity in the polymer does not have the structural unit represented by the general formula (I) from the viewpoint of improving solvent affinity and improving dispersibility, and the general formula ( It has a solvent-affinity block portion having a structural unit copolymerizable with I). In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, or the like can be used. Of these, AB block copolymers or ABA block copolymers are preferable because they are excellent in dispersibility.
The structural unit that can be copolymerized with the general formula (I) is a structural unit represented by the following general formula (II) from the viewpoint of improving the dispersibility and dispersion stability of the coloring material while also improving the heat resistance. Is preferable.

（一般式（ＩＩ）中、Ｒ^１７は、水素原子又はメチル基、Ａは、直接結合又は２価の連結基、Ｒ^１８は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^１９）−ＣＨ（Ｒ^２０）−Ｏ］_ｘ−Ｒ^２１又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^２１で示される１価の基である。Ｒ^１９及びＲ^２０は、それぞれ独立に水素原子又はメチル基であり、Ｒ^２１は、水素原子、あるいは炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、又は−ＣＨ_２ＣＯＯＲ^２２で示される１価の基であり、Ｒ^２２は水素原子又は炭素数１〜５の直鎖状、分岐状、又は環状のアルキル基である。ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。）

(In the general formula (II), R ¹⁷ is a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, R ¹⁸ is an alkyl group having 1 to 18 carbon atoms, and an alkenyl having 2 to 18 carbon atoms. Group, aralkyl group, aryl group, monovalent group represented by-[CH (R ¹⁹ ) -CH (R ²⁰ ) -O] _x- R ²¹ or-[(CH ₂ ) _y- O] _z- R ^21. R ¹⁹ and R ²⁰ are independent hydrogen atoms or methyl groups, respectively, and R ²¹ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, and the like. It is a monovalent group represented by an aryl group, -CHO, -CH ₂ CHO, or -CH ₂ COOR ²² , where R ²² is a hydrogen atom or a linear, branched, or cyclic alkyl having 1 to 5 carbon atoms. Group. X is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18.)

The divalent linking group A of the general formula (II) can be the same as Q in the general formula (I), and the heat resistance of the obtained polymer and propylene glycol preferably used as a solvent can be used. A is preferably a -COO- group because of its solubility in monomethyl ether acetate (PGMEA) and its relatively inexpensive material.

In R ^18, the alkyl group having 1 to 18 carbon atoms, linear, branched, or cyclic, e.g., methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl Group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, cyclopentyl groups, Examples thereof include a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, and a lower alkyl group-substituted adamantyl group.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic.
^{Of these, R 18} is preferably a methyl group, various butyl groups, various hexyl groups, a benzyl group, a cyclohexyl group, and a hydroxyethyl group from the viewpoint of dispersibility and substrate adhesion.

Examples of the aryl group which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xsilyl group and the like. The aryl group preferably has 6 to 24 carbon atoms, and more preferably 6 to 12 carbon atoms.
Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The carbon number of the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.
Examples of the substituent of the aromatic ring such as the aryl group and the aralkyl group include a linear and branched alkyl groups having 1 to 4 carbon atoms, an alkenyl group, a nitro group, a halogen atom and the like.

Further, in the ^{monovalent group represented by R 21} , examples of the substituent which may be possessed include, for example, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, F, Cl, Br and the like. Halogen atoms and the like can be mentioned.
The alkyl group having 1 to 18 carbon atoms and the alkenyl group, aralkyl group and aryl group having 2 to 18 carbon atoms in ^{R 21} may be the same as those in ^{R 18.}
In R ¹⁸ , x, y and z are the same as ^{R 12 in the general formula (I).}

The number of the structural units constituting the solvent-affinity block portion may be appropriately adjusted within the range in which the color material dispersibility is improved. Above all, the number of structural units constituting the solvent-affinity block portion is 10 or more and 200 or less from the viewpoint that the solvent-affinity part and the color material-affinity part act effectively to improve the dispersibility of the color material. It is preferably 10 or more and 100 or less, and further preferably 10 or more and 70 or less.

The solvent-affinity block portion may be selected so as to function as a solvent-affinity site, and the repeating unit constituting the solvent-affinity block portion may consist of one type or two or more types. May include repeating units of.
In the block copolymer used as the dispersant of the present invention, the ratio of the number of units m of the structural unit represented by the general formula (I) to the number n of the other structural units constituting the solvent-friendly block portion. The m / n is preferably in the range of 0.01 or more and 1 or less, and is in the range of 0.05 or more and 0.7 or less from the viewpoint of dispersibility and dispersion stability of the coloring material. preferable.

Further, among them, in the present invention, the dispersant is a polymer containing the structure represented by the general formula (I) and having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less, which has good dispersibility at the time of forming a coating film. It is preferable because it does not deposit foreign matter and improves brightness and contrast.
When the amine value is within the above range, the viscosity is excellent in stability over time and heat resistance, and also in alkali developability and solvent resolubility. In the present invention, the amine value of the dispersant is preferably 80 mgKOH / g or more, more preferably 90 mgKOH / g or more, from the viewpoint of dispersibility and dispersion stability. On the other hand, from the viewpoint of solvent resolubility, the amine value of the dispersant is preferably 110 mgKOH / g or less, and more preferably 105 mgKOH / g or less.
The amine value refers to the number of mg of perchloric acid and equivalent potassium hydroxide required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if the amino group is salt-formed with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so that the block copolymer itself used as the dispersant itself. The amine value of can be measured.

The acid value of the dispersant used in the present invention is preferably 1 mgKOH / g or more as a lower limit from the viewpoint of suppressing the development residue. Above all, the acid value of the dispersant is more preferably 2 mgKOH / g or more because the effect of suppressing the development residue is more excellent. Further, the acid value of the dispersant used in the present invention is 18 mgKOH / g or less as the upper limit of the acid value of the dispersant from the viewpoint of preventing deterioration of development adhesion and solvent resolubility. preferable. Above all, the acid value of the dispersant is more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less, from the viewpoint of improving development adhesion and solvent resolubility.
The dispersant used in the present invention is a block copolymer containing an A block containing a structural unit represented by the general formula (I) and a B block containing a structural unit derived from a carboxy group-containing monomer. The acid value of the block copolymer before salt formation is preferably 1 mgKOH / g or more, and more preferably 2 mgKOH / g or more. This is because the effect of suppressing the development residue is improved. The upper limit of the acid value of the block copolymer before salt formation is preferably 18 mgKOH / g or less, more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less. .. This is because the development adhesion and the solvent resolubility are improved.

When the concentration of the coloring material is increased and the content of the dispersant is increased, the amount of the binder is relatively reduced, so that the colored resin layer is easily peeled off from the underlying substrate during development. When the dispersant contains a B block containing a structural unit derived from a carboxy group-containing monomer and has the specific acid value, the development adhesion is improved. If the acid value is too high, the developability is excellent, but it is presumed that the polarity is too high and peeling is likely to occur during development.

From the above, in the present invention, the dispersant is a polymer containing the structure represented by the general formula (I) and having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less, and has an acid value. When 1 mgKOH / g or more and 18 mgKOH / g or less and the glass transition temperature is 30 ° C. or more, the color material dispersion stability is excellent, the contrast is improved, and the generation of development residue is suppressed when the colored resin composition is prepared. However, it is preferable because it has excellent solvent resolubility and high development adhesion.

As the carboxy group-containing monomer, a monomer that can be copolymerized with a monomer that induces a structural unit represented by the general formula (I) and that contains an unsaturated double bond and a carboxy group can be used. Examples of such a monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, acrylic acid dimer and the like. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic acid anhydride, ω-carboxy-polycaprolactone. Mono (meth) acrylate and the like can also be used. Further, an acid anhydride group-containing monomer such as maleic anhydride or itaconic anhydride may be used as a precursor of the carboxy group. Of these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

In the block copolymer before salt formation, the content ratio of the structural unit derived from the carboxy group-containing monomer may be appropriately set so that the acid value of the block copolymer is within the above-mentioned specific acid value range, and in particular. Although not limited, it is preferably 0.05% by mass or more and 4.5% by mass or less, and 0.07% by mass or more and 3.7% by mass or less, based on the total mass of all the constituent units of the block copolymer. More preferably.
When the content ratio of the structural unit derived from the carboxy group-containing monomer is at least the above lower limit value, the effect of suppressing the development residue is exhibited, and when it is at least the above upper limit value, the development adhesion is deteriorated and the solvent resolubility is deteriorated. Deterioration can be prevented.
The structural unit derived from the carboxy group-containing monomer may have the above-mentioned specific acid value, may consist of one type, or may contain two or more types of structural units.

In the block copolymer, the ratio m / n of the number of units m of the constituent units of the A block and the number of units n of the constituent units of the B block is within the range of 0.05 or more and 1.5 or less. It is preferable, and it is more preferable that it is in the range of 0.1 or more and 1.0 or less from the viewpoint of dispersibility and dispersion stability of the coloring material.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 or more and 20000 or less, and is 2000 or more and 15000 or less, from the viewpoint of improving the dispersibility and dispersion stability of the coloring material. More preferably, it is more preferably 3000 or more and 12000 or less.
Here, the weight average molecular weight (Mw) is determined as a standard polystyrene-equivalent value by gel permeation chromatography (GPC). The macromonomer, salt-type block copolymer, and graft copolymer, which are the raw materials for the block copolymer, are also subjected to the above conditions.

The method for producing the block copolymer is not particularly limited. The block copolymer can be produced by a known method, but it is particularly preferable to produce the block copolymer by the living polymerization method.

As a specific example of a block copolymer having such a block portion composed of a repeating unit having a tertiary amine and a block portion having a solvent affinity, for example, the block copolymer described in Japanese Patent No. 4911253 can be used. It can be mentioned as a suitable one.

In the present invention, from the viewpoint of dispersibility and dispersion stability of the coloring material, at least a part of the amino groups in the polymer containing the repeating unit having the tertiary amine, an organic acid compound and a halogenated hydrocarbon are used. It is also preferable to use a polymer in which a salt is formed as a dispersant (hereinafter, such a polymer may be referred to as a salt-type polymer).
Among them, the dispersibility of the coloring material is that the polymer containing the repeating unit having a tertiary amine is a block copolymer and the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid. It is preferable from the viewpoint of excellent dispersion stability. Specific examples of the organic acid compound used in such a dispersant include the organic acid compounds described in JP-A-2012-236882.
The halogenated hydrocarbon is preferably at least one of allyl halides such as allyl bromide and benzyl chloride and aralkyl halides from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

The dispersant may be used alone or in combination of two or more. Further, when preparing the color material dispersion liquid by using different dispersants for each color material, different dispersants may be used.
The content when the dispersant is used is not particularly limited as long as the coloring material can be uniformly dispersed, but for example, with respect to the total solid content of the colored resin composition for a color filter. It can be used in an amount of 1% by mass to 40% by mass. Further, it is preferably blended in an amount of 2% by mass to 30% by mass, and particularly preferably in a proportion of 3% by mass to 25% by mass. When it is at least the above lower limit value, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the colored resin composition for a color filter is excellent. Further, when it is not more than the above upper limit value, the developability is good. In particular, when forming a colored layer having a high colorant concentration, the content of the dispersant is 2% by mass to 25% by mass, more preferably 3% by mass, based on the total solid content of the colored resin composition for a color filter. It is preferable to mix in a ratio of% to 20% by mass.

<Mercapto compound>
It is preferable that the colored resin composition for a color filter of the present invention further contains a mercapto compound from the viewpoint of improving the effect of suppressing the occurrence of water stains.
Further, when the colored resin composition for a color filter of the present invention is contained as a photosensitive colored resin composition in combination with the oxime ester-based photoinitiator and a mercapto compound, the residual film ratio is improved, and water stains. It is preferable from the viewpoint that the generation suppression effect is further improved, the linearity is further improved when the fine line pattern is formed, and the ability to form the fine line pattern as designed for the mask line width is improved. In addition, "improved linearity" means that the unevenness of the end portion of the colored layer formed in the developing step after applying the coloring composition is small, and the colored layer is formed linearly or substantially linearly.

The mercapto compound can function as a chain transfer agent, and has the property of receiving radicals from slow-reacting radicals to accelerate the reaction and improve curability. As described above, when the coloring material represented by the general formula (1) used in the present invention which exhibits purple color is used, insufficient curing is likely to occur. Therefore, the curability of the coating film by combining with the mercapto compound It is effective in improving.
Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzoimidazole, and 3-mercaptopropionic acid. , Methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis (3-mercaptobutylyloxy) butane, 1,3,5-tris (3-mercaptobutyloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), Examples thereof include pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate).
The mercapto compound may be used alone or in combination of two or more, and among them, one or more selected from the group consisting of polyfunctional mercapto compounds having two or more mercapto groups in one molecule may be used. This is preferable because the crosslink density is high and the effect of suppressing water stains is improved.
Further, a secondary mercapto compound having a secondary mercapto group in which the carbon atom to which the mercapto group is bonded is a secondary carbon atom is preferable because a good water stain suppressing effect can be easily maintained even when stored for a long period of time. Further, it is more preferable that the polyfunctional secondary mercapto compound has two or more secondary mercapto groups in one molecule.

The content of the mercapto compound used in the colored resin composition for a color filter is not particularly limited, but the mercapto compound is 0.2% by mass to 7% by mass with respect to the total solid content of the colored resin composition for a color filter. %, Further, it is preferably in the range of 0.5% by mass to 5% by mass from the viewpoint of sufficiently exerting the above-mentioned effect.

<Arbitrary additive component>
The colored resin composition for a color filter of the present invention may contain various additives as long as the object of the present invention is not impaired.
Examples of the additive include an antioxidant, a polymerization inhibitor, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, a defoaming agent, a silane coupling agent, an ultraviolet absorber, an adhesion accelerator and the like. ..

It is preferable that the colored resin composition for a color filter of the present invention further contains an antioxidant from the viewpoints of improving heat resistance, suppressing fading of the coloring material, and improving brightness. The antioxidant may be appropriately selected from conventionally known ones. Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like, and have heat resistance. From this point of view, it is preferable to use a hindered phenolic antioxidant. It may be a latent antioxidant as described in WO 2014/021023.

Examples of the hindered phenol-based antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF). 1,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris (4-hydroxy-3) , 5-Di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilyzer MDP-S, Sumitomo Chemical Co., Ltd.), 6,6'-thiobis (2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3,5-di-tert-butyl-4-hydroxybenzylphosphone Benzyl acid acid (trade name: Irgamod 195, manufactured by BASF) and the like can be mentioned. Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. ..

When the colored resin composition for a color filter of the present invention is contained as a photosensitive colored resin composition in combination with the oxime ester-based photoinitiator and an antioxidant, the brightness is improved by a synergistic effect, and the residual film. It is preferable from the viewpoint of improving the rate, improving the linearity when forming the fine line pattern, and improving the ability to form the fine line pattern according to the design of the mask line width.

The amount of the antioxidant to be blended is preferably 0.1 part by mass to 10.0 parts by mass, and 0.5 part by mass, based on 100 parts by mass of the total solid content in the colored resin composition. More preferably, it is from 10 parts to 5.0 parts by mass. If it is at least the above lower limit value, it is excellent in heat resistance and light resistance. On the other hand, if it is not more than the above upper limit value, the colored resin composition of the present invention can be a highly sensitive photosensitive resin composition.

When the antioxidant is used in combination with the oxime ester-based photoinitiator, the amount of the antioxidant is 1 part by mass with respect to 100 parts by mass of the total amount of the oxime ester-based photoinitiator. It is preferably ~ 250 parts by mass, more preferably 3 parts by mass to 80 parts by mass, and even more preferably 5 parts by mass to 45 parts by mass. If it is within the above range, the effect of the above combination is excellent.

<Manufacturing method of colored resin composition for color filter>
The method for producing a colored resin composition for a color filter according to the present invention is a method capable of uniformly dissolving or dispersing the above-mentioned coloring material, a binder component, and various additive components used as desired in a solvent. It is well, without particular limitation, and can be prepared by mixing using a known mixing means.

As a method for preparing a colored resin composition for a color filter according to the present invention, for example, (i) various coloring materials used for coloring materials are separately dispersed together with a dispersant in a solvent, or without using a dispersant. By dissolving, a color material dispersion liquid or a color material solution is prepared, while a binder resin composition in which a binder component is added to another solvent is prepared, and the color material dispersion liquid and / or the color material is prepared. A method of mixing the solution, the binder resin composition, and various additive components used as desired, (ii) various coloring materials used for the coloring material are simultaneously co-dispersed or dispersed together with a dispersant in the solvent. A color material dispersion or a color material solution is prepared by simultaneously dissolving without using an agent, while a binder resin composition in which a binder component is added to another solvent is prepared to prepare the color material dispersion. Alternatively, a method of mixing the coloring material solution, the binder resin composition, and various additive components used as desired, (iii) in the solvent, the coloring material, the binder component, and various additive components used as desired. Examples include a method of adding and mixing at the same time, and a method of adding a binder component and various additive components used as desired to the (iv) solvent, mixing them, and then adding a coloring material to the mixture. Can be done.
Among these methods, when the coloring material is dispersed in the solvent, the method (i) or (ii) is preferable from the viewpoint that the agglomeration of the coloring material can be effectively prevented and the coloring material can be uniformly dispersed.

In the production of the colored resin composition for a color filter according to the present invention, the disperser for performing the dispersion treatment is not particularly limited, but for example, a roll mill such as a three-roll mill, a ball mill, a ball mill such as a vibrating ball mill, or a paint shaker. , A bead mill such as a continuous disc type bead mill and a continuous general type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter used is preferably 0.03 mm to 2 mm, more preferably 0.05 mm to 1 mm. Specifically, pre-dispersion may be performed with 1 mm to 2 mm zirconia beads having a relatively large bead diameter, and then main dispersion may be performed with 0.03 mm to 0.1 mm zirconia beads having a relatively small bead diameter. Further, from the viewpoint of dispersibility, it is preferable to filter with a membrane filter of about 5.0 μm to 0.2 μm after dispersion.

2. Color Material Dispersion Liquid The color material dispersion liquid according to the present invention is characterized in that the color material represented by the general formula (1) is dispersed in a solvent by a dispersant having an amine value.
The color material represented by the general formula (1) and the dispersant having an amine value used in the color material dispersion liquid according to the present invention are described in the above-mentioned colored resin composition for a color filter of the present invention. The same thing as the one can be used.

In the color material dispersion liquid of the present invention, the color material affinity portion of the dispersant surrounds the color material centering on the color material represented by the general formula (1), and the solvent affinity of the dispersant is outside the color material. It is presumed that the sex sites are arranged, that is, they form micelles of the coloring material and the dispersant. It is presumed that the amine moiety of the dispersant having an amine value and the ^{5 groups of −L 1} −N ⁻ −L ² −R of the coloring material cause acid-base interaction to stabilize. In this way, in the color material dispersion liquid of the present invention, the color material can be uniformly dispersed in the solvent as fine particles surrounded by the dispersant in a finely divided state. In this case, for example, even a solvent that does not dissolve the coloring material represented by the general formula (1) can be used in combination with the coloring material represented by the general formula (1). It is also possible to contain the coloring material in the solvent at a concentration higher than the solubility.
Further, if a color material dispersion liquid in which the color material is uniformly dispersed in a solvent is used as fine particles surrounded by a dispersant in a finely divided state, the generation of foreign substances in the case of a colored layer is likely to be suppressed. ..

In the color material dispersion liquid of the present invention, the content of the solvent with respect to the total amount of the color material dispersion liquid containing the solvent is usually 50% by mass to 95% by mass, preferably 60% by mass to 85% by mass. If the amount of solvent is too small, the viscosity tends to increase and the dispersibility tends to decrease. Further, if the amount of the solvent is too large, the concentration of the coloring material decreases, and it may be difficult to achieve the target chromaticity coordinates after preparing the resin composition.
The solvent may be used alone or in combination of two or more.

Further, the color material dispersion liquid of the present invention contains, if necessary, a color material other than the color material represented by the general formula (1), a dispersion auxiliary resin, and the like, as long as the effects of the present invention are not impaired. Ingredients may be blended.
The color material other than the color material represented by the general formula (1) is not particularly limited, and for example, the blue color material and other color materials used in the above-mentioned colored resin composition for a color filter of the present invention can be used. Can be mentioned.
Examples of the dispersion auxiliary resin include the alkali-soluble resin exemplified in the above-mentioned colored resin composition for a color filter of the present invention. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant particles to come into contact with each other, which may have the effect of stabilizing the dispersion and reducing the amount of the dispersant due to the effect of stabilizing the dispersion.
Other components include, for example, a surfactant for improving wettability, a silane coupling agent for improving adhesion, a defoaming agent, an anti-repellent agent, an antioxidant, an antioxidant, and an ultraviolet absorber. And so on.

The method for producing the color material dispersion liquid of the present invention is, for example, (i) mixing and stirring the dispersant with a solvent to prepare a dispersant solution, and then adding the dispersant solution to the dispersant solution in the general formula (1). Examples thereof include a method in which the coloring material to be used is mixed with other components as necessary and dispersed using a known stirrer or disperser.
Further, (ii) the dispersant is mixed and stirred with the coloring material represented by the general formula (1) as a solvent to prepare a dispersant solution, while the color represented by the general formula (1) is prepared. A color material solution in which the material is dissolved in a good solvent may be prepared, the dispersant solution and the color material solution may be mixed and stirred using a known stirrer or disperser.
As the disperser for performing the dispersion treatment used in the production of the color material dispersion liquid of the present invention, the same disperser as that used for preparing the colored resin composition for a color filter of the present invention described above is used. Can be mentioned.

The color material dispersion liquid according to the present invention can be used as a preliminary preparation for preparing the above-mentioned colored resin composition for a color filter according to the present invention, which has excellent color material dispersibility. That is, the color material dispersion liquid is pre-prepared (mass of the color material component in the composition) / (other than the color material component in the composition) in the step before preparing the above-mentioned color resin composition for the color filter. It is a colorant dispersion having a high solid content mass ratio. Specifically, the ratio (mass of color material component in composition) / (mass of solid content other than color material component in composition) is usually 1.0 or more. By mixing the color material dispersion liquid and at least the binder component, a colored resin composition having excellent dispersibility can be prepared.

3. 3. Color filter The color filter according to the present invention is a color filter including at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a colored resin for a color filter according to the present invention. It is characterized by having a colored layer which is a cured product of the composition.
The color filter according to the present invention has a colored layer formed by curing the colored resin composition for a color filter according to the present invention, and therefore has excellent brightness.

Such a color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a substrate 1, a light-shielding portion 2, and a colored layer 3.

<Colored layer>
At least one of the colored layers used in the color filter of the present invention is a cured product of the colored resin composition for a color filter according to the present invention.
The colored layer is usually formed in the opening of a light-shielding portion on a substrate, which will be described later, and is usually composed of a colored pattern of three or more colors.
The arrangement of the colored layers is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a 4-pixel arrangement type. Further, the width, area and the like of the colored layer can be arbitrarily set.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and the viscosity of the colored resin composition, etc., but is usually preferably in the range of 1 μm to 5 μm.

The colored layer can be formed by the following method, for example, when the colored resin composition for a color filter is a photosensitive resin composition.
First, the above-mentioned colored resin composition for a color filter of the present invention is applied onto a substrate described later by using a coating means such as a spray coating method, a dip coating method, a bar coating method, a call coating method, and a spin coating method. , Form a wet coating.
Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to the wet coating film through a mask having a predetermined pattern to cause a photopolymerization reaction of an alkali-soluble resin, a polyfunctional monomer, or the like. A coating film of a colored resin composition. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
In addition, heat treatment may be performed in order to accelerate the polymerization reaction after exposure. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition to be used, the thickness of the coating film, and the like.

Next, a coating film is formed in a desired pattern by developing with a developing solution to dissolve and remove the unexposed portion. As the developing solution, a solution in which an alkali is usually dissolved in water or a water-soluble solvent is used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. Moreover, a general method can be adopted as a developing method.
After the development treatment, the developer is usually washed and the cured coating film of the colored resin composition is dried to form a colored layer. After the development treatment, a heat treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited and are appropriately selected depending on the intended use of the coating film.

<Shading part>
The light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate described later, and can be the same as that used as a light-shielding portion in a general color filter.
The pattern shape of the light-shielding portion is not particularly limited, and examples thereof include a striped shape and a matrix shape. Examples of the light-shielding portion include a black pigment dispersed or dissolved in a binder resin, a metal thin film such as chromium and chromium oxide, and the like. This metal thin film may be a CrOx film (x is an arbitrary number) and a Cr film in which two layers are laminated, and a CrOx film (x is an arbitrary number) having a further reduced reflectance, CrNy. A film (y is an arbitrary number) and a Cr film may be laminated in three layers.
When the light-shielding portion is a black color material dispersed or dissolved in a binder resin, the method for forming the light-shielding portion is not particularly limited as long as the light-shielding portion can be patterned. For example, a photolithography method, a printing method, an inkjet method, etc. using a colored resin composition for a light-shielding portion can be mentioned.

In the above case, when the printing method or the inkjet method is used as the method for forming the light-shielding portion, the binder resin includes, for example, polymethylmethacrylate resin, polyacrylate resin, polycarbonate resin, melamine resin epoxy resin, polyurethane resin, and polyester. Examples thereof include resins and polyamide resins.

Further, in the above case, when the photolithography method is used as the method for forming the light-shielding portion, the binder resin is, for example, reactive with acrylate-based, methacrylate-based, polyvinyl chloride-based, or cyclized rubber-based. A photosensitive resin having a vinyl group is used. In this case, a photopolymerization initiator may be added to the colored resin composition for a light-shielding portion containing a black coloring material and a photosensitive resin, and if necessary, a sensitizer, a cross-linking agent, and a polymerization inhibitor may be added. , Etc. may be added.

On the other hand, when the light-shielding portion is a metal thin film, the method for forming the light-shielding portion may be any method capable of patterning the light-shielding portion, and is not particularly limited. For example, a photolithography method or vapor deposition using a mask. Law, printing method, etc. can be mentioned.

The film thickness of the light-shielding portion is set to about 0.2 μm to 0.4 μm in the case of a metal thin film, and about 0.5 μm to 2 μm in the case of a black color material dispersed or dissolved in a binder resin. Set.

<Board>
As the substrate, a transparent substrate, a silicon substrate, which will be described later, and a transparent substrate or a silicon substrate on which an aluminum, silver, silver / copper / palladium alloy thin film, or the like is formed are used. Another color filter layer, a resin layer, a transistor such as a TFT, a circuit, or the like may be formed on these substrates.
The transparent substrate in the color filter of the present invention may be a substrate that is transparent to visible light, and is not particularly limited, and a transparent substrate used in a general color filter can be used. Specifically, a transparent rigid material having no flexibility such as quartz glass, non-alkali glass, or synthetic quartz plate, or a transparent flexible material having flexibility such as a transparent resin film, an optical resin plate, or a flexible glass. The material is mentioned.
The thickness of the transparent substrate is not particularly limited, but one of about 100 μm to 1 mm can be used depending on the use of the color filter of the present invention.
In addition to the substrate, the light-shielding portion, and the colored layer, the color filter of the present invention may have, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like.

4. Liquid Crystal Display Device The liquid crystal display device of the present invention is characterized by having the color filter according to the present invention described above, an opposing substrate, and a liquid crystal layer formed between the color filter and the opposing substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention has a liquid crystal layer formed between a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and the color filter 10 and the counter substrate 20. It has 30 and.
The liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and can be generally known as a liquid crystal display device using a color filter.

The drive system of the liquid crystal display device of the present invention is not particularly limited, and a drive system generally used for the liquid crystal display device can be adopted. Examples of such a drive system include a TN system, an IPS system, an OCB system, an MVA system, and the like. In the present invention, any of these methods can be preferably used.
Further, as the facing substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention and the like.
Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and a mixture thereof can be used depending on the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.

5. Organic light emitting display device The organic light emitting display device according to the present invention is characterized by having the above-mentioned color filter according to the present invention and an organic light emitting body.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view showing an example of the organic light emitting display device of the present invention. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method of laminating the organic light emitting body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which the organic light emitting body 80 formed on another substrate is bonded onto the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations of the organic light emitter 80, known ones can be appropriately used. The organic light emitting display device 100 produced in this manner can be applied to, for example, both a passive drive type organic EL display and an active drive type organic EL display.
The organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and can be generally known as an organic light emitting display device using a color filter.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.

(Synthesis Example 1: Synthesis of Color Material A)
Intermediate I-1 represented by the following structural formula was synthesized by the following procedure.
18.0 parts by mass of the sulfofluorane compound of the following chemical formula (3), 312 parts by mass of methanol, and 10.8 parts by mass of 2,6-xylidine were charged in a 500 ml four-necked flask and refluxed for 30 hours. This reaction solution was filtered at 60 ° C. to remove insoluble matter, and then the solvent was removed under reduced pressure until the reaction solution became about 70 ml, and the mixture was poured into 200 parts by mass of 6% hydrochloric acid. Then, 600 parts by mass of water was added, and the mixture was stirred at room temperature for 30 minutes, and then the wet cake was collected by filtration. This wet cake is suspended in 100 parts by mass of water, stirred at 60 ° C. for 2 hours, collected again, washed with hot water at 60 ° C., and dried. .5 parts by mass was obtained.

Next, a mixture of 20 parts by mass of Intermediate I-1, 135.3 parts by mass of 1-methyl-2-pyrrolidinone, 7.8 parts by mass of potassium carbonate and 17.4 parts by mass of ethyl iodide was stirred at 80 ° C. for 2 hours. Did. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and then the reaction solution was added dropwise to 541.2 parts by mass of 17.5% hydrochloric acid at 0 to 10 ° C., and the mixture was stirred for 1 hour. Then, the precipitate was collected by filtration, and the residue was dried at 60 ° C. for 24 hours to obtain 20.4 parts by mass of crystals.
20 parts by mass of the obtained crystals and 106 parts by mass of phosphorus oxychloride were placed in a flask and stirred at 60 ° C. for 2 hours. The obtained reaction solution was allowed to cool to room temperature, the reaction solution was added dropwise to 1500 parts by mass of ice water, and the mixture was stirred for 30 minutes. The obtained crystals were separated by filtration, washed with 200 parts by mass of water, and dried for 10 hours. 7 parts by mass of the crystal and 1.7 parts by mass of trifluoromethylsulfonamide were dissolved in 40 parts by mass of chloroform, 1.55 parts by mass of triethylamine was added dropwise, and the mixture was stirred at room temperature for 1 hour. Then, 100 parts by mass of water was added to the obtained reaction solution and washed with water, and then the organic layer was separated. The organic layer was dried over sodium sulfate, purified, and concentrated under reduced pressure to obtain 7.2 parts by mass of a coloring material A having the following chemical formula. (Yield 80%)

(Synthesis example 2: Synthesis of color material B)
In Synthesis Example 1, 7.4 parts by mass of the coloring material B having the following chemical formula was used in the same manner as in Synthesis Example 1 except that 17.4 parts by mass of ethyl iodide was changed to 18.9 parts by mass of n-propyl iodide. Obtained.

(Synthesis Example 3: Synthesis of Color Material C)
In Synthesis Example 1, 7.7 parts by mass of the coloring material C having the following chemical formula was used in the same manner as in Synthesis Example 1 except that 17.4 parts by mass of ethyl iodide was changed to 20.5 parts by mass of n-butyl iodide. Obtained.

(Synthesis Example 4: Synthesis of Color Material D)
In Synthesis Example 1, 7.9 parts by mass of the coloring material D having the following chemical formula was obtained in the same manner as in Synthesis Example 1 except that 17.4 parts by mass of ethyl iodide was changed to 23.4 parts by mass of cyclohexyl iodide. ..

(Synthesis Example 5: Synthesis of Color Material E)
First, Intermediate I-2 represented by the following structural formula was synthesized by the following procedure.
Intermediate of Synthesis Example 1 except that 10.8 parts by mass of 2,6-xylidine was replaced with 6.0 parts by mass of 2,6-diisopropylaniline in the step of synthesizing Intermediate I-1 of Synthesis Example 1. In the same manner as I-1, 26.8 parts by mass of intermediate I-2 having the following chemical formula was obtained.

Next, in Synthesis Example 1, 20 parts by mass of Intermediate I-1 was changed to 20 parts by mass of Intermediate I-2, and 17.4 parts by mass of ethyl iodide was changed to 14.6 parts by mass of ethyl iodide. A 6.8 parts by mass of a coloring material E having the following chemical formula was obtained in the same manner as in Synthesis Example 1 except for the above.

(Comparative Synthesis Example 1: Synthesis of Comparative Color Material F)
20 parts by mass of Intermediate I-1 and 106 parts by mass of phosphorus oxychloride were placed in a flask and stirred at 60 ° C. for 2 hours. The obtained reaction solution was allowed to cool to room temperature, the reaction solution was added dropwise to 1500 parts by mass of ice water, and the mixture was stirred for 30 minutes. The obtained crystals were separated by filtration, washed with 200 parts by mass of water, and dried for 10 hours. 7 parts by mass of the crystal and 1.7 parts by mass of trifluoromethylsulfonamide were dissolved in 40 parts by mass of chloroform, 1.55 parts by mass of triethylamine was added dropwise, and the mixture was stirred at room temperature for 1 hour. Then, 100 parts by mass of water was added to the obtained reaction solution and washed with water, and then the organic layer was separated. The organic layer was dried over sodium sulfate, purified, and concentrated under reduced pressure to obtain 7.5 parts by mass of a comparative color material F having the following chemical formula. (Yield 80%)

(Comparative Synthesis Example 2: Synthesis of Comparative Color Material G)
First, Intermediate I-3 represented by the following structural formula was synthesized by the following procedure.
In the step of synthesizing the intermediate I-1 of Synthesis Example 1, 5.4 parts by mass of 2,6-xylidine and 4.8 parts by mass of o-toluidine were used instead of 10.8 parts by mass of 2,6-xylidine. 21.9 parts by mass of Intermediate I-3 having the following chemical formula was obtained in the same manner as in Intermediate I-1 of Synthesis Example 1.

Next, a mixture of 20 parts by mass of the intermediate I-3, 135.3 parts by mass of 1-methyl-2-pyrrolidinone, 7.8 parts by mass of potassium carbonate and 16.2 parts by mass of methyl iodide was mixed at 80 ° C. for 2 hours. , Stirred. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and then the reaction solution was added dropwise to 541.2 parts by mass of 17.5% hydrochloric acid at 0 to 10 ° C., and the mixture was stirred for 1 hour. Then, the precipitate was collected by filtration and the residue was dried at 60 ° C. for 24 hours to obtain 16.7 parts by mass of the comparative coloring material G having the following chemical formula (yield 80%).

(Comparative Synthesis Example 3: Synthesis of Comparative Color Material H)
First, Intermediate I-4 represented by the following structural formula was synthesized by the following procedure.
6. In the step of synthesizing the intermediate I-1 of Synthesis Example 1, instead of 10.8 parts by mass of 2,6-xylidine, 5.4 parts by mass of 2,6-xylidine and 2-methyl-6-ethylaniline. An intermediate I-4 23.0 parts by mass having the following chemical formula was obtained in the same manner as the intermediate I-1 of Synthesis Example 1 except that 0 parts by mass was used.

Next, a mixture of 20 parts by mass of the intermediate I-4, 135.3 parts by mass of 1-methyl-2-pyrrolidinone, 7.8 parts by mass of potassium carbonate and 16.2 parts by mass of methyl iodide was added at 80 ° C. for 2 hours. , Stirred. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and then the reaction solution was added dropwise to 541.2 parts by mass of 17.5% hydrochloric acid at 0 to 10 ° C., and the mixture was stirred for 1 hour. Then, the precipitate was collected by filtration and the residue was dried at 60 ° C. for 24 hours to obtain 16.6 parts by mass of the comparative coloring material H having the following chemical formula (yield 80%).

<Evaluation: Solubility in solvent>
The solubility of the synthesized color materials A to E and the comparative color materials F to H in the following solvents was evaluated by the following procedure.
0.2 g of each coloring material was put into a 20 mL sample tube bottle, then 10 g of each solvent was weighed and put into a bottle, and after sealing, the mixture was treated with ultrasonic waves for 3 minutes. The obtained liquid was stored in a water bath at 23 ° C. for 60 minutes, and then visually confirmed. The results are shown in Table 1.
Solvent 1: Propylene glycol monomethyl ether acetate solvent 2: Propylene glycol monomethyl ether solvent 3: 3-methoxy-3-methyl-1-butyl acetate solvent 4: Diethylene glycol ethyl methyl ether solvent 5: Ethyl 3-ethoxypropionate (evaluation criteria)
A: All dissolved B: Partially dissolved and precipitated C: Almost dissolved and precipitated

From the results in Table 1, the coloring materials A to E, which are the coloring materials represented by the general formula (1) used in the present invention, are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol ethyl methyl ether, respectively. It was also shown to be excellent in solvent solubility even in a low polar solvent having no alcoholic hydroxyl group, such as ethyl 3-ethoxypropionate.

(Preparation Example 1: Preparation of Photosensitive Binder Component (CR-1))
As an alkali-soluble resin, a methacrylate / methyl methacrylate / cyclohexyl methacrylate copolymer (molar ratio: 13.8 / 26.2 / 50.0, weight average molecular weight: 9000, acid value: 90 mgKOH / g, active ingredient content 40 Mass%) 40.0 parts by mass, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., "KAYARAD DPHA") 48.0 parts by mass as a polyfunctional monomer, 2-methyl-1- [4-] as a photoinitiator (Methylthio) phenyl] -2-morpholinopropan-1-one (BASF Japan, "IRGACURE907") 12.0 parts by mass, diethylthioxanthone (Nippon Kayakusha, "DETX-S") 4.0% by mass After adding 96.0 parts by mass of PGMEA as a part and a solvent, the mixture was mixed until uniform to obtain a photosensitive binder component (CR-1).

(Reference Example 1: Preparation of Colored Resin Composition)
A colorant solution was prepared by dissolving 0.85 parts by mass of the colorant A obtained in Synthesis Example 1 in 72.3 parts by mass of PGMEA, while the photosensitive binder component (CR-) obtained in Preparation Example 1 was prepared. 1) 26.6 parts by mass, 0.2 parts by mass of the silane coupling agent KBM-503 (manufactured by Shinetsu Silicone), and 0.02 parts by mass of the surfactant Megafuck F559 (manufactured by DIC) are mixed, and the above-mentioned color is further mixed. By mixing the material solutions, the colored resin composition of Reference Example 1 was obtained.

(Example 2, Examples 4 to 6, and Comparative Example 1: Preparation of colored resin composition)
In Reference Example 1, the colored resin compositions of Examples 2 and 4 to 6 and the comparison were carried out in the same manner as in Reference Example 1 except that the coloring material shown in Table 2 was used instead of the coloring material A. A comparative colored resin composition of Example 1 was obtained.

(Example 3: Preparation of colored resin composition)
(1) Preparation of Coloring Material Dispersion Solution 3.5 parts by mass of Coloring Material B obtained in Synthesis Example 2, 5.3 parts by mass of BYK-LPN21116 (40% by mass of non-volatile content manufactured by Big Chemie), PGMEA26 in a 70 ml mayonnaise bottle. .. Add 35 parts by mass of zirconia beads with a diameter of 2 mm and 2 parts by mass, pre-crush with a paint shaker (manufactured by Asada Steel) for 1 hour, transfer the mixed solution to another 30 ml mayonnaise bottle, and transfer to another 30 ml mayonnaise bottle to obtain a diameter of 0.1 mm. 70 parts by mass of zirconia beads were added and shaken with a paint shaker for 5 hours to obtain a color material dispersion liquid.

(2) Preparation of Colored Resin Composition 25.3 parts by mass of photosensitive binder component (CR-1) obtained in Preparation Example 1, 0.2 parts by mass of silane coupling agent KBM-503 (manufactured by Shinetsu Silicone), interface By mixing 0.02 parts by mass of activator Megafuck F559 (manufactured by DIC) and 66.0 parts by mass of PGMEA, and further mixing 8.5 parts by mass of the colorant dispersion obtained in (1) above. , The colored resin composition of Example 3 was obtained.

For the colored resin compositions obtained from each Example and Comparative Example, the optical properties and the generation of foreign substances in the colored layer were evaluated as follows. The results of each evaluation are shown in Table 2.

[Evaluation method]
<Evaluation of optical characteristics>
The optical characteristics were evaluated as follows. Each of the colored resin compositions was applied onto a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") having a thickness of 0.7 mm using a spin coater. After removing the solvent of the substrate after coating with a vacuum dryer, heat drying was performed on a hot plate at 80 ° C. for 3 minutes. A cured film was obtained by irradiating ultraviolet rays of ^{60 mJ / cm 2} using an ultra-high pressure mercury lamp without using a photomask. The film thickness (T; μm) after drying and curing was adjusted so that the chromaticity after post-baking, which will be described later, was y = 0.17. The glass plate on which the colored layer was formed was post-baked in a clean oven at 230 ° C. for 30 minutes, and the chromaticity (x, y) and brightness (Y) of the obtained colored layer were measured by using an Olympus microspectroscopy measuring device OSP-SP200. Measured using.

<Evaluation of foreign matter generation>
Each of the colored resin compositions was applied onto a glass substrate using a spin coater so that the film thickness would be 2 μm after drying, and then the coating film after removing the solvent with a vacuum dryer was visually confirmed.
Regarding the substrate to be produced when evaluating the optical characteristics, the coating film after removing the solvent with a vacuum dryer was visually confirmed to evaluate the generation of foreign substances.
(Evaluation criteria)
A: No precipitation on the coating film after vacuum drying B: Precipitation on a part of the coating film after vacuum drying C: Precipitation on the entire surface of the coating film after vacuum drying

From the results in Table 2, when the coloring materials A to E, which are the coloring materials represented by the general formula (1) used in the present invention, are used, a colored layer in which the generation of foreign substances is suppressed is obtained. It was shown to be.

(Preparation Example 2: Synthesis of Blue Color Material 1)
(1) Synthesis of Intermediate 1 With reference to the method for producing Intermediate 3 and Intermediate 4 described in International Publication No. 2012/144521, 15.9 g (yield) of Intermediate 1 represented by the following chemical formula (a) was obtained. Rate 70%) Obtained.
It was confirmed from the following analysis results that the obtained compound was the target compound.
-MS (ESI) (m / z): 511 (+), divalent / elemental analysis value: CHN measured value (78.13%, 7.48%, 7.78%); theoretical value (78.06%) , 7.75%, 7.69%)

(2) Synthesis of Blue Color Material 1 5.00 g (4.58 mmol) of Intermediate 1 was added to 300 ml of water and dissolved at 90 ° C. to prepare a solution of Intermediate 2. _{Next, add 10.44 g (3.05 mmol) of phosphotungstic acid / n-hydrate H 3} [PW ₁₂ O ₄₀ ] / nH ₂ O (n = 30) manufactured by Nippon Inorganic Chemicals Co., Ltd. to 100 mL of water and stir at 90 ° C. Then, an aqueous solution of phosphotungstic acid was prepared. An aqueous solution of phosphotungstic acid was mixed with the above two intermediate solutions at 90 ° C., and the resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 g (yield 98%) of the blue color material 1 represented by the following chemical formula (b).
It was confirmed from the following analysis results that the obtained compound was the target compound. (Mole ratio W / Mo = 100/0)
-MS (ESI) (m / z): 510 (+), divalent / elemental analysis value: CHN measured value (41.55%, 5.34%, 4.32%); theoretical value (41.66%) 5.17%, 4.11%)
^{Further, it was confirmed by 31} P-NMR that the polyacid structure of phosphotungstic acid was maintained even after becoming the blue color material 1.

(Preparation Example 3: Synthesis of Antioxidant B)
Pentaerytritor tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010, manufactured by BASF) 0.01 mol, di-tert-butyl dicarbonate 0.05 mol and 30 g of pyridine was mixed, 0.025 mol of 4-dimethylaminopyridine was added at room temperature under a nitrogen atmosphere, and the mixture was stirred at 60 ° C. for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, 200 g of chloroform was added, and oil-water separation was performed. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and 100 g of methanol was added to the residue for crystallization. The obtained white powdery crystals were dried under reduced pressure at 60 ° C. for 3 hours.
A potential antioxidant B represented by the chemical formula (c) was obtained. The structure of the obtained antioxidant B was confirmed by IR and NMR.

(Preparation Example 4: Synthesis of Block Copolymer A)
Add 250 parts by mass of THF and 0.6 parts by mass of lithium chloride to a 500 mL round bottom 4-port separable flask equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and perform sufficient nitrogen substitution. rice field. After cooling the reaction flask to −60 ° C., 4.9 parts by mass of butyl lithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 29.1 parts by mass of 2- (trimethylsilyloxy) ethyl methacrylate (TMSMA), and 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA) of the B-block monomer. Parts, 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA) over 60 minutes using an addition funnel. Dropped. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to obtain a solid content of 30% by mass. Add 32.5 parts by mass of water, raise the temperature to 100 ° C. and react for 7 hours to deprotect the EEMA-derived structural unit to make it a methacrylic acid (MAA) -derived structural unit, and deprotect the TMSMA-derived structural unit. It was used as a constituent unit derived from 2-hydroxyethyl methacrylate (HEMA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, filtered, and vacuum dried to purify the block copolymer A (acid value 8 mgKOH / g) containing the structure represented by the general formula (1). , Tg 38 ° C.) was obtained. When the block copolymer A thus obtained was confirmed by GPC (gel permeation chromatography), the weight average molecular weight Mw was 7730. The amine value was 95 mgKOH / g.

(Preparation Example 5: Preparation of Blue Color Material Dispersion Liquid (A))
In a 70 ml mayonnaise bottle, 4.6 parts by mass of commercially available pigment blue 15: 6 pigment, BYK-LPN21116 (40% by mass of non-volatile content manufactured by Big Chemie), 6.8 parts by mass, 23.6 parts by mass of PGMEA, zirconia beads 35 having a diameter of 2 mm Add parts by mass, pre-crush with a paint shaker (made by Asada Steel) for 1 hour, transfer the mixture to another 70 ml mayonnaise bottle, add 70 parts by mass of zirconia beads with a diameter of 0.1 mm to the paint shaker. The mixture was shaken for 5 hours to obtain the blue color material dispersion (A) of Preparation Example 5. 0.1 part by mass of the obtained blue color material dispersion (A) was diluted with 9.9 parts by mass of PGMEA, and the particle size distribution was measured using a Microtrack UPA particle size distribution meter (manufactured by Nikkiso Co., Ltd.). The evaluation was performed with a 50% average particle size, and the volume conversion (MV) was 47 nm.

(Preparation Example 6: Preparation of Blue Color Material Dispersion Liquid (B))
In a 70 ml mayonnaise bottle, 24.8 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) and 5.3 parts by mass of block copolymer A solution (amine value 95 mgKOH / g, non-volatile content 45% by mass) were placed and stirred. Add 0.36 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) (0.6 molar equivalent to the tertiary amino group of the block copolymer), and stir at room temperature for 30 minutes. A salt-type block copolymer solution was obtained.
Next, 4.6 parts by mass of the blue color material 1 and 35 parts by mass of zirconia beads having a particle size of 2 mm were added, and the mixture was shaken with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as preliminary crushing, and then the particle size was 0.1 mm. The zirconia beads were changed to 70 parts of the above zirconia beads and dispersed for 4 hours with a paint shaker as the main crushing to obtain a blue color material dispersion liquid (B).
0.1 parts by mass of each of the obtained blue color material dispersion liquid (B) was diluted with 9.9 parts by mass of PGMEA, and the particle size distribution was measured using a Microtrack UPA particle size distribution meter (manufactured by Nikkiso Co., Ltd.). The evaluation was performed with a 50% average particle size, and the result of volume conversion (MV) was 114 nmm.

(Reference Example 7: Preparation of Colored Resin Composition)
A color material solution was prepared by dissolving 0.40 parts by mass of the color material A obtained in Synthesis Example 1 in 55.0 parts by mass of PGMEA. On the other hand, 16.5 parts by mass of the blue color material dispersion liquid (A) obtained in Preparation Example 5, 27.8 parts by mass of the photosensitive binder component (CR-1) obtained in Preparation Example 1, and a silane coupling agent. By mixing 0.3 parts by mass of KBM-503 (manufactured by Shinetsu Silicone) and 0.03 parts by mass of the surfactant Megafuck F559 (manufactured by DIC), and further mixing the coloring material solution with this, the reference example 7 A colored resin composition was obtained.

(Examples 8 to 11, Comparative Examples 2 to 4: Preparation of colored resin composition)
In Reference Example 7, the colored resin compositions of Examples 8 to 11 are the same as in Reference Example 7, except that the type and content of the xanthene-based coloring material and the content of other components are changed as shown in Table 3. A product and a comparative colored resin composition of Comparative Examples 2 to 4 were obtained.

(Examples 12 to 16: Preparation of colored resin composition)
In Example 9, coloring of Examples 12 to 13 was carried out in the same manner as in Example 9, except that the type of xanthene-based coloring material was changed and at least one of the addition of the antioxidant was changed as shown in Table 4. A resin composition was obtained.
Regarding the addition of the antioxidant, the antioxidant A: hindered phenolic antioxidant (pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name) : Irganox 1010, manufactured by BASF)) was added so as to be 2% by mass based on the solid content of the colored resin composition.
Further, in Example 9, 2%, 5%, and 10%, respectively, in 0.47 parts by mass of the coloring material C were replaced with phthalocyanine dyes (tetraazaporphyrin metal complex TAP-SP manufactured by Yamada Chemical Industry Co., Ltd.). , The colored resin compositions of Examples 14 to 16 were obtained in the same manner as in Example 9.

With respect to the colored resin compositions obtained in Reference Example 7, Examples 8 to 16 and Comparative Examples 2 to 4, the optical characteristics and contrast were evaluated as follows, and the evaluation of the generation of foreign matter in the colored layer was performed with Reference Example 1. It was done in the same way. The results of each evaluation are shown in Table 4.

[Evaluation method]
<Optical characterization, contrast evaluation>
The optical characteristics were evaluated as follows. Each of the colored resin compositions was applied onto a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") having a thickness of 0.7 mm using a spin coater. Then, it was heated and dried on a hot plate at 80 ° C. for 3 minutes. A cured film was obtained by irradiating ultraviolet rays of ^{60 mJ / cm 2} using an ultra-high pressure mercury lamp without using a photomask. The film thickness (T; μm) after drying and curing was adjusted so that the chromaticity after post-baking, which will be described later, was y = 0.085. The glass plate on which the colored layer was formed was post-baked in a clean oven at 230 ° C. for 30 minutes, and the contrast, chromaticity (x, y) and brightness (Y) of the obtained colored layer were measured by Tsubosaka Electric's contrast measuring device CT. The measurement was performed using -1B and an Olympus microspectroscopy measuring device OSP-SP200.

(Example 17: Preparation of colored resin composition)
A coloring material solution was prepared by dissolving 0.12 parts by mass of the coloring material B obtained in Synthesis Example 2 in 53.1 parts by mass of PGMEA. On the other hand, 19.4 parts by mass of the blue color material dispersion liquid (B) obtained in Preparation Example 6, 27.0 parts by mass of the photosensitive binder component (CR-1) obtained in Preparation Example 1, and a silane coupling agent. By mixing 0.3 parts by mass of KBM-503 (manufactured by Shin-Etsu Silicone) and 0.03 parts by mass of the surfactant Megafuck F559 (manufactured by DIC), and further mixing the coloring material solution with this, the case of Example 17 A colored resin composition was obtained.

(Examples 18 to 23, Comparative Examples 5 to 6: Preparation of colored resin composition)
In Example 17, the same procedure as in Example 17 except that at least one of the type of the xanthene-based colorant, the addition of the antioxidant, and the addition of the phthalocyanine dye was changed as shown in Table 5. , The colored resin compositions of Examples 18 to 23, and the comparative colored resin compositions of Comparative Examples 5 to 6 were obtained.
Regarding the addition of the antioxidant, the antioxidant A: hindered phenolic antioxidant (pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name) : Irganox 1010, manufactured by BASF)) or the antioxidant B of Preparation Example 3 was added so as to be 2% by mass based on the solid content of the colored resin composition. Regarding the addition of the phthalocyanine dye, in Example 18 or 20, 5% of 0.12 parts by mass of the coloring material C was replaced with the phthalocyanine dye (tetraazaporphyrin metal complex TAP-SP manufactured by Yamada Chemical Industry Co., Ltd.). The colored resin compositions of Examples 22 to 23 were obtained in the same manner as in Example 18 or 20 except for the above.

With respect to the colored resin compositions obtained in Examples 17 to 23 and Comparative Examples 5 to 6, the optical characteristics and contrast were evaluated in the same manner as in Reference Example 7, and the generation of foreign matter in the colored layer was evaluated in the same manner as in Reference Example 1. went. The results of each evaluation are shown in Table 5.

(Example 24: Preparation of colored resin composition)
A coloring material solution was prepared by dissolving 0.21 parts by mass of the coloring material B obtained in Synthesis Example 2 in 53.6 parts by mass of PGMEA. On the other hand, 9.4 parts by mass of the blue color material dispersion (A) obtained in Preparation Example 5, 9.4 parts by mass of the blue color material dispersion (B) obtained in Preparation Example 6, were obtained in Preparation Example 1. 27.1 parts by mass of the photosensitive binder component (CR-1), 0.3 parts by mass of the silane coupling agent KBM-503 (manufactured by Shinetsu Silicone), 0.03 parts by mass of the surfactant Megafuck F559 (manufactured by DIC) Was mixed, and the colorant solution was further mixed therewith to obtain the colored resin composition of Example 24.

(Example 25 and Comparative Example 7: Preparation of colored resin composition)
In Example 24, the colored resin composition of Example 25 and the comparative colored resin of Comparative Example 7 were used in the same manner as in Example 24 except that the coloring material shown in Table 6 was used instead of the coloring material B. The composition was obtained.

With respect to the colored resin compositions obtained in Examples 24 to 25 and Comparative Example 7, the optical characteristics and contrast were evaluated in the same manner as in Reference Example 7, and the generation of foreign matter in the colored layer was evaluated in the same manner as in Reference Example 1. .. The results of each evaluation are shown in Table 6.

(Preparation Example 7: Preparation of Photosensitive Binder Component (CR-2))
In Preparation Example 1, the amount of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (manufactured by BASF Japan, "IRGACURE907") was 6.0 parts by mass, and the oxime was used. A photosensitive binder component (CR-2) was obtained in the same manner as in Preparation Example 1 except that 6.0 parts by mass of an ester-based initiator (“ADEKA Arkuru's NCI-930” manufactured by ADEKA) was added.

(Example 26: Preparation of colored resin composition)
The colored resin composition of Example 26 is the same as in Example 20 except that the photosensitive binder component (CR-1) is changed to the photosensitive binder component (CR-2) of Preparation Example 7 in Example 20. Got

The colored resin compositions obtained in Examples 20 and 26 were evaluated for the residual film ratio as shown below. The results of each evaluation are shown in Table 7.

[Evaluation method]
<Evaluation of residual film ratio>
The colored resin composition is applied onto a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater, and then dried at 80 ° C. for 3 minutes using a hot plate on the glass substrate. A coating film was formed. An ultra-high pressure mercury lamp was used to irradiate the entire surface with ultraviolet rays of ^{60 mJ / cm 2 without using a photomask to form a coating film after exposure.} Then, a 0.05 wt% potassium hydroxide aqueous solution was spin-developed as a developing solution, and the developer was indirectly liquid-developed for 60 seconds and then washed with pure water to develop and form a coating film after development. Then, it was post-baked in a clean oven at 230 ° C. for 25 minutes to form a cured coating film (colored layer) having a thickness of 3.0 μm. In the process of forming the coating film, the film thickness (E) after exposure, the film thickness (D) after development, and the film thickness (B) after post-baking are determined by the stylus profiler P-16 (manufactured by KLA-Tencor). The film thickness after development (D) / film thickness after exposure (E) was calculated.

(Preparation Example 8: Preparation of Photosensitive Binder Component (CR-3))
As an alkali-soluble resin, a methacrylate / methyl methacrylate / cyclohexyl methacrylate copolymer (molar ratio: 13.8 / 26.2 / 50.0, weight average molecular weight: 9000, acid value: 90 mgKOH / g, active ingredient content 40 Mass%) 40.0 parts by mass, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., "KAYARAD DPHA") 48.0 parts by mass as a polyfunctional monomer, oxime ester-based initiator (manufactured by ADEKA) as a photoinitiator , "Adeca Arcurus NCI-930") 5.6 parts by mass, oxime ester-based initiator (manufactured by Joshu Strong Electronics New Materials Co., Ltd., "TR-PBG-3057") 5.6 parts by mass, diethylthioxanthone (Nippon Kayaku) 2.0 parts by mass of "DETX-S"), 2.0 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate), 0.8 parts by mass of antioxidant IRGANOX1010 (BASF), and solvent. After adding 96.0 parts by mass of PGMEA, the mixture was mixed until uniform to obtain a photosensitive binder component (CR-3).

(Preparation Example 9: Preparation of Photosensitive Binder Component (CR-4))
In the preparation of the photosensitive binder component (CR-3) of Preparation Example 8, a polyamide having the repeating unit of the general formula (A) instead of the methacrylic acid / methyl methacrylate / cyclohexyl methacrylate copolymer as the alkali-soluble resin. Changed to imide resin solution (solid content 44.1% by mass) (trade name: EMG-1015, manufactured by DIC Co., Ltd., aliphatic carboxylic acid-containing polyamide-imide, acid value 149 KOHmg / g in terms of solid content, number average molecular weight 4900) Then, a photosensitive binder component CR-4 was obtained in the same manner as in Preparation Example 8 except that the amount used was adjusted so that the solid content was the same by mass.

(Preparation Example 10: Preparation of Photosensitive Binder Component (CR-5))
In the preparation of the photosensitive binder component (CR-3) of Preparation Example 8, instead of the methacrylic acid / methyl methacrylate / cyclohexyl methacrylate copolymer as the alkali-soluble resin, an alkali-soluble resin F solution (carboxy group containing a cardo structure) Epoxy (meth) acrylate resin with, part number INR-16M manufactured by Nagase Chemtech Co., Ltd., solid content 54.5%), and the amount used is adjusted so that the solid content is the same mass part. A photosensitive binder component CR-5 was obtained in the same manner as in Preparation Example 8.

(Preparation Example 11: Preparation of Photosensitive Binder Component (CR-6))
In the preparation of the photosensitive binder component (CR-3) of Preparation Example 8, 5.6 parts by mass of an oxime ester-based initiator (manufactured by ADEKA, "Adeca Arcurus NCI-930") as a photoinitiator, an oxime ester-based initiator Instead of 5.6 parts by mass of the agent ("TR-PBG-3057" manufactured by Changshu Power Electronics New Materials Co., Ltd.) and 2.0 parts by mass of diethylthioxanthone ("DETX-S" manufactured by Nippon Kayaku Co., Ltd.), an oxime ester. 5. 5.6 parts by mass of system initiator (manufactured by Changshu Strong Electronics New Materials Co., Ltd., "TR-PBG-365"), oxime ester-based initiator (manufactured by Joshu Strong Electronics New Materials Co., Ltd., "TR-PBG-3057") 5. Except for changing to 6 parts by mass and 2.0 parts by mass of diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., "DETX-S") and adjusting the amount used so that the solid content is the same by mass. A photosensitive binder component CR-6 was obtained in the same manner as in Preparation Example 8.

(Preparation Example 12: Preparation of Photosensitive Binder Component (CR-7))
In the preparation of the photosensitive binder component (CR-3) of Preparation Example 8, 5.6 parts by mass of an oxime ester-based initiator (manufactured by ADEKA, "Adeca Arcurus NCI-930") as a photoinitiator, an oxime ester-based initiator Instead of 5.6 parts by mass of the agent ("TR-PBG-3057" manufactured by Changshu Power Electronics New Materials Co., Ltd.) and 2.0 parts by mass of diethylthioxanthone ("DETX-S" manufactured by Nippon Kayaku Co., Ltd.), an oxime ester. 5.6 parts by mass of system initiator (manufactured by Changshu Strong Electronics New Materials Co., Ltd., "TR-PBG-304"), 5.6 parts by mass of oxime ester-based initiator (manufactured by Joshu Strong Electronics New Materials Co., Ltd., TR-PBG-365 ") 5.6 Prepared except by changing to 2.0 parts by mass and 2.0 parts by mass of diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., "DETX-S") and adjusting the amount used so that the solid content is the same by mass. A photosensitive binder component CR-7 was obtained in the same manner as in Example 8.

(Preparation Example 13: Preparation of Photosensitive Binder Component (CR-8))
In the preparation of the photosensitive binder component (CR-3) of Preparation Example 8, 5.6 parts by mass of an oxime ester-based initiator (manufactured by ADEKA, “Adeca Arcurus NCI-930”) as a photoinitiator, an oxime ester-based initiator Instead of 5.6 parts by mass of the agent ("TR-PBG-3057" manufactured by Changshu Power Electronics New Materials Co., Ltd.) and 2.0 parts by mass of diethylthioxanthone ("DETX-S" manufactured by Nippon Kayaku Co., Ltd.), an oxime ester. 5.6 parts by mass of system initiator (manufactured by Changshu Strong Electronics New Materials Co., Ltd., "TR-PBG-304"), 5.6 parts by mass of oxime ester-based initiator (manufactured by Joshu Strong Electronics New Materials Co., Ltd., TR-PBG-3057) 5.6 Prepared except by changing to 2.0 parts by mass and 2.0 parts by mass of diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., "DETX-S") and adjusting the amount used so that the solid content is the same by mass. A photosensitive binder component CR-8 was obtained in the same manner as in Example 8.

(Preparation Example 14: Preparation of Photosensitive Binder Component (CR-9))
In the preparation of the photosensitive binder component (CR-3) of Preparation Example 8, 5.6 parts by mass of an oxime ester-based initiator (manufactured by ADEKA, “ADEKA ARCLUS NCI-930”) as a photoinitiator, an oxime ester-based initiator Instead of 5.6 parts by mass of the agent ("TR-PBG-3057" manufactured by Changshu Strong Electronics New Materials Co., Ltd.) and 2.0 parts by mass of diethylthioxanthone ("DETX-S" manufactured by Nippon Kayaku Co., Ltd.), an oxime ester. System initiator (manufactured by Changshu Strong Electronics New Materials Co., Ltd., "TR-PBG-304") 6.6 parts by mass, oxime ester-based initiator (manufactured by Joshu Strong Electronics New Materials Co., Ltd., TR-PBG-3057 ") 6.6 A photosensitive binder component CR-9 was obtained in the same manner as in Preparation Example 8 except that the amount was changed to parts by mass and the amount used was adjusted so that the solid content was the same parts by mass.

(Examples 27 to 33: Preparation of colored resin composition)
In Example 25, the photosensitive binder component (CR-1) was changed to the photosensitive binder components (CR-3) to (CR-9) of Preparation Examples 8 to 14 in the same manner as in Example 25. , The colored resin compositions of Examples 27 to 33 were obtained.

With respect to the colored resin compositions obtained in Examples 27 to 33, the optical characteristics and the contrast were evaluated in the same manner as in Reference Example 7, and the residual film ratio was evaluated in the same manner as in Example 26. The results of each evaluation are shown in Table 8.

(Summary of results)
From the results of Tables 4 to 6, when the coloring materials A to E, which are the coloring materials represented by the general formula (1) used in the present invention, are used, the generation of foreign substances is suppressed. It was shown that a layer was obtained. On the other hand, when the comparative color material F described in Patent Document 2 and the comparative color materials G and H described in Patent Document 1 were used, respectively, a colored layer in which foreign matter was generated was obtained.
From the results of Tables 4 to 6, when the coloring materials A to E, which are the coloring materials represented by the general formula (1) used in the present invention, are used, a colored layer having improved brightness can be obtained. It was shown to be. On the other hand, when the comparative color material F described in Patent Document 2 and the comparative color materials G and H described in Patent Document 1 are used, respectively, a colored layer having inferior brightness as compared with the examples is obtained. Was done.
Among the examples, the brightness tends to be improved when the aliphatic hydrocarbon group contained in any of the substituents of ^{R 1} and R ² and R ³ and R ^{4 is an alkyl group having 3 or more carbon atoms.} In particular, when R ¹ and R ² are n-propyl groups or n-butyl groups, the brightness tends to be improved.

On the other hand, even in the examples, it was shown that the brightness was further improved when the antioxidant was added.
Further, when a colored layer is formed by combining the coloring material represented by the general formula (1) used in the present invention and a pigment, further addition of a phthalocyanine dye can suppress fluorescence, and contrast can be achieved. Was shown to be significantly improved.
When the coloring material represented by the general formula (1) used in the present invention is combined with a lake pigment (blue coloring material 1) which is a salt-forming compound of a dye to form a colored layer, fluorescence is suppressed. It was shown that the contrast was superior to that when combined with the pigment. Further, it was shown that the contrast is improved by further adding a phthalocyanine dye to the color material represented by the general formula (1) and the lake pigment (blue color material 1) which is a salt-forming compound of the dye. ..

Further, from the results in Table 7, it was shown that when an oxime ester-based initiator was used as the initiator in the combination of the binder components, the residual film ratio during development of the colored layer was improved.
Further, from the results in Table 8, when the polyamide-imide resin is used as the alkali-soluble resin or the epoxy (meth) acrylate resin having a carboxy group containing a cardo structure is used in the combination of the binder components, the brightness is further increased. Was shown to be improved and the contrast was also improved.
Further, from the results in Table 8, it was shown that in the combination of the binder components, the brightness was improved when two or more kinds of oxime ester-based initiators and an antioxidant were used in combination as the initiator. In particular, the combined use of two types of oxime ester-based photoinitiators having a diphenyl sulfide skeleton or the combined use of an oxime ester-based photoinitiator having a diphenyl sulfide skeleton and an oxime ester-based photoinitiator having a fluorene skeleton has high brightness and heat resistance. The sex has increased.
Further, in the combination of the binder components, in Example 33 in which two or more kinds of oxime ester-based initiators, a mercapto compound, and an antioxidant were used in combination as the initiator, the residual film ratio was improved and water stain was observed. The inhibitory effect was high, and the ability to form a fine line pattern as designed for the mask line width was improved. Further, in Examples 27 to 32 in which two or more kinds of oxime ester-based initiators, a thioxanthene-based initiator, a mercapto compound, and an antioxidant were used in combination, the residual film ratio was further improved and water stain was observed. The inhibitory effect was high, and the ability to form a fine line pattern as designed for the mask line width was improved.

1 Substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposite substrate 30 Liquid crystal layer 40 Liquid crystal display 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emission display device

Claims (10)

Coloring for a color filter, which contains a color material (A), a binder component (B), and a solvent (C), and the color material (A) contains a color material represented by the following general formula (1). Resin composition.

(In the general formula (1), R ¹ and R ² are each independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent, and R ³ and R ⁴ are independent of each other. , An aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and the aromatic hydrocarbon group or the aromatic heterocyclic group of R ³ and R ⁴ is an aliphatic hydrocarbon group, respectively. Substituted. ^{Any one of the aliphatic hydrocarbon groups contained in R 1} , R ² , R ³ and R ⁴ is an alkyl group having 3 or more carbon atoms. L ¹ and L ² are independent of each other. a direct bond, -SO ₂ -, or a -CO-, ^{R 5} is a halogenated aliphatic hydrocarbon group). The colored resin composition for a color filter according to claim 1, wherein the color material (A) further contains a blue color material. The colored resin composition for a color filter according to claim 1 or 2, wherein the coloring material (A) contains at least one of a phthalocyanine pigment and a lake pigment of a dye. The color filter according to any one of claims 1 to 3, wherein the color material (A) contains at least one selected from the group consisting of anthraquinone dye, phthalocyanine dye, triarylmethane dye, and cyanine dye. Colored resin composition for. The invention according to any one of claims 1 to 4, wherein the binder component (B) contains an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and the photoinitiator contains a thioxanthone-based initiator. Colored resin composition for color filters. The colored resin composition for a color filter according to any one of claims 1 to 5, further comprising an antioxidant. The group in which the solvent (C) consists of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, and 3-methoxybutyl acetate. The colored resin composition for a color filter according to any one of claims 1 to 6, which comprises at least one selected from. A color material dispersion liquid in which a color material represented by the following general formula (1) is dispersed in a solvent by a dispersant having an amine value.

(In the general formula (1), R ¹ and R ² are each independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent, and R ³ and R ⁴ are independent of each other. , An aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and the aromatic hydrocarbon group or the aromatic heterocyclic group of R ³ and R ⁴ is an aliphatic hydrocarbon group, respectively. Substituted. ^{Any one of the aliphatic hydrocarbon groups contained in R 1} , R ² , R ³ and R ⁴ is an alkyl group having 3 or more carbon atoms. L ¹ and L ² are independent of each other. a direct bond, -SO ₂ -, or a -CO-, ^{R 5} is a halogenated aliphatic hydrocarbon group). A color filter comprising a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the colored resin composition for a color filter according to any one of claims 1 to 7. A color filter characterized by having a colored layer made of a cured product. A display device comprising the color filter according to claim 9.

Images