WO2018124087A1

WO2018124087A1 - Colorant dispersion liquid for color filters, coloring resin composition for color filters, color filter and display device

Info

Publication number: WO2018124087A1
Application number: PCT/JP2017/046687
Authority: WO
Inventors: 中村　和彦; 渚井上; 亘田尻
Original assignee: 株式会社Ｄｎｐファインケミカル
Priority date: 2016-12-28
Filing date: 2017-12-26
Publication date: 2018-07-05
Also published as: JP7094891B2; TW201840740A; TWI748029B; CN110062900A; JPWO2018124087A1

Abstract

Provided is a coloring resin composition for color filters, which has excellent colorant dispersion stability, and which is capable of forming a colored layer that has improved contrast, while being reduced in the retardation value. A coloring resin composition for color filters, which contains a colorant, a dispersant, a binder component and a solvent, and wherein: the colorant contains a red colorant and a yellow colorant; the yellow colorant contains at least one anion selected from the group consisting of mono-, di-, tri- and tetra-anions of specific azo compounds and tautomeric forms of the azo compounds, ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a melamine derivative; and the dispersant is a polymer that has a specific constituent unit.

Description

Color material dispersion for color filter, colored resin composition for color filter, color filter, and display device

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

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (cell phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has been attracting attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.

Many conventional display devices comply with sRGB (IEC 61966-2-1), which is an international standard for color space. However, in order to obtain an expression that is closer to the real thing and has a demand for further improvement in color reproducibility, compared to sRGB, AdobeRGB has a wide color reproduction range in the green direction, and has a wide color reproduction range in the red and green directions. DCI (Digital Cinema Initiatives) and BT (Broadcasting Service Television). The demand for display devices corresponding to 2020 is increasing.

Here, the color filter used in the liquid crystal display device generally defines a transparent substrate, a colored layer formed on the transparent substrate, which is composed of colored patterns of three primary colors of red, green, and blue, and each colored pattern. As described above, the light shielding portion is formed on the transparent substrate.
As a method for forming such a colored layer, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and the like are known. Among these, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, etc., a pigment dispersion method having excellent characteristics on average is most widely adopted.

On the other hand, the liquid crystal display device has a problem of viewing angle dependency due to the refractive index anisotropy of the liquid crystal cell and the polarizing plate as a specific problem. This problem of viewing angle dependency is a problem that the color and contrast of an image that is visually recognized change when the liquid crystal display device is viewed from the front and when viewed from an oblique direction. Such a problem of viewing angle characteristics has become more serious as the liquid crystal display device has recently been enlarged.
In order to improve such a viewing angle dependency problem, a method of incorporating a retardation film into a liquid crystal display device has been widely used. However, since the color filter used in the liquid crystal display device has a different phase difference depending on the coloring pattern of each color of the colored layer, when the above retardation film is used, the difference in the retardation of each color coloring pattern is compensated. It is difficult to completely solve the problem of viewing angle dependency.

In particular, since many red color materials are easily crystallized due to their chemical structure, there is a problem that a red colored layer tends to have a larger retardation value in the thickness direction than other colored layers.
In addition, in order to widen the color reproduction range using the red color material that has been used in the past, when creating red pixels that are included in the red chromaticity region of yellow color or bluish color with high color density, the pigment concentration However, there is a problem that the contrast and brightness are lowered or the plate-making property is deteriorated.

Patent Document 1 discloses C.I. as a red pigment. I. Pigment Red 177 (hereinafter sometimes abbreviated as PG177) and 1: 1 complex of azobarbituric acid with nickel, compatible isomers, and at least one of these compounds in the crystal lattice of other compounds. There is disclosed a color filter using in combination a pigment (CI Pigment Yellow 150 derivative (Ni complex)) made of at least one crystal selected from the group consisting of inserted crystals. However, if an attempt is made to express a deep red color using this pigment, it is necessary to use a very high concentration pigment, the thickness direction retardation value increases, the contrast decreases, and the plate-making property deteriorates. There was a problem.

On the other hand, Patent Document 2 includes, as a novel metal azo pigment, a dianion of a specific azo compound and an adduct of a metal azo compound composed of at least two metal ions of Zn ²⁺ and Ni ²⁺ and melamine or a derivative thereof, A metal azo pigment having a specific signal and no specific signal in an X-ray diffraction diagram is described.

JP 2010-144057 A JP 2014-12838 A

The present invention is excellent in color material dispersion stability and uses a color material dispersion for color filters that can form a colored layer with improved contrast while the retardation value is reduced, and the color material dispersion for the color filters. Color filter colored resin composition capable of forming a colored layer with excellent color reproducibility with improved contrast while the retardation value is reduced, while the retardation value is reduced using the colored resin composition for color filter To provide a color filter with improved contrast and excellent color reproducibility, and a display device with improved contrast and excellent color reproducibility while reducing the phase difference value by using the color filter With the goal.

A color material dispersion for a color filter according to the present invention is a color material dispersion containing a color material, a dispersant, and a solvent,
The color material includes a red color material and a yellow color material,
The yellow color material includes at least one anion selected from the group consisting of mono-, di-, tri-, and tetraanions of an azo compound represented by the following general formula (A) and an azo compound having a tautomer structure thereof: An ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (B): Including
The dispersing agent is a color material dispersion for a color filter, which is a polymer having a structural unit represented by the following general formula (I).

The colored resin composition for a color filter according to the present invention is a colored resin composition for a color filter containing a coloring material, a dispersant, a binder component, and a solvent,
The color material includes a red color material and a yellow color material,
The yellow color material includes at least one anion selected from the group consisting of mono-, di-, tri-, and tetraanions of an azo compound represented by the following general formula (A) and an azo compound having a tautomer structure thereof: An ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (B): Including
The dispersant is a colored resin composition for a color filter, which is a polymer having a structural unit represented by the following general formula (I).

(In the general formula (A), each R ^a is independently —OH, —NH ₂ , —NH—CN, acylamino, alkylamino, or arylamino, and each R ^b is independently —OH or — NH _2. )

(In the general formula (B), each R ^c is independently a hydrogen atom or an alkyl group.)

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, R ² and R ³ are each independently a hydrogen atom or a hydrocarbon that may contain a hetero atom. Represents a group, and R ² and R ³ may combine with each other to form a ring structure.)

The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a colored resin composition for a color filter according to the present invention. It is the coloring layer which is a hardened | cured material of this.

The present invention provides a display device comprising the color filter according to the present invention.

According to the present invention, the color material dispersion liquid for color filters that is excellent in color material dispersion stability and can form a colored layer with improved contrast while the retardation value is reduced, and the color material dispersion liquid for color filters are used. The color resin composition for color filters capable of forming a colored layer with excellent color reproducibility with improved contrast while the phase difference value is reduced, and the phase difference value is reduced using the color resin composition for color filter However, a color filter with improved contrast and excellent color reproducibility and a display device with improved contrast and excellent color reproducibility while reducing the phase difference value by using the color filter. can do.

FIG. 1 is a schematic view showing an example of the color filter of the present invention. FIG. 2 is a schematic view showing an example of the display device of the present invention. FIG. 3 is a schematic view showing another example of the display device of the present invention.

Hereinafter, the color filter color material dispersion, the color filter colored resin composition, the color filter, and the display device according to the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.
In addition, C.I. I. Pigment Red is “PR”, C.I. I. Pigment Orange as “PO”, C.I. I. Pigment Yellow is abbreviated as “PY” where appropriate.

[Colorant dispersion]
A color material dispersion for a color filter according to the present invention is a color material dispersion containing a color material, a dispersant, and a solvent,
The color material includes a red color material and a yellow color material,
The yellow color material includes at least one anion selected from the group consisting of mono-, di-, tri-, and tetraanions of an azo compound represented by the following general formula (A) and an azo compound having a tautomer structure thereof: An ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (B): Including
The dispersing agent is a color material dispersion for a color filter, which is a polymer having a structural unit represented by the following general formula (I).

Since the color material dispersion of the present invention is used in combination with the specific color material and a polymer having a structural unit represented by the general formula (I) as a dispersant, the color material dispersion stability is improved. It is possible to form a colored layer with excellent contrast while reducing the retardation value.
Since many red color materials generally have an annular planar structure, since they are easy to crystallize when forming a colored layer as a color material dispersion for a color filter, the retardation in the thickness direction of the obtained colored layer The value tends to increase.
On the other hand, in the color material dispersion of the present invention, the red color material includes a specific yellow color material containing two or more kinds of metal ions and a weight having a specific structural unit represented by the general formula (I). Since the combination of the dispersant, which is a coalescence, is used, the interaction between the red color material and the specific yellow color material containing two or more kinds of metal ions causes the red color material and the yellow color material to be crystallized. Colored layer with improved contrast while reducing phase difference value because growth is suppressed and atomization is possible, and red color material and yellow color material are atomized and dispersed in combination with the dispersant. It is estimated that can be formed.
Conventionally, in the case where the metal forming the metal complex containing the azo compound represented by the general formula (A) is a single color material, it is difficult to atomize because of high crystallinity, and it is difficult to improve contrast. It was. Further, the retardation value of the colored layer obtained by combining with the red color material tends to be high. On the other hand, in this invention, the specific yellow color material containing 2 or more types of metal ions is used with respect to the anion of the azo compound represented by general formula (A). When the yellow color material contains two or more kinds of metal ions, not only the crystal growth of the yellow color material is suppressed, but also the crystal growth of the red color material is suppressed, and further, the specific dispersant is combined. It is presumed that they are atomized in the colorant dispersion.
In the present invention, the red color material is combined with the specific yellow color material to obtain a P / V ratio ((color material component mass in the composition) / (solid other than the color material component in the composition). Even if the (mass ratio) ratio) is suppressed, red pixels included in the high chromaticity red chromaticity region can be produced.
It is estimated that the retardation value in the thickness direction of the colored layer is reduced due to the synergistic effect that the P / V ratio is reduced in the colored layer and the crystal growth of the red color material is suppressed. .
In addition, since the total content of the color material components in the colored resin composition can be suppressed, the content of the binder component can be relatively increased, so that the platemaking property is improved and the adhesion to the substrate is improved. It becomes possible to form a higher colored layer.

The color material dispersion of the present invention contains at least a color material, a dispersant, and a solvent, and may further contain other components as long as the effects of the present invention are not impaired. .
Hereinafter, each component of the color material dispersion of the present invention will be described in detail in order.

<Color material>
In the present invention, the color material includes a red color material and a yellow color material,
The yellow color material includes at least one anion selected from the group consisting of mono-, di-, tri-, and tetraanions of an azo compound represented by the following general formula (A) and an azo compound having a tautomer structure thereof: An ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (B): It is characterized by including.
In the present invention, since the specific yellow color material is used as a yellow color material, a decrease in luminance can be suppressed when combined with a red color material, and crystallization is suppressed and atomization is possible. Since it is excellent in dispersibility when combined with a specific dispersant described later, the contrast can be improved and the retardation value can be reduced.

Examples of the acyl group in the acylamino group in the general formula (A) include, for example, an alkylcarbonyl group, a phenylcarbonyl group, an alkylsulfonyl group, a phenylsulfonyl group, an alkyl, phenyl, or a carbamoyl group that may be substituted with naphthyl, an alkyl , Sulfamoyl group optionally substituted with phenyl or naphthyl, guanyl group optionally substituted with alkyl, phenyl or naphthyl, and the like. The alkyl group preferably has 1 to 6 carbon atoms. The alkyl group may be substituted with, for example, a halogen such as F, Cl, or Br, —OH, —CN, —NH ₂ , and / or an alkoxy group having 1 to 6 carbon atoms. The phenyl group and naphthyl group are, for example, halogen such as F, Cl and Br, —OH, —CN, —NH ₂ , —NO ₂ , an alkyl group having 1 to 6 carbon atoms, and / or 1 carbon atom. It may be substituted with 6 or less alkoxy groups.
The alkyl group in the alkylamino group in the general formula (A) preferably has 1 to 6 carbon atoms. The alkyl group may be substituted with, for example, a halogen such as F, Cl, or Br, —OH, —CN, —NH ₂ , and / or an alkoxy group having 1 to 6 carbon atoms.
Examples of the aryl group in the arylamino group in the general formula (A) include a phenyl group and a naphthyl group. These aryl groups include, for example, halogens such as F, Cl, and Br, —OH, and those having 1 to 6 carbon atoms. The alkyl group, an alkoxy group having 1 to 6 carbon atoms, —NH ₂ , —NO _2, and —CN may be substituted.

In the azo compound represented by the general formula (A) and the azo compound having a tautomer structure thereof, each R ^a is independently —OH, —NH ₂ , —NH—CN, or alkylamino. it is preferable from the viewpoint comprising a reddish hue, the two R ^a may be different even in the same, respectively.
In the general formula (A), two R ^{a s} are, in terms of hue, when both are —OH, both are —NH—CN, or one is —OH and one is —NH—. More preferably, it is CN, and even more preferably both are —OH.

In the azo compound represented by the general formula (A) and the azo compound having a tautomer structure thereof, R ^b is more preferably —OH from the viewpoint of hue.

As the at least two kinds of metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, among them, a metal that becomes a divalent or trivalent cation is used. It is preferable to include at least one, preferably at least one selected from the group consisting of Ni, Cu, and Zn, and more preferably at least Ni.
Furthermore, it is preferable that Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn are further included. Furthermore, it is preferable that at least one metal selected from the group consisting of Zn, Cu, Al and Fe is included. In particular, the at least two metals are preferably Ni and Zn, or Ni and Cu.

In the yellow color material used in the present invention, the content ratio of at least two metals may be appropriately adjusted.
Among these, from the viewpoint of reddish hue, the yellow color material used in the present invention is selected from the group consisting of Ni and further Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn. The content ratio with the at least one metal is preferably such that Ni: the other at least one metal is contained in a molar ratio of 97: 3 to 10:90, and more preferably a mole of 90:10 to 10:90. It is preferable to include by ratio.
Among these, from the viewpoint of a reddish hue, Ni and Zn are preferably included in a molar ratio of Ni: Zn of 90:10 to 10:90, and more preferably 80:20 to 20:80. preferable.
Alternatively, from the viewpoint of a reddish hue, Ni and Cu are preferably included in a molar ratio of Ni: Cu of 97: 3 to 10:90, and more preferably in a molar ratio of 96: 4 to 20:80. preferable.
When the yellow color material has a red hue, it is easy to produce a red pixel included in the high chromaticity red chromaticity region even if the P / V ratio is suppressed.

The yellow color material used in the present invention may further contain metal ions different from the specific metal ions. The yellow color material used in the present invention may contain, for example, at least one metal ion selected from the group consisting of Li, Cs, Mg, Na, K, Ca, Sr, Ba, and La. .

As an aspect in which at least two kinds of metal ions are included in the yellow color material, there are a case where at least two kinds of metal ions are contained in a common crystal lattice, and a case where one kind of metal ion is included in another crystal lattice. An example is a case where crystals containing ions are aggregated. Among them, the case where at least two kinds of metal ions are contained in a common crystal lattice is preferable from the viewpoint of further improving the contrast. Whether the common crystal lattice includes at least two kinds of metal ions or whether another crystal lattice includes one type of metal ion each aggregated. For example, it can be appropriately determined by using an X-ray diffraction method with reference to JP-A-2014-12838.

The yellow color material used in the present invention further contains a compound represented by the following general formula (B). The yellow color material used in the present invention comprises a metal complex comprising an anion of an azo compound represented by the general formula (A) and an azo compound having a tautomeric structure thereof and a specific metal ion, and the following general formula (B The compound molecule | numerator with the compound represented by this is included. The bonds between these molecules can be formed, for example, by intermolecular interactions, by Lewis acid-base interactions, or by coordinate bonds. Alternatively, a structure such as an inclusion compound in which a guest molecule is incorporated in a lattice constituting a host molecule may be used. Alternatively, a mixed substitution crystal may be formed in which two substances form a joint crystal, and atoms of the second component are located at regular lattice positions of the first component.

The alkyl group for R ^c is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be substituted with an —OH group.
Among these, R ^c is preferably a hydrogen atom.

The content of the compound represented by the general formula (B) is generally based on 1 mol of the azo compound represented by the general formula (A) and the azo compound having a tautomeric structure thereof. 5 mol to 300 mol, preferably 10 mol to 250 mol, and more preferably 100 mol to 200 mol.

The yellow color material used in the present invention further includes urea and substituted ureas such as phenylurea and dodecylurea, and polycondensates thereof with aldehydes, particularly formaldehyde; heterocycles such as barbituric acid and benzimidazo. Ron, benzimidazolone-5-sulfonic acid, 2,3-dihydroxyquinoxaline, 2,3-dihydroxyquinoxaline-6-sulfonic acid, carbazole, carbazole-3,6-disulfonic acid, 2-hydroxyquinoline, 2,4- Contains dihydroxyquinoline, caprolactam, melamine, 6-phenyl-1,3,5-triazine-2,4-diamine, 6-methyl-1,3,5-triazine-2,4-diamine, cyanuric acid, etc. May be.
Further, the yellow color material used in the present invention further includes a water-soluble polymer such as ethylene-propylene oxide block polymer, polyvinyl alcohol, poly (meth) acrylic acid such as carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methyl. -And modified cellulose such as ethyl hydroxyethyl cellulose may be included.

The yellow color material used in the present invention can be prepared by referring to, for example, JP-A-2014-12838.

On the other hand, the red color material used in the present invention has a P / V (red color material mass / solid content mass other than red color material) ratio = 0.2 and a spectral transmittance spectrum of a coating film having a thickness of 2.5 μm. Is used, a colorant having a transmittance at a wavelength of 520 nm of 20% or less and a transmittance of a wavelength of 640 nm of 70% or more is used. The red color material used in the present invention is a slightly yellowish red color material (an orange material with strong redness). I. A coloring material denoted as pigment orange is also included.

In addition, in order to measure the color of a red color material as a single unit, an appropriate dispersant, binder component and solvent are mixed with the red color material to prepare a coating solution, which is then coated on a transparent substrate. May be dried and cured as necessary. As a binder component, a non-curable thermoplastic resin composition may be used as long as a transparent coating film capable of performing colorimetry can be formed, or a photo-curable (photosensitive) or thermosetting resin composition. May be used. In addition, in the colored resin composition of the present invention to be described later, by using a composition containing only a red color material as a color material, a coating film containing only a red color material as a color material may be formed and colorimetry may be performed. it can. Specifically, for example, the solid content used in the resin composition of Example 1 described later can be used as a solid content other than the red color material.
As a transparent coating film including a dispersant and a binder component that can perform colorimetry, for example, the film thickness is 2.0 μm, and the transmittance of the spectral transmittance spectrum at 380 to 780 nm is 95% or more. can do.
The spectral transmittance spectrum can be measured using a spectroscopic measurement device (for example, an Olympus microscope OSP-SP200). The measurement condition is a C light source.

The red color material used in the present invention is not particularly limited. Examples include perylene pigments and thioindigo pigments. In particular, the red color material used in the present invention is at least one selected from the group consisting of a diketopyrrolopyrrole pigment, a naphthol azo pigment, an anthraquinone pigment, and a perylene pigment from the viewpoint of suppressing the P / V ratio. It is preferable to include a seed, and further, from the viewpoint of easily forming a hue of high color density and high brightness, it further includes at least one selected from the group consisting of a diketopyrrolopyrrole pigment and an anthraquinone pigment. preferable.

Examples of the diketopyrrolopyrrole pigment include those represented by the following general formula (1).

(In the general formula (1), A ³ and A ⁴ are each independently a halogen atom, methyl group, ethyl group, tert-butyl group, phenyl group, N, N-dimethylamino group, trifluoromethyl group, or A cyano group, k and k ′ each independently represent an integer of 0 or more and 5 or less, and when k and k ′ are each an integer of 2 or more, a plurality of A ³ and A ⁴ may be the same May be different.)

Specific examples of the diketopyrrolopyrrole pigment include C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 270, C.I. I. Pigment red 272, C.I. I. Pigment orange 71, C.I. I. Pigment Orange 73, and diketopyrrolopyrrole pigment (BrDPP) represented by the following chemical formula (2).

Examples of the naphthol-based azo pigment include C.I. I. Pigment red 144, C.I. I. Pigment red 166, C.I. I. Pigment red 214, C.I. I. Pigment red 242, C.I. I. Pigment red 21, C.I. I. Pigment red 2, C.I. I. Pigment red 112, C.I. I. Pigment red 114, C.I. I. Pigment red 5, C.I. I. Pigment red 146, C.I. I. Pigment red 170, C.I. I. Pigment orange 38, C.I. I. Pigment red 187, C.I. I. Pigment red 150, C.I. I. And CI Pigment Red 185.
Other azo pigments include C.I. I. Pigment red 38, C.I. I. Pigment red 41 etc. are mentioned.

The anthraquinone pigments include C.I. I. Pigment red 177, C.I. I. Pigment red 168, C.I. I. And CI Pigment Orange 51.

As the perylene pigment, C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 190, C.I. I. And CI Pigment Red 224.

As the red color material, C.I. I. Pigment red 254, C.I. I. Pigment red 264, C.I. I. Pigment Red 272, a diketopyrrolopyrrole pigment (BrDPP) represented by the above chemical formula (2), C.I. I. Pigment red 242, C.I. I. Pigment orange 38, C.I. I. Pigment red 177, and C.I. I. It is preferable to use one or more red color materials selected from the group consisting of CI Pigment Red 179. I. Pigment Red 254, a diketopyrrolopyrrole pigment (BrDPP) represented by the above chemical formula (2), C.I. I. A combination with Pigment Red 177 is preferably used.
C. I. Pigment Red 254, a diketopyrrolopyrrole pigment (BrDPP) represented by the above chemical formula (2), C.I. I. The content ratio in the case of combining with Pigment Red 177 is not particularly limited as long as it is appropriately adjusted according to the desired color material. I. Pigment Red 254 is 10 to 80 parts by mass, the diketopyrrolopyrrole pigment (BrDPP) represented by the chemical formula (2) is 10 to 70 parts by mass, and C.I. I. It is preferable that the pigment red 177 is 10 parts by mass or more and 60 parts by mass or less. If it is in the said range, the effect of the said combination is excellent. In addition, the content rate of the said red color material is a preferable rate at the time of setting it as the below-mentioned colored resin composition, A colored resin composition can be manufactured using 2 or more types of color material dispersions suitably mixed. Therefore, the color material dispersion itself is preferably used even if it does not have the same content ratio as that of the colored resin composition described later.

In the color material dispersion of the present invention, a red color material and the specific yellow color material are used in combination as a color material, but other color materials such as those exemplified in the colored resin composition described below are used in combination. May be. As other color materials, for example, other yellow color materials, orange color materials not included in the red color material, and the like are preferably used. The yellow color material is preferably used.

In the color material dispersion of the present invention, each content ratio of the red color material and the specific yellow color material, and the content ratio in the case of using other color materials are the same content ratio as that of the color resin composition described later. It is preferable to do. However, two or more colorant dispersions can be appropriately mixed and used to produce a colored resin composition, so that the colorant dispersion is preferably used even if the content ratio is not the same as that of the later-described colored resin composition.

The average primary particle size of the color material used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a color layer of a color filter, and varies depending on the type of color material used. Is preferably in the range of 10 nm to 100 nm, more preferably 15 nm to 60 nm. When the average primary particle diameter of the color material is in the above range, a display device including a color filter manufactured using the color material dispersion of the present invention can be made with high contrast and high quality. .

Moreover, although the average dispersed particle diameter of the color material in the color material dispersion varies depending on the type of the color material used, it is preferably in the range of 10 nm to 100 nm, and preferably in the range of 15 nm to 60 nm. More preferred.
The average dispersed particle size of the color material in the color material dispersion is the dispersed particle size of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is. For particle size measurement with a laser light scattering particle size distribution meter, the color material dispersion is appropriately diluted to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times). Etc.) and can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distribution particle size here is a volume average particle size.

In the color material dispersion of the present invention, the content of the color material is not particularly limited. The content of the color material is 5 parts by mass or more and 80 parts by mass or less, more preferably 8 parts by mass or more and 70 parts by mass with respect to 100 parts by mass of the total solid content in the color material dispersion from the viewpoint of dispersibility and dispersion stability. It is preferable to mix | blend in the ratio below a mass part.
In particular, when forming a coating film or a colored layer having a high color material concentration, it is 30 parts by mass or more and 80 parts by mass or less, more preferably 40 parts by mass or more with respect to 100 parts by mass of the total solid content in the color material dispersion. It is preferable to mix at a ratio of 75 parts by mass or less.

<Dispersant>
In the present invention, a polymer having a structural unit represented by the general formula (I) is used as a dispersant. The structural unit represented by the general formula (I) has basicity and functions as an adsorption site for a coloring material.
By using the polymer having the structural unit represented by the general formula (I), the color material dispersion of the present invention improves the adsorption performance to the color material, and improves the dispersibility and dispersion stability of the color material. To do.

In general formula (I), A is a divalent linking group. Examples of the divalent linking group in A include an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH— group, a —COO— group, and an ether group having a carbon atom number of 1 to 10 (—R ′). —OR ″ —: R ′ and R ″ are each independently an alkylene group) and combinations thereof.
Among these, from the viewpoint of dispersibility, A in the general formula (I) is preferably a divalent linking group containing a —CONH— group or a —COO— group.

Examples of the hydrocarbon group in the hydrocarbon group that may include a hetero atom in R ² and R ³ include an alkyl group, an aralkyl group, and an aryl group.
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. It is preferably 1 or more and 18 or less, and more preferably a methyl group or an ethyl group.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. The number of carbon atoms in the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less. The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.
The hydrocarbon group containing a hetero atom has a structure in which a carbon atom in the hydrocarbon group is replaced with a hetero atom. Examples of the hetero atom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.
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, or a bromine atom.

The phrase “R ² and R ³ are bonded to each other to form a ring structure” means that R ² and R ³ form a ring structure through a nitrogen atom. The ring structure formed by R ² and R ³ may contain a hetero atom. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

In the present invention, among them, R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ² and R ³ are bonded to form a pyrrolidine ring. , A piperidine ring and a morpholine ring are preferable, and among them, at least one of R ² and R ³ is an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ² and R ^3. Are preferably bonded to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

Examples of the structural unit represented by the general formula (I) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and other alkyl group-substituted amino groups. Examples include group-containing (meth) acrylates, alkyl group-substituted amino group-containing (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and the like. Of these, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.
The structural unit represented by the general formula (I) may be composed of one type or may include two or more types of structural units.

The polymer having the structural unit represented by the general formula (I) preferably further includes a portion having solvent affinity from the viewpoint of improving dispersibility. As the solvent affinity site, a monomer having an ethylenically unsaturated bond that can be polymerized with a monomer that derives the structural unit represented by the general formula (I) is selected depending on the solvent so as to have solvent affinity. It is preferable to select and use as appropriate. As a standard, it is preferable to introduce a solvent-affinity site so that the solubility of the polymer at 23 ° C. is 50 (g / 100 g solvent) or more with respect to the solvent used in combination.
As the polymer used in the present invention, among others, a block copolymer can be formed from the viewpoint that the dispersibility and dispersion stability of the coloring material and the heat resistance of the resin composition can be improved and a colored layer having high brightness and high contrast can be formed. Or a graft copolymer is preferable and a block copolymer is particularly preferable. Hereinafter, particularly preferred block copolymers will be described in detail.

(Block copolymer)
When the block containing the structural unit represented by the general formula (I) is an A block, the structural unit represented by the general formula (I) is basic and the A block has an adsorption site for a coloring material. Function as. On the other hand, the B block not containing the structural unit represented by the general formula (I) functions as a block having solvent affinity. 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, and the like can be used. Among these, an AB block copolymer or an ABA block copolymer is preferable in terms of excellent dispersibility.

Examples of the structural unit constituting the B block include a monomer having an unsaturated double bond copolymerizable with the monomer that derives the structural unit represented by the general formula (I). The structural unit represented by (II) is preferred.

(In the general formula (II), A ′ is a direct bond or a divalent linking group, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ^8. Each of R ⁶ and R ⁷ is independently a hydrogen atom or a methyl group. R ⁸ is a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or a carbon atom number of 1 or more and 5 or less. It is an alkyl group.
The hydrocarbon group may have a substituent.
x represents an integer of 1 to 30, y represents an integer of 1 to 5, and z represents an integer of 1 to 18. )

The divalent linking group A ′ in the general formula (II) can be the same as A in the general formula (I). Among them, A ′ is preferably a divalent linking group containing a direct bond, —CONH— group, or —COO— group from the viewpoint of solubility in an organic solvent. From the viewpoint of heat resistance of the obtained polymer, solubility in propylene glycol monomethyl ether acetate (PGMEA) suitably used as a solvent, and a relatively inexpensive material, A ′ may be a —COO— group. preferable.

The hydrocarbon group for R ⁵ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Examples include 2-ethylhexyl group, 2-ethoxyethyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, adamantyl group, and lower alkyl group-substituted adamantyl group.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, and a propenyl group. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the polymer obtained, it is preferable that there is a double bond at the terminal of the alkenyl group.
Examples of the aliphatic hydrocarbon substituent such as an alkyl group or an alkenyl group include a nitro group and a halogen atom.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group, and may further have a substituent. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less.
Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, Furthermore, you may have a substituent. The number of carbon atoms in the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less.
Examples of the substituent on the aromatic ring such as an aryl group and an aralkyl group include straight chain and branched alkyl groups having 1 to 4 carbon atoms, alkenyl groups, nitro groups, and halogen atoms.
The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

In the above R ⁵ , x is an integer of 1 or more and 30 or less, preferably an integer of 1 or more and 26 or less, more preferably an integer of 1 or more and 18 or less, still more preferably 1 or more and 4 or less, particularly preferably 1 or more and 2 Y is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 4 or less, more preferably 2 or 3. z is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less.

The hydrocarbon group for R ⁸ can be the same as that shown for R ⁵ . Among these, the hydrocarbon group for R ⁸ is preferably an alkyl group having 1 to 18 carbon atoms from the viewpoint of excellent developability.
R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be linear, branched or cyclic.
Moreover, R ⁵ in the structural unit represented by the general formula (II) may be the same or different from each other.

The R ⁵ is preferably selected so as to be excellent in compatibility with a solvent described later. Specifically, for example, the solvent is generally used as a solvent for a colored resin composition for a color filter. When a commonly used solvent such as glycol ether acetate, ether or ester is used, a methyl group, an ethyl group, an isobutyl group, an n-butyl group, a 2-ethylhexyl group, a benzyl group or the like is preferable.
In the structural unit constituting the B block, as R ⁵ , — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z — It contains what is R ⁸ is, excellent developability, from the viewpoint of excellent suppression of development residue.

Furthermore, R ⁵ may be substituted with a substituent such as an alkoxy group, a hydroxyl group, an epoxy group, or an isocyanate group as long as the dispersion performance of the block copolymer is not hindered. After the synthesis of the polymer, the substituent may be added by reacting with the compound having the substituent.

In the present invention, the glass transition temperature (Tg) of the solvent-compatible block part of the block copolymer may be appropriately selected. From the viewpoint of heat resistance, the glass transition temperature (Tg) of the solvent-compatible block part is preferably 80 ° C. or higher, and more preferably 100 ° C. or higher.
The glass transition temperature (Tg) of the solvent-affinity block part in the present invention can be calculated by the following formula. Similarly, the glass transition temperature of the colorant affinity block portion and the block copolymer can be calculated.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the solvent-affinity block portion. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. The homopolymer glass transition temperature value (Tgi) of each monomer may adopt the value of Polymer Handbook (3rd Edition) (by J. Brandrup, EH Immergut (Wiley-Interscience, 1989)). it can.

The number of structural units constituting the solvent affinity block may be appropriately adjusted within a range where the colorant dispersibility is improved. Among them, the number of structural units constituting the solvent-affinity block part is 10 or more and 200 or less from the viewpoint that the solvent-affinity part and the colorant affinity part act effectively and improve the dispersibility of the colorant. Preferably, it is 10 or more and 100 or less, more preferably 10 or more and 70 or less.

The solvent-affinity block part may be selected so as to function as a solvent-affinity site, and the repeating unit constituting the solvent-affinity block part may be composed of one kind, or two or more kinds. The repeating unit may be included.

In particular, in the present invention, the dispersant is a polymer having a structure represented by the general formula (II) and having an amine value of 40 mgKOH / g to 120 mgKOH / g. It is preferable from the viewpoint of improving luminance and contrast without depositing foreign matters.
When the amine value is within the above range, the viscosity is excellent in stability over time and heat resistance, and is also excellent 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, more preferably 105 mgKOH / g or less.
The amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of a sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if it is an amino group that forms a salt with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so that the block copolymer itself used as the dispersant is 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 the effect of suppressing development residue. Among them, the acid value of the dispersant is more preferably 2 mgKOH / g or more from the viewpoint of more excellent development residue suppression effect. On the other hand, the acid value of the dispersant is preferably 0 mgKOH / g from the viewpoint of dispersibility and dispersion stability. In addition, 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 in development adhesion and solvent resolubility. preferable. Among these, the acid value of the dispersant is more preferably 12 mgKOH / g or less, and even more preferably 8 mgKOH / g or less, from the viewpoint that the development adhesion and the solvent re-solubility are improved.
In the dispersant used in the present invention, 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. On the other hand, the acid value of the block copolymer before salt formation is preferably 0 mgKOH / g from the viewpoint of dispersibility and dispersion stability. The upper limit of the acid value of the block copolymer before salt formation is preferably 18 mgKOH / g or less, more preferably 12 mgKOH / g or less, and even more preferably 8 mgKOH / g or less. . This is because the development adhesiveness and the solvent resolubility are improved.

Moreover, in this invention, it is preferable that the glass transition temperature of a dispersing agent is 30 degreeC or more from the point which image development adhesiveness improves. That is, whether the dispersant is a block copolymer before salt formation or a salt block copolymer, the glass transition temperature is preferably 30 ° C. or higher. When the glass transition temperature of the dispersant is low, it is particularly close to the developer temperature (usually about 23 ° C.), and the development adhesion may be lowered. This is presumably because when the glass transition temperature is close to the developer temperature, the movement of the dispersant increases during development, resulting in poor development adhesion. When the glass transition temperature is 30 ° C. or higher, the molecular motion of the dispersant during development is suppressed, so that it is estimated that the decrease in development adhesion is suppressed.
The glass transition temperature of the dispersant is preferably 32 ° C. or higher, more preferably 35 ° C. or higher, from the viewpoint of development adhesion. On the other hand, the temperature is preferably 200 ° C. or lower from the viewpoint of operability during use, such as easy precision weighing.
The glass transition temperature of the dispersant in the present invention can be determined by measuring by differential scanning calorimetry (DSC) according to JIS K7121.

When the colorant concentration is increased and the dispersant content is increased, the amount of the binder is relatively decreased, so that the colored resin layer is easily peeled off from the base 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 and glass transition temperature, 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 easily occurs during development.

From the above, in the present invention, the dispersant is a polymer having a 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 an acid value. 1 mgKOH / g or more and 18 mgKOH / g or less and a glass transition temperature of 30 ° C. or more is excellent in colorant dispersion stability, improves contrast, and suppresses generation of development residue when a colored resin composition is obtained. However, it is preferable from the viewpoint of excellent solvent resolubility and high development adhesion.

As the carboxy group-containing monomer, a monomer that can be copolymerized with a monomer having a structural unit represented by the general formula (I) and contains an unsaturated double bond and a carboxy group can be used. Examples of such monomers include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like. Also, 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 anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use acid anhydride group containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group. Among 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 range of the specific acid value. Although it is not limited, it is preferable that it is 0.05 mass% or more and 4.5 mass% or less with respect to the total mass of all the structural units of a block copolymer, and is 0.07 mass% or more and 3.7 mass% or less. More preferably.
Since the content ratio of the structural unit derived from the carboxy group-containing monomer is not less than the lower limit value, the effect of suppressing the development residue is expressed, and since it is not more than the upper limit value, the development adhesiveness is deteriorated and the solvent resolubility is reduced. Deterioration can be prevented.
In addition, the structural unit derived from a carboxy group containing monomer should just become said specific acid value, may consist of 1 type, and may contain 2 or more types of structural units.

Moreover, the monomer whose glass transition temperature (Tgi) of the homopolymer of the monomer is 10 ° C. or higher from the viewpoint that the glass transition temperature of the dispersant used in the present invention is a specific value or higher and development adhesion is improved. Is preferably 75% by mass or more, and more preferably 85% by mass or more in the B block.

In the block copolymer, the ratio m / n of the unit number m of the structural unit of the A block and the unit number n of the structural unit of the B block is in the range of 0.05 to 1.5. In view of the dispersibility and dispersion stability of the coloring material, it is more preferably within the range of 0.1 to 1.0.

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 preferably 2000 or more and 15000 or less, from the viewpoint of improving the colorant dispersibility and dispersion stability. 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 that 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. Although a block copolymer can be produced by a known method, it is preferable to produce it by a living polymerization method. This is because chain transfer and deactivation are unlikely to occur, a copolymer having a uniform molecular weight can be produced, and dispersibility and the like can be improved. Examples of the living polymerization method include a living anionic polymerization method such as a living radical polymerization method and a group transfer polymerization method, and a living cation polymerization method. A copolymer can be produced by sequentially polymerizing monomers by these methods. For example, a block copolymer can be produced by first producing the A block and polymerizing the structural units constituting the B block into the A block. In the above production method, the order of polymerization of the A block and the B block can be reversed. Also, the A block and the B block can be manufactured separately, and then the A block and the B block can be coupled.

Specific examples of the block copolymer having a block part containing the structural unit represented by the general formula (I) and a block part having a solvent affinity include, for example, those described in Japanese Patent No. 4911253 A block copolymer can be mentioned as a suitable thing.

In the present invention, from the viewpoint of the dispersibility and dispersion stability of the color material, at least a part of the amino groups in the polymer containing the structural unit represented by the general formula (I), an organic acid compound, It is also preferable to use a salt formed with a halogenated hydrocarbon as a dispersant (hereinafter, such a polymer may be referred to as a salt-type polymer).
Among them, the polymer containing a 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. And preferred from the viewpoint of excellent dispersion stability. Specific examples of the organic acid compound used for such a dispersant include, for example, organic acid compounds described in JP 2012-236882 A and the like.
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.

In the color material dispersion of the present invention, as the dispersant, at least one polymer having the structural unit represented by the general formula (I) is used, and the content thereof is the type of the color material to be used, and further described below. It is appropriately selected according to the solid content concentration in the colored resin composition for color filter to be performed.
The content of the dispersant is 3 parts by mass or more and 45 parts by mass or less, more preferably 5 parts by mass or more and 35 parts by mass with respect to 100 parts by mass of the total solid content in the colorant dispersion from the viewpoint of dispersibility and dispersion stability. It is preferable to mix | blend in the ratio of the mass part or less.
In particular, when forming a coating film or a colored layer having a high color material concentration, the content of the dispersant is 3 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the total solid content in the color material dispersion. More preferably, it is blended at a ratio of 5 parts by mass or more and 20 parts by mass or less.
In the present invention, the solid content is everything except the above-mentioned solvent, and includes monomers dissolved in the solvent.

<Solvent>
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the colorant dispersion and can dissolve or disperse them. A solvent can be used individually or in combination of 2 or more types.
Specific examples of the solvent include, for example, 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; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoate Glycol ether acetate solvents such as cis-3-methyl-1-butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate; carbitol acetates such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA) Solvents: diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl 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 monomer Glycol ether solvents such as ether and dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; tetrahydrofuran and the like Cyclic ether solvents such as: unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane; aromatic hydrocarbons such as toluene and xylene Organic solvents such as Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used from the viewpoint of solubility of other components. Among them, the solvent used in the present invention includes propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, butyl carbitol acetate (BCA), 3-methoxy It should be at least one selected from the group consisting of -3-methyl-1-butyl acetate, ethyl lactate, methyl 2-hydroxypropionate, and 3-methoxybutyl acetate. It is preferable from the point of aptitude.

It is also preferable to use a mixed solvent containing two or more kinds of solvents from the viewpoints of developability and solvent re-solubility.

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

As the second solvent (a solvent other than the first solvent), a solvent having an alcoholic hydroxyl group or a solvent having a boiling point of 150 ° C. or higher is preferable. A 2nd solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.

When a solvent having an alcoholic hydroxyl group is used as the second solvent, the dispersibility is improved and the solvent resolubility is likely to be improved.
Examples of the solvent having an alcoholic hydroxyl group include the alcohol solvent, the carbitol solvent, and the glycol ether solvent. Specific examples include propylene glycol monomethyl ether (boiling point 121 ° C.), 3-methoxy- Examples include 3-methyl-1-butanol (boiling point 174 ° C.).

In the case of using a mixed solvent, 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 still more preferably 2% by mass or less in the total solvent. Moreover, 0.1 mass% or more is preferable, 0.3 mass% or more is more preferable, and 1 mass% or more is still more preferable.
Within the above range, the solubility of the dispersant tends to be good, and since the dissolution of the dispersant in the first solvent is not hindered, the dispersion stability tends to be good.

When the first solvent is a solvent having a boiling point of less than 150 ° C., use of a solvent having a boiling point of 150 ° C. or more as the second solvent makes it difficult for drying unevenness to occur, hardly causes foreign matter, and tends to improve the solvent resolubility. .
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.

When using a mixed solvent, 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. Moreover, 3 mass% or more is preferable, 5 mass% or more is more preferable, and 10 mass% or more is still more preferable.
Within the above range, drying unevenness is unlikely to occur, and the drying time does not become too long and the productivity tends to be good.

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

In the color material dispersion of the present invention, the solvent as described above is usually preferably in the range of 55% by mass to 95% by mass with respect to the total amount of the color material dispersion containing the solvent. It is preferably in the range of not less than mass% and not more than 90 mass%, more preferably in the range of not less than 70 mass% and not more than 88 mass%. When there is too little solvent, a viscosity will rise and a dispersibility will fall easily. Moreover, when there are too many solvents, color material density | concentration will fall and it may be difficult to achieve to a target chromaticity coordinate.

<Other ingredients>
As long as the effect of this invention is not impaired, you may mix | blend a dispersion auxiliary resin and another component with the coloring material dispersion liquid of this invention as needed.
Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified by a colored resin composition for a color filter described later. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant particles to come into contact with each other, and may have the effect of stabilizing the dispersion or reducing the dispersant due to the dispersion stabilizing effect.
Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, and UV absorbers. Etc.

The color material dispersion of the present invention is used as a preliminary preparation for preparing a colored resin composition for a color filter described later. That is, the color material dispersion is P / V (color material component mass in the composition) / (color material in the composition), which is preliminarily prepared in the previous stage of preparing the color resin composition for color filter described later. It is a colorant dispersion having a high ratio (solid content other than components). Specifically, the ratio of (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 colorant dispersion and each component described below, a colored resin composition for color filters having excellent dispersibility can be prepared.

[Production method of colorant dispersion]
In the present invention, the method for producing the color material dispersion is not particularly limited as long as the color material is a method for obtaining a color material dispersion dispersed in a solvent with the dispersant. Especially, it is preferable to set it as either of the following two manufacturing methods from the point which is excellent in the dispersibility and dispersion stability of a coloring material.

That is, the first method for producing a colorant dispersion according to the present invention includes a step of preparing the dispersant and a step of dispersing the colorant in the presence of the dispersant in a solvent. . Two or more kinds of color materials may be co-dispersed in the presence of the dispersant in a solvent, or one or more kinds of color materials are dispersed or co-dispersed, and then two or more kinds of color material dispersions are mixed. By doing so, the colorant dispersion of the present invention may be obtained.

In addition, when a dispersant that is a salt type block copolymer is used, the second method for producing the colorant dispersion according to the present invention includes a solvent, the block copolymer, the organic acid compound, and halogenated carbonization. While mixing hydrogen and a coloring material, salt formation of at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) with the organic acid compound or the halogenated hydrocarbon is performed. And a step of dispersing the coloring material. Even when the color material is dispersed while forming such a salt, two or more kinds of color materials may be co-dispersed, or after one or more kinds of color materials are dispersed or co-dispersed, two or more kinds of colors are dispersed. The color material dispersion of the present invention may be obtained by mixing the material dispersion.

In the first production method and the second production method, the color material can be dispersed using a conventionally known disperser.
Specific examples of the dispersing machine include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibration ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 mm or more and 3.0 mm or less, more preferably 0.05 or more and 2.0 mm or less.

[Colored resin composition for color filter]
The colored resin composition for a color filter according to the present invention is a colored resin composition for a color filter containing a coloring material, a dispersant, a binder component, and a solvent,
The color material includes a red color material and a yellow color material,
The yellow color material is at least one anion selected from the group consisting of mono-, di-, tri- and tetraanions of the azo compound represented by the general formula (A) and the azo compound having a tautomer structure thereof; An ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the general formula (B) Including
The dispersant is a polymer having a structural unit represented by the general formula (I).
The colored resin composition for a color filter of the present invention is excellent in color material dispersion stability like the color material dispersion of the present invention, and as described in the section of the color material dispersion of the present invention, the phase difference While the value is reduced, it is possible to form a colored layer having high luminance and high contrast and excellent color reproducibility.

The colored resin composition for a color filter of the present invention contains at least a colorant, a dispersant, a binder component, and a solvent, and further contains other components as long as the effects of the present invention are not impaired. You may do it. Hereinafter, although each component contained in the colored resin composition for a color filter of the present invention will be described, the red color material that is an essential component among the color materials, the specific yellow color material, the dispersant, and the solvent are described above. Since it is the same as that described in the color material dispersion of the present invention, the description here is omitted.

<Color material>
The color material in the colored resin composition for a color filter of the present invention includes a red color material and the specific yellow color material as essential components, but in order to adjust the color tone, other color materials are used in combination. Also good.
It is not particularly limited as long as it can form a desired color when forming the color layer of the color filter, and various organic pigments, inorganic pigments, dispersible dyes may be used alone or in combination of two or more. Can be used. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. Examples of the organic pigment include compounds classified as pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. .) Can be listed with numbers.
The dispersible dyes include dyes that are dispersible by imparting various substituents to the dyes or insolubilizing in a solvent by using a known lake (chlorination) technique, and low solubility. Examples thereof include dyes that can be dispersed by using in combination with a solvent. By using such a dispersible dye in combination with the dispersant, the dispersibility and dispersion stability of the dye can be improved.
The dispersible dye can be appropriately selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.
As a guide, if the amount of dye dissolved in 10 g of solvent (or mixed solvent) is 10 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

Among other color materials, other yellow color materials and orange color materials not included in the red color material are preferably used.
Examples of other color materials include, but are not limited to, the following.
Other yellow color materials include C.I. I.

Pigment Yellow

1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185 and the like.

In the colored resin composition for a color filter of the present invention, the content ratio of the red color material relative to the entire color material is not particularly limited as long as it is appropriately adjusted according to the desired chromaticity.
Among them, it is preferable that the red color material is contained in an amount of 35% by mass to 99% by mass with respect to the total amount of the color material from the viewpoint of increasing the color reproducibility and increasing the contrast while reducing the retardation value. More preferably, it is contained in an amount of not less than 98% by mass and not more than 98% by mass, and still more preferably not less than 45% by mass and not more than 97% by mass.

Further, the total content of the yellow color material is 1% by mass or more and 65% by mass or less with respect to the total amount of the color material from the viewpoint of widening the color reproducibility and increasing the contrast while the retardation value is reduced. Is preferably 2% by mass or more and 60% by mass or less, more preferably 3% by mass or more and 55% by mass or less.
Further preferred.

The colored resin composition for a color filter of the present invention comprises mono-, di-, tri- and tetraanions of the azo compound represented by the general formula (A) in the yellow color material and the azo compound having a tautomer structure thereof. At least one anion selected from the group and ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn; The total content of the compound represented by the formula (B) (the specific yellow color material) may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, the total content of the specific yellow color material is 10% by mass or more and 100% by mass with respect to the total amount of the yellow color material from the viewpoint of increasing the color reproducibility and increasing the contrast while the retardation value is reduced. Is preferably 15% by mass or more and 100% by mass or less, more preferably 20% by mass or more and 100% by mass or less, and further preferably 25% by mass or more and 100% by mass or less. Even more preferred.

Moreover, in the colored resin composition for color filters of this invention, in the range which does not impair the effect of this invention, other color materials other than a red color material and a yellow color material are further included in the color material. However, the total content of the red color material and the yellow color material is preferably 60% by mass or more and 100% by mass or less and 70% by mass or more and 100% by mass or less with respect to the total color material. Is more preferable, and it is still more preferable that it is 80 to 100 mass%.

<Binder component>
The colored resin composition for a color filter of the present invention contains a binder component in order to impart film formability and adhesion to the surface to be coated. In order to impart sufficient hardness to the coating film, it is preferable to contain a curable binder component. It does not specifically limit as a curable binder component, The curable binder component used in forming the coloring layer of a conventionally well-known color filter can be used suitably.
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 light, electron beam, and the like, and a thermosetting resin that can be polymerized and cured by heating. What contains the thermosetting binder component to contain can be used.

When using a photolithography process when forming a colored layer, the photosensitive binder component which has alkali developability is used suitably. In addition, you may further use a thermosetting binder component for the photosensitive binder component.
Examples of the photosensitive binder component include a positive photosensitive binder component and a negative 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 photosensitizing 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 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, and can be appropriately selected from those that act as a binder resin and are soluble in an alkali developer used for pattern formation.
In the present invention, the alkali-soluble resin can be based on an acid value of 40 mgKOH / g or more.
A preferred alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group, and specifically, acrylic resins such as an acrylic copolymer having a carboxy group and a styrene-acrylic copolymer having a carboxy group. And epoxy (meth) acrylate resins having a carboxy group. Among these, particularly preferred are 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. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. In addition, acrylic resins such as acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination.

An acrylic resin such as an acrylic copolymer having a structural unit having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group includes, for example, a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, a copolymer. It is a (co) polymer obtained by (co) polymerizing other polymerizable monomers by a known method.
Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. It is done. Also, 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 anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. By having a hydrocarbon ring that is a bulky group in the alkali-soluble resin, shrinkage during curing is suppressed, peeling from the substrate is eased, and substrate adhesion is improved. Further, the present inventors have found that the use of an alkali-soluble resin having a hydrocarbon ring suppresses the solvent resistance of the obtained colored layer, particularly the swelling of the colored layer. Although the action is unclear, the bulky hydrocarbon ring in the colored layer suppresses the movement of molecules in the colored layer, resulting in an increase in the strength of the coating and suppression of swelling by the solvent. It is estimated that.
Examples of such hydrocarbon rings include aliphatic hydrocarbon rings that may have a substituent, aromatic hydrocarbon rings that may have a substituent, and combinations thereof. May have a substituent such as an alkyl group, a carbonyl group, a carboxyl 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 a divalent or higher group.

Specific examples of the hydrocarbon ring include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), and adamantane. Ring: aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, phenanthrene, fluorene, etc .; chain polycycle such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, cardo structure (9,9-diarylfluorene), etc. Is mentioned.

When an aliphatic hydrocarbon ring is included as the hydrocarbon ring, it is preferable from the viewpoint of improving the heat resistance and adhesion of the colored layer and improving the luminance of the obtained colored layer.
Moreover, when the said cardo structure is included, the sclerosis | hardenability of a colored layer improves and it is especially preferable from the point which improves solvent resistance (NMP swelling suppression).

The alkali-soluble resin preferably has a bridged 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 bridged cyclic hydrocarbon ring include norbornane, isobornane, adamantane, tricyclo [5.2.1.0 (2,6)] decane, tricyclo [5.2.1.0 (2,6)]. Decene, tricyclopentene, tricyclopentane, tricyclopentadiene, dicyclopentadiene; groups in which a part of these groups are substituted with a substituent are mentioned.
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, and a halogen atom.

The lower limit of the number of carbon atoms in the crosslinked cyclic 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 alkali developer. The upper limit is preferably 12 or less, and particularly preferably 10 or less.

The alkali-soluble resin preferably has a maleimide structure represented by the following general formula (III).

[In General Formula (III), R ^M represents an optionally substituted hydrocarbon ring. ]

When the alkali-soluble resin has a maleimide structure represented by the general formula (III), it has a nitrogen atom in the hydrocarbon ring, and therefore is a basic polymer that has a structural unit represented by the general formula (I). The compatibility with the dispersant is very good, the development speed is high, and the effect of suppressing development residue is improved.

In R ^M of the general formula (III), specific examples of the optionally substituted hydrocarbon ring, those similar to the specific example of the hydrocarbon ring.
For example, an aliphatic hydrocarbon ring such as cyclopentyl group, cyclohexyl group, cyclooctyl group, phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, methoxyphenyl group, benzyl group, hydroxyphenyl group, An aromatic hydrocarbon ring such as a naphthyl group, and a group in which a part of these groups is substituted with a substituent are exemplified.

In the alkali-soluble resin used in the present invention, it is easy to adjust the amount of each constituent unit by using an acrylic copolymer having a constituent unit having a hydrocarbon ring separately from the constituent unit having a carboxy group. This is preferable because the amount of the structural unit having a hydrocarbon ring is increased to easily improve the function of the structural unit.
The acrylic copolymer having a structural unit having a carboxy group and the hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned “other monomer capable of copolymerization”. be able to.

Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl. (Meth) acrylate, styrene, etc. are mentioned. From the point that the cross-sectional shape of the colored layer after development has a large effect of being maintained in the heat treatment, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl ( It is preferable to use at least one selected from (meth) acrylate, benzyl (meth) acrylate, and styrene.

The alkali-soluble resin used in the present invention preferably has an ethylenic double bond in the side chain. In the case of having an ethylenic double bond, the alkali-soluble resins, or the alkali-soluble resin and the polyfunctional monomer can form a cross-linked bond in the curing step of the resin composition at the time of producing the color filter. The film strength of the cured film is further improved and the development resistance is improved, and the thermal contraction of the cured film is suppressed and the adhesiveness with the substrate is excellent.
The method for introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method of introducing an ethylenic double bond into a side chain by adding a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, to the carboxyl group of the alkali-soluble resin Or by introducing a structural unit having a hydroxyl group into a copolymer, adding a compound having an isocyanate group and an ethylenic double bond in the molecule, and introducing an ethylenic double bond into the side chain. Etc.

The alkali-soluble resin of the present invention may further contain other structural units such as a structural unit having an ester group such as methyl (meth) acrylate and ethyl (meth) acrylate. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the colored resin composition for a color filter, but also functions as a component that improves the solubility in a solvent and further the solvent resolubility.

The alkali-soluble resin in the present invention is preferably an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, It is an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxyl group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenic double bond. Is more preferable.

The alkali-soluble resin can be made into an alkali-soluble resin having desired performance by appropriately adjusting the charged amount of each structural unit.

The charged amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 5% by mass or more and more preferably 10% by mass or more with respect to the total amount of the monomer from the viewpoint of obtaining a good pattern. On the other hand, from the viewpoint of suppressing film roughness on the pattern surface after development, the amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 50% by mass or less, and 40% by mass or less with respect to the total amount of monomers. More preferably.
When the proportion of the carboxyl group-containing ethylenically unsaturated monomer is equal to or higher than the lower limit, the coating film obtained has sufficient solubility in an alkaline developer, and the proportion of the carboxyl group-containing ethylenically unsaturated monomer is the upper limit. When it is below, there is a tendency that the formed pattern is not easily detached from the substrate and the pattern surface is not easily roughened during development with an alkali developer.

In addition, in an acrylic resin such as an acrylic copolymer having a structural unit having an ethylenic double bond and a styrene-acrylic copolymer, which is more preferably used as an alkali-soluble resin, an epoxy group and an ethylenic double bond are used. The amount of the compound having a bond is preferably 10% by mass or more and 95% by mass or less, and more preferably 15% by mass or more and 90% by mass or less with respect to the charged amount of the carboxyl group-containing ethylenically unsaturated monomer.

The preferred weight average molecular weight (Mw) of the carboxy group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. If it is less than 1,000, the binder function after curing may be remarkably lowered. If it exceeds 50,000, pattern formation may be difficult during development with an alkali developer.
The weight average molecular weight (Mw) of the carboxy group-containing copolymer can be measured by a Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxy group, Epoxy (meth) obtained by making the reaction product of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride can be appropriately selected from known ones. The epoxy (meth) acrylate resin having a carboxy group may be used alone or in combination of two or more.

The alkali-soluble resin is preferably selected from those having an acid value of 50 mgKOH / g or more from the viewpoint of developability (solubility) with respect to an alkaline aqueous solution used for the developer. The alkali-soluble resin preferably has an acid value of 70 mgKOH / g or more and 300 mgKOH / g or less from the viewpoint of developability (solubility) with respect to an aqueous alkali solution used for the developer and adhesion to the substrate. It is preferable that it is 80 mgKOH / g or more and 280 mgKOH / g or less.
In the present invention, the acid value can be measured according to JIS K 0070.

The ethylenically unsaturated bond equivalent in the case where the side chain of the alkali-soluble resin has an ethylenically unsaturated group improves the film strength of the cured film, improves the development resistance, and obtains the effect of excellent adhesion to the substrate. From the viewpoint, it is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. When the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Moreover, since the ratio of other structural units, such as the structural unit which has the said carboxy group, and the structural unit which has a hydrocarbon ring, can be relatively increased if it is 100 or more, it is excellent in developability and heat resistance. Yes.
Here, the ethylenically unsaturated bond equivalent is a weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).

Formula (1)
Ethylenically unsaturated bond equivalent (g / mol) = W (g) / M (mol)
(In Formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).)

The ethylenically unsaturated bond equivalent is determined, for example, by measuring the number of ethylenic double bonds contained in 1 g of the alkali-soluble resin in accordance with the test method for the iodine value described in JIS K 0070: 1992. It may be calculated.

The alkali-soluble resin used in the colored resin composition for color filters may be used alone or in combination of two or more, and the content is not particularly limited, but for color filters. The alkali-soluble resin is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 40% by mass or less, based on the total solid content of the colored resin composition. When the content of the alkali-soluble resin is not less than the above lower limit, sufficient alkali developability can be easily obtained, and when the content of the alkali-soluble resin is not more than the above upper limit, film roughness or lack of pattern can be caused during development. It is easy to suppress.

(Polyfunctional monomer)
The polyfunctional monomer used in the colored resin composition for a color filter is not particularly limited as long as it can be polymerized by the photoinitiator, and a compound having two or more ethylenically unsaturated double bonds is usually used. A polyfunctional (meth) acrylate is preferably used, and particularly has two or more acryloyl groups or methacryloyl groups.
Such polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples include those described in JP2013-029832A.

These polyfunctional (meth) acrylates may be used alone or in combination of two or more. Moreover, when the photocurability (high sensitivity) is requested | required of the colored resin composition for color filters of this invention, a polyfunctional monomer has three (trifunctional) or more of the double bond which can superpose | polymerize. Preferred are poly (meth) acrylates of polyhydric alcohols having a valence of 3 or more and their dicarboxylic acid modified products. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meta) ) Acrylate, modified succinic acid of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate Dipentaeri modified from succinic acid Ritoruhekisa (meth) acrylate are preferable.

Although there is no restriction | limiting in particular in content of the said polyfunctional monomer used in the colored resin composition for color filters, Preferably a polyfunctional monomer is 5 mass% or more and 60 with respect to the solid content whole quantity of the colored resin composition for color filters. It is within the range of 10% by mass or less and more preferably 40% by mass or less. When the content of the polyfunctional monomer is not less than the above lower limit, photocuring proceeds sufficiently, and the exposed portion can suppress elution during development, and when the content of the polyfunctional monomer is not more than the above upper limit, alkali development Sex is enough.

(Photoinitiator)
There is no restriction | limiting in particular as an initiator used in the colored resin composition for color filters of this invention, From the conventionally known various initiators, it can be used 1 type or in combination of 2 or more types.
Initiators include aromatic ketones, benzoin ethers, halomethyl oxadiazole compounds, α-amino ketones, biimidazoles, N, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone, etc. Can do. 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. , Biimidazoles such as 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, halo such as 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole Methyloxadiazole compounds, halomethyl-S-triazine compounds such as 2- (4-butoxy-naphth-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-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4 -Benzoyl-4'-methyldiphenyl sulfide, benzylmethyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 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- For example, propanone.
Among them, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1- Butanone, 4,4′-bis (diethylamino) benzophenone, and diethylthioxanthone are preferably used. Furthermore, a sensitivity is obtained by combining an α-aminoacetophenone initiator such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one with a thioxanthone initiator such as diethylthioxanthone. It is preferable from the viewpoint of suppressing adjustment and water stain and improving development resistance.
The total content of α-aminoacetophenone initiator and thioxanthone initiator is preferably 5% by mass or more and 15% by mass or less based on the total solid content of the colored resin composition. When the amount of the initiator is 15% by mass or less, sublimates during the production process are 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 photoinitiator from the viewpoint of improving sensitivity. By using an oxime ester photoinitiator, in-plane line width variations are easily suppressed when forming a fine line pattern. Furthermore, by using an oxime ester photoinitiator, the development resistance is improved, and the effect of suppressing the occurrence of water stain tends to be increased. In addition, water stain means that, when a component that enhances alkali developability is used, a trace of water stain is generated after rinsing with pure water after alkali development. Such a water stain disappears after post-baking, so there is no problem as a product. Arise. Therefore, if the inspection sensitivity of the inspection apparatus is lowered in the appearance inspection, the yield of the final color filter product is lowered as a result, which becomes a problem.
As the oxime ester-based photoinitiator, those having an aromatic ring are preferable from the viewpoint of reducing contamination of the colored resin composition for color filters and degradation of the apparatus due to decomposition products, and having condensed rings including aromatic rings. More preferred are those having a condensed ring containing a benzene ring and a heterocycle.
Examples of oxime ester photoinitiators include 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime), JP 2000-80068 A, JP 2001-233842 A, Special Table 2010-527339, Special Table 2010-527338, It can be appropriately selected from oxime ester photoinitiators described in JP2013-041153A. As commercially available products, Irgacure OXE-02 having a carbazole skeleton (manufactured by BASF), Adeka Arcles NCI-831 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changzhou Power Electronics Co., Ltd.), ADEKA having a diphenyl sulfide skeleton ARKULS NCI-930 (manufactured by ADEKA), TR-PBG-345, TR-PBG-3057 (manufactured by Changzhou Power Electronics New Materials), Irgacure OXE-01 (manufactured by BASF), TR-PBG- having a fluorene skeleton 365 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.) or the like may be used. In particular, it is preferable to use an oxime ester photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton from the viewpoint of luminance. It is preferable to use an oxime ester photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.
Further, it is preferable to use two or more kinds of oxime ester photoinitiators in terms of easily improving luminance and development resistance and having a high effect of suppressing water stain generation. In particular, the combined use of two types of oxime ester photoinitiators having a diphenyl sulfide skeleton, or the combined use of an oxime ester photoinitiator having a diphenyl sulfide skeleton and an oxime ester photoinitiator having a fluorene skeleton is high in luminance and heat resistance. It is preferable from the point of high property. In addition, the combined use of an oxime ester-based photoinitiator having a carbazole skeleton and an oxime ester-based photoinitiator having a fluorene skeleton or an oxime ester-based photoinitiator having a diphenyl sulfide is excellent in sensitivity and water stain generation suppression effect. Is preferable.

In addition, it is preferable to use a photoinitiator having a tertiary amine structure in combination with an oxime ester photoinitiator from the viewpoint of suppressing water stain and improving sensitivity. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure that is an oxygen quencher in the molecule, radicals generated from the initiator are hardly deactivated by oxygen, and sensitivity can be improved. is there. Examples of commercially available photoinitiators having the tertiary amine structure include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-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, Kawaguchi Pharmaceutical).
In addition, combining an oxime ester photoinitiator with a thioxanthone initiator is preferable from the viewpoint of adjusting sensitivity, suppressing water stain, and improving development resistance. Two or more oxime ester photoinitiators and a thioxanthone photoinitiator are preferable. A combination of initiators is preferable in that brightness and development resistance are improved, sensitivity adjustment is easy, water stain generation suppression effect is high, and development resistance 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 or more and 100 parts by mass or less, preferably 5 parts by mass with respect to 100 parts by mass of the polyfunctional monomer. The amount is 60 parts by mass or less. If this content is not less than the above lower limit, the photocuring is sufficiently advanced and the exposed portion is prevented from being eluted during development, while if it is not more than the above upper limit, the yellowing of the resulting colored layer is weakened and the luminance is reduced. It can suppress that it falls.
Moreover, as a photoinitiator used in the colored resin composition for color filters of the present invention, the total content of two or more oxime ester photoinitiators is based on the total solid content of the colored resin composition for color filters. 0.1% by mass or more and 12.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less in the range of sufficiently exhibiting the combined effect of these photoinitiators. To preferred.

The binder component used in the colored resin composition for a color filter of the present invention preferably has a total content of 35% by mass to 97% by mass with respect to the total solid content of the colored resin composition for a color filter. It is more preferable to blend in a proportion of not less than mass% and not more than 96 mass%. If it is more than the said lower limit, the colored layer excellent in hardness and the adhesiveness with a board | substrate can be obtained. Moreover, if it is below the said upper limit, it is excellent in developability and generation | occurrence | production of the fine wrinkles by heat shrink is also suppressed.

<Optional components>
The colored resin composition for a color filter may contain various additives as necessary.
Examples of additives include, in addition to antioxidants, mercapto compounds, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters. Etc.

It is preferable that the colored resin composition for a color filter of the present invention further contains an antioxidant because heat resistance is improved, fading of the coloring material is suppressed, and luminance is improved. Moreover, it is preferable that the colored resin composition for color filters of the present invention further contains an antioxidant from the viewpoint of improving the adhesion of the SiN substrate.
The antioxidant may be appropriately selected from conventionally known antioxidants. Specific examples of antioxidants include, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like. From the viewpoint, it is preferable to use a hindered phenol-based antioxidant.

The hindered phenol antioxidant contains at least one phenol structure, and has a structure in which a substituent having 4 or more carbon atoms is substituted on at least one of the 2-position and 6-position of the hydroxyl group of the phenol structure. Means an antioxidant.
Specific examples of the hindered phenol antioxidant include, for example, dibutylhydroxytoluene (BHT), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010, 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), 6- (4-hydroxy-3,5-di-tert-butylanilino) -2 , 4-Bis (octylthio) -1,3,5-triazine (trade name: Irganox 565) BASF), 2,2′-thiodiethylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1035, manufactured by BASF), 1,2-bis [3- (4-hydroxy-3,5-di-tert-butylphenyl) propionyl] hydrazine (trade name: Irganox MD1024, manufactured by BASF), 3- (4-hydroxy-3,5-diisopropylphenyl) propionic acid Octyl (trade name: Irganox 1135, manufactured by BASF), 4,6-bis (octylthiomethyl) -o-cresol (trade name: Irganox 1520L, manufactured by BASF), N, N′-hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide] (trade name: Irganox) 1098, manufactured by BASF), 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 259, manufactured by BASF), 1-dimethyl- 2-[(3-tert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: ADK STAB AO-80 , Manufactured by Adeka), bis (3-tert-butyl-4-hydroxy-5-methylbenzenepropionic acid) ethylene bis (oxyethylene) (trade name: Irganox 245, manufactured by BASF), 1,3,5-tris [ [4- (1,1-dimethylethyl) -3-hydroxy-2,6-dimethylphenyl] methyl] -1,3,5-triazine- , 4,6 (1H, 3H, 5H) -trione (trade name: Irganox 1790, manufactured by BASF), 2,2′-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilyzer MDP- S, manufactured by 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-hydroxy Diethyl benzylphosphonate (trade name: Irgamod 195, manufactured by BASF), 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl acrylate (trade name: Sumilizer GM, manufactured by Sumitomo Chemical Co., Ltd., 4,4'-thiobis (6-tert-butyl-m-cresol) (trade name: Sumilizer WX R, manufactured by Sumitomo Chemical Co., Ltd.), 6,6'-di -tert- butyl-4,4'-Buchiridenji -m- cresol (trade name: ADK STAB AO-40, manufactured by ADEKA), and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.
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. .
In addition, a hindered phenol antioxidant having a molecular weight of 1000 or less and a molecular weight per phenolic hydroxyl group of 280 equivalents or less, and further a molecular weight of 500 or less and a molecular weight per phenolic hydroxyl group of 200 equivalents or less. Is preferable because a colored layer with improved brightness and contrast can be formed while the retardation value is reduced. Such an antioxidant has high fluidity and many active points per weight, so that radical trapping suppresses color material aggregation due to rapid curing shrinkage during exposure and post-baking, It is presumed that the above effect is easily obtained due to suppression of yellowing. Examples of such an antioxidant include 6,6′-di-tert-butyl-4,4′-butylidene di-m-cresol (trade name: ADK STAB AO-40, manufactured by ADEKA).

In the present invention, it is preferable to use a latent antioxidant as the antioxidant because a colored layer with improved contrast can be formed while the retardation value is reduced. The use of a latent antioxidant increases the radical trapping effect, especially during post-baking, so it is estimated that the above effect is likely to be obtained due to the suppression of color material aggregation due to rapid curing shrinkage during post-baking. Is done. In the present invention, the latent antioxidant is a compound having a protecting group that can be removed by heating, and exhibiting an antioxidant function when the protecting group is eliminated. Among them, those which are easy to remove the protecting group by heating at 150 ° C. or higher are preferable. For example, the latent antioxidant as described in international publication 2014/021023 is mentioned.
Examples of the latent antioxidant suitably used in the present invention include latent hindered phenol antioxidants in which the phenolic hydroxyl group of the hindered phenol antioxidant is protected with a protecting group that can be removed by heating. . As latent hindered phenolic antioxidants, phenolic hydroxyl groups of hindered phenolic antioxidants, acid anhydrides, acid chlorides, Boc reagents, alkyl halide compounds, silyl chloride compounds, allyl ether compounds, etc. And the reaction product. As the latent hindered phenol antioxidant, a structure in which the hydrogen of the phenol group of the hindered phenol antioxidant is substituted with a carbamate protecting group such as a t-butoxycarbonyl group is preferably used. Examples include, but are not limited to, the following chemical formulas (a) to (c).

The method for producing the latent antioxidant is not particularly limited. For example, JP-A-57-111375, JP-A-3-173843, JP-A-6-128195, JP-A-7-207771, JP-A-7-252191, Special Tables. Obtained by reacting a phenolic compound produced by the method described in each publication of 2004-501128 with an acid anhydride, acid chloride, Boc reagent, alkyl halide compound, silyl chloride compound, allyl ether compound, etc. Can do. Moreover, you may use a commercial item.

The colored resin composition for a color filter of the present invention is preferably used as a colored resin composition in combination with the oxime ester photoinitiator and an antioxidant from the viewpoint of improving luminance by a synergistic effect.

As content of antioxidant, it is preferable that antioxidant is 0.05 mass part or more and 10.00 mass part or less with respect to 100 mass parts of total solids in a colored resin composition, 0.10 More preferably, it is at least part by mass and no more than 5.00 parts by mass. If it is more than the said lower limit, it is excellent in heat resistance and light resistance. On the other hand, if it is below the said upper limit, the colored resin composition of this invention can be made into a highly sensitive photosensitive resin composition.

When the antioxidant is used in combination with the oxime ester photoinitiator, the content of the antioxidant is 1 part by mass of the antioxidant with respect to 100 parts by mass of the total amount of the oxime ester photoinitiator. It is preferably 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and still more preferably 5 parts by mass or more and 45 parts by mass or less. If it is in the said range, it is excellent in the effect of the said combination.

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 stain.
In addition, the colored resin composition for a color filter of the present invention contains a combination of the oxime ester photoinitiator and a mercapto compound as a photosensitive colored resin composition, which improves development resistance and generates water stains. This is preferable because the suppression effect is further improved, and when forming a fine line pattern, the linearity is further improved, and the ability to form a fine line pattern as designed for the mask line width is improved. “Improved linearity” means that the end of the colored layer formed in the development step after applying the colored composition has few irregularities and is linear or substantially linear.

The mercapto compound can function as a chain transfer agent, and has the property of receiving radicals from slowly reacting radicals to accelerate the reaction and improve curability.
Examples of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, and 3-mercaptopropionic acid. Methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxy Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), Pentaeri Lithol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) and the like.
As the mercapto compound, one or a combination of two or more may be used. 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. It is preferable from the viewpoint that the crosslink density is increased and the effect of suppressing water stain is improved.
In addition, 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 from the viewpoint that even when stored for a long period of time, a good water stain suppression effect is easily maintained. Further, a polyfunctional secondary mercapto compound having two or more secondary mercapto groups in one molecule is more preferable.

The content of the mercapto compound used in the colored resin composition for color filter is not particularly limited, but the mercapto compound is 0.2% by mass or more and 7% by mass with respect to the total solid content of the colored resin composition for color filter. % Or less, and more preferably in the range of 0.5% by mass or more and 5% by mass or less from the viewpoint of sufficiently exhibiting the above effects.

Further, it is preferable that the colored resin composition for a color filter of the present invention further contains an ultraviolet absorber from the viewpoint that a colored layer with improved contrast can be formed while the retardation value is reduced. The effect of improving these characteristics is presumed to be due to suppression of color material aggregation due to rapid curing shrinkage in the exposure process. What is necessary is just to select an ultraviolet absorber suitably from a conventionally well-known thing. Specific examples of the ultraviolet absorber include benzotriazole compounds, benzophenone compounds, triazine compounds, and the like. Among them, it is preferable to use a benzotriazole-based compound from the viewpoint that a colored layer with improved contrast can be formed while the retardation value is reduced.

Examples of the benzotriazole compounds include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3 [3- t-Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-t-butyl-4-hydroxy-5- (5- Chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3- t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2- Droxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H -Benzotriazol-2-yl)-(1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester compounds, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3 3-tetramethylbutyl) phenol and the like, but are not limited thereto.
Examples of commercially available products include “TINUVIN P”, “TINUVIN PS”, “TINUVIN 109”, “TINUVIN 234”, “TINUVIN 326”, “TINUVIN 328”, “TINUVIN 329”, and “TINUVIN 384-2” manufactured by BASF. ”,“ TINUVIN 900 ”,“ TINUVIN 928 ”,“ TINUVIN 99-2 ”,“ TINUVIN 1130 ”, and the like.

As the benzotriazole-based compound, a benzotriazole-based compound represented by the following general formula (IV) is preferable because a colored layer with improved contrast can be formed while the retardation value is reduced.

(In the general formula (IV), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a phenyl group, and X represents a hydrogen atom or a chlorine atom. .)

In general formula (IV), among them, R ¹² is preferably a methyl group, a t-butyl group, a t-amyl group, a t-octyl group, or an α, α-dimethylbenzyl group, and R ¹¹ is a hydrogen atom An atom, a t-butyl group, a t-amyl group, or an α, α-dimethylbenzyl group is preferable.

Although there is no restriction | limiting in particular in content of the ultraviolet absorber used in the colored resin composition for color filters, an ultraviolet absorber is 0.05 mass part or more with respect to 100 mass parts of total solids in a colored resin composition. It is preferably 10.00 parts by mass or less, and more preferably 0.10 parts by mass or more and 5.00 parts by mass or less. If it is more than the said lower limit, it is excellent in heat resistance and light resistance. On the other hand, if it is below the said upper limit, the colored resin composition of this invention can be made into a highly sensitive photosensitive resin composition.

The colored resin composition for a color filter of the present invention is preferably used as a colored resin composition in combination with the oxime ester photoinitiator and an ultraviolet absorber from the viewpoint of improving luminance by a synergistic effect.

When the ultraviolet absorber is used in combination with the oxime ester photoinitiator, the content of the ultraviolet absorber is 1 part by mass with respect to 100 parts by mass of the total amount of the oxime ester photoinitiator. The amount is preferably 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and still more preferably 5 parts by mass or more and 45 parts by mass or less. If it is in the said range, it is excellent in the effect of the said combination.

Specific examples of the surfactant and the plasticizer include those described in JP 2013-029832 A, for example.

Examples of silane coupling agents include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403. KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicone), and the like. Of these, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103 having a methacrylic group and an acrylic group are preferable from the viewpoint of adhesion of the SiN substrate.

The content of the silane coupling agent is preferably 0.05 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the total solid content in the colored resin composition. More preferably, it is 1 part by mass or more and 5.0 parts by mass or less. If it is more than the said lower limit and below the said upper limit, it is excellent in the adhesiveness of SiN.

<Combination ratio of each component in the colored resin composition for color filter>
The total content of the color material is 3% by mass or more and 65% by mass or less, more preferably 4% by mass or more and 60% by mass or less, based on the total solid content of the colored resin composition for color filters. Is preferred. If it is more than the said lower limit, the colored layer at the time of apply | coating the colored resin composition for color filters to predetermined | prescribed film thickness (usually 1.0 micrometer or more and 5.0 micrometers or less) has sufficient color density. Moreover, if it is below the said upper limit, while being excellent in storage stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. In the case of forming a colored layer having a particularly high color material concentration, the content of the color material is 15% by mass or more and 65% by mass or less, more preferably 25% by mass with respect to the total solid content of the color resin composition for color filters. It is preferable to mix | blend in the ratio of the mass% or more and 60 mass% or less.
Further, the content of the dispersant is not particularly limited as long as it can uniformly disperse the coloring material. For example, the content of the dispersant is 1 with respect to the total solid content of the colored resin composition for a color filter. It can be used in the range of mass% to 40 mass%. Furthermore, it is preferable to mix | blend in the ratio of 2 mass% or more and 30 mass% or less with respect to solid content whole quantity of the colored resin composition for color filters, and it is preferable to mix | blend especially in the ratio of 3 mass% or more and 25 mass% or less. . If it is more than the said lower limit, it is excellent in the dispersibility and dispersion stability of a color material, and is excellent in the storage stability of the colored resin composition for color filters. Moreover, if it is below the said upper limit, developability will become favorable. When a colored layer having a particularly high colorant concentration is formed, the content of the dispersing agent is 2% by mass or more and 25% by mass or less, more preferably 3%, based on the total solid content of the colored resin composition for color filters. It is preferable to mix in a proportion of not less than 20% by mass and not more than 20% by mass.
Moreover, what is necessary is just to set content of a solvent suitably in the range which can form a colored layer accurately. Usually, it is preferably in the range of 55% by mass to 95% by mass with respect to the total amount of the colored resin composition for a color filter containing the solvent, and in particular, in the range of 65% by mass to 88% by mass. More preferably. When the content of the solvent is within the above range, the coating property can be excellent.

In the colored resin composition for a color filter of the present invention, the P / V ratio ((color material component mass in the composition) / (solid content mass other than color material components in the composition) ratio) is degassed or From the viewpoint of heat shrinkage, it is preferably 0.1 or more, and more preferably 0.2 or more. On the other hand, it is excellent in suppression of retardation and manufacturing convenience, that is, solvent resolubility, development. From the viewpoint of excellent residue, development adhesion, development resistance, water stain occurrence suppression effect, etc., it is preferably 0.8 or less, more preferably 0.7 or less, from the point of development residue, development adhesion It is still more preferable that it is 0.6 or less.

<Curing film of colored resin composition for color filter>
The colored resin composition for color filters has chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source, where x = 0.550 to 0.700 and y = 0.290 to 0.450. It is preferable that a cured film in the range can be formed.
Among these, from the viewpoint of improving color reproducibility, the chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source are x = 0.570 to 0.693, y = 0.300 to 0. It is preferable that a cured film in the range of .426 can be formed, and a cured film in the range of x = 0.600 to 0.690 and y = 0.300 to 0.348 can be further formed. It is more preferable that a cured film in the range of x = 0.630 to 0.690 and y = 0.300 to 0.329 can be formed.

The cured film of the colored resin composition for a color filter has a thickness of 2.8 μm or less, and in the chromaticity coordinates in the XYZ color system of JIS Z8701 measured with a C light source with a single pixel, x = 0.570 to 0.693, y = 0.300 to 0.426, and a color space in which the stimulus value Y is in the range of 9.0 ≦ Y can be displayed, and x = 0.600 to 0.690. Y = 0.300 to 0.348 and a color space in which the stimulus value Y is in the range of 9.5 ≦ Y is more preferable. In addition, the film thickness of the cured film here is a film after applying the colored resin composition for color filter, drying, exposing to cure the polyfunctional monomer, and then post-baking in a clean oven at 230 ° C. for 30 minutes. Thickness.
In the chromaticity coordinates in the XYZ color system of JIS Z8701 measured with a C light source at a single pixel, the film thickness is 2.8 μm or less, x = 0.570 to 0.693, y = 0.300 As a blending ratio or combination that is favorable for displaying a color space in the range of .about.0.426 and stimulation value Y 9.0.ltoreq.Y, the red colorant is 45.0% by mass or more and 98% of the total colorant. 0.0 mass% or less, the specific yellow color material is preferably 2.0 mass% or more and 55.0 mass% or less, and the red color material is 50.0 mass% or more and 95.0 mass% or less, The specific yellow color material is preferably 5.0% by mass or more and 50.0% by mass or less, and in particular, the red color material is 55.0% by mass or more and 90.0% by mass or less, and the specific yellow color material. Is preferably 10.0% by mass or more and 45.0% by mass or less.

<Method for producing colored resin composition for color filter>
The method for producing the colored resin composition for a color filter of the present invention is not particularly limited. For example, the color material dispersion of the present invention includes an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and as necessary. It can be obtained by adding other components and mixing them using a known mixing means. Alternatively, using the dispersant, each color material dispersion liquid is prepared, and each color material dispersion liquid, a binder component, and other components as necessary, using a known mixing means. It can be obtained by mixing.

[Color filter]
The color filter according to the present invention is a color filter comprising 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 has a colored layer which is a cured product.

Such a color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic 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 part 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, that is, a colored layer formed by curing the colored resin composition. .
The colored layer is usually formed in an opening of a light-shielding part on the substrate to be described later, and is usually composed of a colored pattern of three or more colors.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the colored resin composition for a color filter, 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.
First, the above-described colored resin composition for a color filter of the present invention is applied onto a substrate described later using a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. Apply to form a wet coating. Of these, spin coating and die coating can be preferably used.
Next, after drying the wet coating film using a hot plate or an oven, it is exposed through a mask having a predetermined pattern and cured by photopolymerization of an alkali-soluble resin and a polyfunctional monomer. Let it be a coating film. 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.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition for the color filter to be used, the thickness of the coating film, and the like.

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, the developer is usually washed and the cured coating film of the colored resin composition for color filters is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

(Shading part)
The light shielding part in the color filter of the present invention is formed in a pattern on a substrate to be described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. The light shielding part may be a metal thin film such as chromium by sputtering, vacuum deposition or the like. Alternatively, the light shielding part may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring the photosensitive resist, etc. is there.

The thickness of the light-shielding part 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 where a black pigment is dispersed or dissolved in a binder resin. Set by.

(substrate)
As the substrate, a transparent substrate or a silicon substrate, which will be described later, or an aluminum, silver, or silver / copper / palladium alloy thin film formed on the substrate is used. On these substrates, another color filter layer, a resin layer, a transistor such as a TFT, a circuit, or the like may be formed.

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, transparent flexible rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible flexible materials such as transparent resin films, optical resin plates, and flexible glasses. Materials.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing about 100 micrometers or more and 1 mm or less can be used, for example.
The color filter of the present invention includes, for example, an overcoat layer, a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, etc., in addition to the substrate, the light shielding portion, and the colored layer. Also good.

[Display device]
The display device according to the present invention includes the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as a liquid crystal display device and an organic light emitting display device. In the present invention, even in a horizontal electric field type liquid crystal display device, various display defects such as a liquid crystal orientation disorder caused by the electrical characteristics of the green pixel and a burn-in phenomenon caused by a switching threshold shift are suppressed. The device is preferably selected.

<Liquid crystal display device>
The liquid crystal display device of the present invention includes the color filter according to the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic diagram illustrating an example of a display device of the present invention, and is a schematic diagram illustrating an example of a liquid crystal display device. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be employed. Examples of such a drive method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used.
Further, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.

As a method for forming a 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.

<Organic light-emitting display device>
An organic light emitting display device according to the present invention includes the above-described color filter according to the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram illustrating another example of the display device of the present invention, and is a schematic diagram illustrating an example of an organic light emitting display device. 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 emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method for laminating the organic light emitter 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which an organic light emitter 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 in the organic light emitting body 80, known structures can be appropriately used. The organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a known configuration as an organic light emitting display device that generally uses a color filter.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
In addition, the acid value of the block copolymer before salt formation was calculated | required by the method according to the method of JISK0070.
The amine value of the block copolymer before salt formation was determined by a method according to the method described in JIS K 7237.
The weight average molecular weight (Mw) of the block copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method of the present invention described above.
The glass transition temperature (Tg) of the block copolymer before salt formation and after salt formation is determined by differential scanning calorimetry (DSC) (EXSTAR DSC 7020, manufactured by SII Nanotechnology Co., Ltd.) according to the method described in JIS K7121. It measured using.

(Production Example 1 Preparation of Azo Derivative 1)
23.1 g diazobarbituric acid and 19.2 g barbituric acid were introduced into 550 g distilled water. Subsequently, it adjusted so that it might become azobarbituric acid (0.3 mol) using potassium hydroxide aqueous solution, and mixed with 750 g of distilled water. 5 g of 30% hydrochloric acid was added dropwise. Thereafter, 38.7 g of melamine was introduced. Next, 0.57 mol nickel chloride solution and 0.03 mol copper chloride solution were mixed and added, and stirred at a temperature of 80 ° C. for 8 hours. The pigment was isolated by filtration, washed, dried at 120 ° C., and ground in a mortar to obtain Azo derivative 1 (azo pigment with Ni: Cu = 95: 5 (molar ratio)).

(Production Example 2 Preparation of Azo Derivative 2)
Production Example 1 except that 0.39 mol nickel chloride solution and 0.21 mol zinc chloride solution were used instead of 0.57 mol nickel chloride solution and 0.03 mol copper chloride solution. In the same manner as in Example 1, Azo derivative 2 (azo pigment with Ni: Zn = 65: 35 (molar ratio)) was obtained.

(Production Example 3 Preparation of Azo Derivative 3)
Production Example 1 except that instead of 0.57 mol nickel chloride solution and 0.03 mol copper chloride solution, 0.42 mol nickel chloride solution and 0.18 mol copper chloride solution were used. In the same manner as in Example 1, Azo derivative 3 (NizoCu = 70: 30 (molar ratio) azo pigment) was obtained.

(Production Example 4 Preparation of Azo Derivative 4)
Production Example 1 except that a 0.21 mol nickel chloride solution and a 0.39 mol zinc chloride solution were used in place of the 0.57 mol nickel chloride solution and the 0.03 mol copper chloride solution. In the same manner as in Example 1, Azo derivative 4 (azo pigment with Ni: Zn = 35: 65 (molar ratio)) was obtained.

(Synthesis Example 1: Preparation of Dispersant a)
Add 250 parts by weight of THF and 0.6 parts by weight of lithium chloride to a 500 mL round bottom 4-neck separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and perform sufficient nitrogen replacement. It was. After cooling the reaction flask to −60 ° C., 4.9 parts by mass of butyllithium (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. B block monomer 1-ethoxyethyl methacrylate (EEMA) 3.3 parts by weight, 2-hydroxyethyl methacrylate (HEMA) 18.2 parts by weight, 2-ethylhexyl methacrylate (EHMA) 4.2 parts by weight, methacryl 7.0 parts by mass of n-butyl acid (BMA), 24.7 parts by mass of benzyl methacrylate (BzMA), and 13.3 parts by mass of methyl methacrylate (MMA) were added dropwise over 60 minutes using an addition funnel. . After 30 minutes, 30.8 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the 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, diluted with PGMEA to obtain a solid content solution of 30% by mass. 32.5 parts by mass of water was added, the temperature was raised to 100 ° C., and the reaction was carried out for 7 hours. The obtained block copolymer PGMEA solution is reprecipitated in hexane, purified by filtration and vacuum drying, and a structural unit derived from a block containing a structural unit represented by the general formula (I) and a carboxy group-containing monomer A block copolymer A-1 (acid value: 12 mgKOH / g, Tg: 44 ° C.) containing a B block having a solvophilic property was contained. The block copolymer A-1 thus obtained was confirmed by GPC (gel permeation chromatography), and the weight average molecular weight Mw was 8100. The amine value was 110 mgKOH / g.
29.35 parts by mass of block copolymer A-1 was dissolved in 29.35 parts by mass of PGMEA in a 100 mL round bottom flask, and 1.59 parts by mass of phenylphosphonic acid (manufactured by Tokyo Chemical Industry) 0.1 mol) was added to 1 mol of the DMMA unit of the combined A-1, and the mixture was stirred at a reaction temperature of 30 ° C. for 20 hours to obtain a salt type block copolymer A-1 (dispersant a) solution. Specifically, the amine value after salt formation was calculated as follows.
Into an NMR sample tube, 1 g of a solution prepared by mixing 9 parts by mass of salt-type block copolymer A-1 (solid after reprecipitation) and 91 parts by mass of chloroform-D1 NMR was added, and the ¹³ C-NMR spectrum was measured by nuclear magnetic field. Using a resonance apparatus (manufactured by JEOL Ltd., FT NMR, JNM-AL400), the measurement was performed under conditions of room temperature and 10,000 times of integration. Of the obtained spectral data, the integrated value of the carbon atom peak adjacent to the non-salt-formed nitrogen atom and the carbon atom peak adjacent to the salt-formed nitrogen atom at the terminal nitrogen site (amino group) From the ratio, the ratio of the number of amino groups that are salt-formed to the total number of amino groups is calculated, and is not different from the theoretical salt-forming ratio (the two acidic groups of all phenylphosphonic acids are different from the DMMA of the block copolymer A-1). It was confirmed that a salt was formed with the terminal nitrogen site).
The amine value after salt formation was calculated as 88 mgKOH / g by subtracting the amine value (22 mgKOH / g) of 0.20 mol of DMMA unit from the amine value 110 mgKOH / g before salt formation. The acid value of the block copolymer A-1 after salt formation is the same as that of the block copolymer A-1 before salt formation. Table 1 shows the acid value, amine value, and Tg of the block copolymer A-1 before and after salt formation.

(Synthesis Examples 2 to 4: Production of dispersants b to d)
In Synthesis Example 1, except that the content is changed to the contents shown in Table 1, in the same manner as in Synthesis Example 1, salt copolymers before salt formation A-2 to A-4, and salt-type block copolymer A-2 (Dispersant b) to A-4 (dispersant d) solutions were synthesized. Note that 1-ethoxyethyl methacrylate (EEMA) was used in Synthesis Example 2 at 2.8 parts by mass, Synthesis Example 3 at 2.2 parts by mass, and Synthesis Example 4 at 1.1 parts by mass. Table 1 shows the acid value, amine value, and Tg of the obtained block copolymer before and after salt formation.

(Synthesis Example 5: Preparation of dispersant e)
A 500 ml 4-neck separable flask was decompressed and dried, and then replaced with Ar (argon).
While flowing Ar, 100 g of dehydrated THF, 2.0 g of methyltrimethylsilyldimethylketene acetal, 0.15 ml of 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), and 0.2 g of mesitylene were added. Using a dropping funnel, 13.4 parts by weight of 2-ethylhexyl methacrylate (EHMA), 14.3 parts by weight of n-butyl methacrylate (BMA), 9.9 parts by weight of benzyl methacrylate (BzMA), methacrylic acid Methyl (MMA) 35.7 parts by mass was added dropwise over 45 minutes. As the reaction progressed, heat was generated, so the temperature was kept below 40 ° C. by cooling with ice. After 1 hour, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 15 minutes. After reacting for 1 hour, 5 g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain block copolymer A-5. The weight average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 8,350, and the amine value was 95 mgKOH / g.
In a 100 mL round bottom flask, 29.35 parts by mass of block copolymer A-5 was dissolved in 29.35 parts by mass of PGMEA, and 3.17 parts by mass of phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry Co., Ltd.) 0.20 mol) is added to 1 mol of DMMA unit of copolymer A-5, and the mixture is stirred at a reaction temperature of 30 ° C. for 20 hours to obtain a salt block copolymer A-5 (dispersant e) solution. It was. The amine value after salt formation was calculated in the same manner as in Synthesis Example 1. Table 1 shows the acid value, amine value, and Tg of the obtained block copolymer before and after salt formation.

(Synthesis Example 6: Preparation of dispersant f)
In Synthesis Example 5, instead of phenylphosphonic acid, 3.80 parts by mass of benzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) (benzyl chloride is 0.3 mol with respect to 1 mol of DMMA unit of block copolymer A-5) is used. A salt type block copolymer A-6 (dispersant f) solution was synthesized in the same manner as in Synthesis Example 5 except for the above. Table 1 shows the acid value, amine value, and Tg of the obtained block copolymer before and after salt formation.

(Synthesis Example 7: Preparation of Dispersant g)
In Synthesis Example 5, 13.4 parts by mass of 2-ethylhexyl methacrylate (EHMA), 14.3 parts by mass of n-butyl methacrylate (BMA), 9.9 parts by mass of benzyl methacrylate (BzMA), and methyl methacrylate ( MMA) 35.7 parts by mass n-butyl methacrylate (BMA) 7.6 parts by mass, methyl methacrylate (MMA) 32.9 parts by mass, and PME-1000 (methoxy polyethylene glycol monomethacrylate (polyethylene glycol) The number of chain repetitions n≈23), trade name Blemmer PME-1000, manufactured by NOF Co., Ltd., 39.9 parts by mass, and dimethylaminoethyl methacrylate (DMMA) was replaced with 26.7 parts by mass, 19.6 parts by mass Except for the use, in the same manner as in Synthesis Example 5, the block copolymer A-7 before salt formation and the salt block Copolymer A-7 was obtained (dispersing agent g) solution. The amine value after salt formation was calculated in the same manner as in Synthesis Example 1. Table 1 shows the acid value, amine value, and Tg of the obtained block copolymer before and after salt formation.

(Synthesis Example 8: Preparation of alkali-soluble resin A solution)
A mixed solution of 40 parts by mass of BzMA, 15 parts by mass of MMA, 25 parts by mass of MAA, and 3 parts by mass of AIBN was dropped into a polymerization tank containing 150 parts by mass of PGMEA at 100 ° C. for 3 hours in a nitrogen stream. did. After completion of dropping, the mixture was further heated at 100 ° C. for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution was 7000.
Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol are added to the obtained polymer solution, and heated at 110 ° C. for 10 hours to react. Air was bubbled through the solution. The obtained alkali-soluble resin A is a resin in which a side chain having an ethylenic double bond is introduced into the main chain formed by copolymerization of BzMA, MMA, and MAA using GMA, and has a solid content of 42.6 mass. %, Acid value 74 mgKOH / g, and weight average molecular weight 12000. The weight average molecular weight was measured with a Shodex GPC System-21H (polypropylene) using polystyrene as a standard substance and THF as an eluent. The acid value was measured based on JIS K 0070.

(Synthesis Example 9: Preparation of alkali-soluble resin B solution)
Instead of using 40 parts by mass of BzMA as a comonomer species during polymerization in Synthesis Example 8, Synthesis Example 8 was used except that 20 parts by mass of styrene and 20 parts by mass of N-phenylmaleimide (Tokyo Chemical Industry Co., Ltd.) were used. Similarly, an alkali-soluble resin B solution was obtained. The solid content was 42.6% by mass, the acid value was 74 mgKOH / g, and the weight average molecular weight was 12,000.

(Synthesis Example 10: Synthesis of Latent Antioxidant (Compound a))
A phenol compound represented by the following chemical formula (3) 0.01 mol, di-tert-butyl dicarbonate 0.05 mol and 30 g of pyridine were mixed, and 0.025 mol of 4-dimethylaminopyridine was added at room temperature under a nitrogen atmosphere. Stir at 0 ° C. for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, and 200 g of chloroform was added to perform oil / water separation. 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 powder crystals were dried under reduced pressure at 60 ° C. for 3 hours to obtain a latent antioxidant (compound a) represented by the chemical formula (a). The structure of the obtained latent antioxidant was confirmed by IR and NMR.

Example 1
(1) Production of Colorant Dispersion R1 6.23 parts by mass of Dispersant a solution of Synthesis Example 1 as a dispersant and diketopyrrolopyrrole pigment (BrDPP, product represented by the following chemical formula (2) as a red colorant Name Irgaphor RED S 3621CF, manufactured by BASF) 2.57 parts by mass, C.I. I. Pigment Red 254 (trade name Hostaperm Red D2B-COF LV3781, manufactured by CLARIANT) 3.86 parts by mass, C.I. I. 2.08 parts by mass of Pigment Red 177 (trade name Chromophthal Red A2B, manufactured by BASF), 4.49 parts by mass of Azo derivative 2 obtained in Production Example 2 as a yellow color material, and alkali-soluble obtained in Synthesis Example 8 14.59 parts by mass of the resin A solution, 66.12 parts by mass of PGMEA, and 100 parts by mass of 2.0 mm zirconia beads were put into a mayonnaise bin, and pre-crushed with a paint shaker (manufactured by Asada Tekko Co., Ltd.). Shake for 1 hour, then take out zirconia beads with a particle size of 2.0 mm, add 200 parts by mass of zirconia beads with a particle size of 0.1 mm, and similarly disperse in a paint shaker for 4 hours as a main crushing. Dispersion R1 was obtained.

(2) Production of Colored Resin Composition R1 for Color Filter 11.29 parts by mass of the colorant dispersion R1 obtained in (1) above and 1.90 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 8 Parts, polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.) 0.60 parts by mass, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Photoinitiator: trade name Irgacure 907 (IRG907), manufactured by BASF) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: 0.04 parts by mass of Irgacure 369 (IRG369), manufactured by BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- 0.02 parts by mass of (O-acetyloxime) (photoinitiator: trade name Adeka Arcles NCI-831 (NCI831), manufactured by ADEKA), fluorosurfactant (trade name: Megafuck F559, manufactured by DIC Corporation) ) 0.07 parts by mass, silane coupling agent (trade name KBM-503, manufactured by Shin-Etsu Silicone) 0.07 parts by mass, mercapto compound (pentaerythritol tetrakis (3-mercaptobutyrate)) 0.05 parts by mass, PGMEA And 5.92 parts by mass of 3-methoxy-3-methyl-1-butyl acetate were added to obtain a colored resin composition R1 for color filters.
(3) Formation of colored layer The colored resin composition R1 obtained in the above (2) is placed on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After applying using a spin coater, it is dried at 80 ° C. for 3 minutes using a hot plate, irradiated with 60 mJ / cm ² of ultraviolet light using an ultrahigh pressure mercury lamp, and further post-baked for 30 minutes in a 230 ° C. clean oven. Thus, the colored layer R1 was formed by adjusting the film thickness so that the film thickness after curing was 2.10 μm.

(Examples 2 to 11, Comparative Example 1)
(1) Production of Color Material Dispersions R2 to R9 and RC1 In Examples 2 to 6 and Comparative Example 1, instead of the dispersant a solution in Example 1 (1), as shown in Table 2, respectively. In the same manner as in (1) of Example 1, except that the type and amount of the dispersant were changed so that the solid content was the same part by mass, and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass. Color material dispersions R2 to R6 were obtained.
Examples 7 to 9 are the same as Example (3) (1) except that, in Example 3 (1), the color material type and amount used were changed as shown in Table 2, respectively. Thus, colorant dispersions R7 to R9 were obtained.
Moreover, in Comparative Example 1, as shown in Table 2 in Example 1 (1), instead of the dispersant a solution, the type and amount of the dispersant are set to be equal to parts by mass. The color material dispersion RC1 was obtained in the same manner as (1) of Example 1 except that the amount of PGMEA was adjusted so that the total amount was 100 parts by mass, and the type and amount of color material were changed. It was.
(2) Production of Colored Resin Compositions R2 to R11 and RC1 for Color Filters In Examples 2 to 9 and Comparative Example 1, Table 2 shows the color material dispersion R1 in (2) of Example 1 respectively. Thus, using the colorant dispersions R2 to R9 and RC1, the amount of the alkali-soluble resin is adjusted so that the P / V ratio becomes the value shown in Table 2 in order to make the film thickness 2.10 μm. Except for the adjustment, color resin compositions R2 to R9 and RC1 for color filters were obtained in the same manner as (2) of Example 1.
Further, in Example 10, instead of using the alkali-soluble resin A solution in Example 3, the alkali-soluble resin B solution obtained in Synthesis Example 9 was used, and an antioxidant (trade name IRGANOX 1010 (1010)) was used. A colored resin composition R10 for color filters was obtained in the same manner as (2) of Example 3 except that 0.03 parts by mass of BASF) was added.
Further, in Example 11, as shown in Table 2 for the photoinitiator in Example 10, instead of 0.04 parts by mass of IRG369, an oxime ester photoinitiator (trade name TR-PBG-365 ( PBG365), manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) and 0.04 parts by mass of NCI831, instead of 0.02 parts by mass of oxime ester initiator (trade name TR-PBG-3057 (PBG3057), Changzhou Powerful Electronics) A colored resin composition R11 for a color filter was obtained in the same manner as in (2) of Example 10 except that 0.02 parts by mass of Shinbunshi Co., Ltd. was used.
(3) Formation of colored layer In (1) of Example 1, (3) in Example 1 except that the colored resin compositions R2 to R11 and RC1 were used instead of the colored resin composition R1, respectively. Similarly, colored layers R2 to R11 and RC1 were obtained.

Here, each abbreviation in the table is as follows.
Y150 derivative: C.I. I. Pigment Yellow 150 Derivative (Ni Complex) (trade name: LEVASCREEN YELLOW G01, LANXESS Co., Ltd.)
Byk-161: Trade name Disperbyk-161 (urethane-based dispersant, solid content 30% by mass, manufactured by Big Chemie)
Solvent A: Propylene glycol monomethyl ether acetate (PGMEA)
Solvent B: 3-methoxy-3-methyl-1-butyl acetate

(Examples 12 to 23)
(1) Production of Color Material Dispersions R12 to R23 In Examples 12 to 23, as shown in Table 3 in Example 1 (1), the types and blending amounts of color materials were changed, and the total amount Color material dispersions R12 to R23 were obtained in the same manner as in Example 3 (1) except that the amount of PGMEA was adjusted to 100 parts by mass.
(2) Production of Colored Resin Compositions R12 to R23 for Color Filter The above color material dispersions R12 to R23 were used in place of the color material dispersion R3 in (2) of Example 11, and the film thickness was 2.50 μm. Therefore, a colored resin composition for a color filter was prepared in the same manner as in (2) of Example 11 except that the amount of the alkali-soluble resin was adjusted so that the P / V ratio was the value shown in Table 3. R12 to R23 were obtained.
(3) Formation of colored layer In the same manner as (3) of Example 11 except that the colored resin compositions R12 to R23 were used in place of the colored resin composition R11 in (3) of Example 11. Thus, colored layers R12 to R23 were obtained.

(Comparative Examples 2 to 7)
(1) Production of Color Material Dispersions RC2 to RC7 In Comparative Examples 2 to 7, the type and use of the dispersant instead of the dispersant a solution as shown in Table 3 in (1) of Example 1 The amount was changed so that the solid content was the same part by mass, and as shown in Table 3, the color material type and blending amount were changed, and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass. In the same manner as in Example 1 (1), colorant dispersions RC2 to RC7 were obtained.
(2) Production of Colored Resin Compositions RC2 to RC7 for Color Filter The above color material dispersions RC2 to RC7 were used in place of the color material dispersion R3 in (2) of Example 11 and the film thickness was 2.50 μm. Therefore, a colored resin composition for a color filter was prepared in the same manner as in (2) of Example 11 except that the amount of the alkali-soluble resin was adjusted so that the P / V ratio was the value shown in Table 3. RC2 to RC7 were obtained.
(3) Formation of colored layer In the same manner as (3) of Example 11 except that the colored resin composition RC2 to RC7 were used in place of the colored resin composition R11 in (3) of Example 11. Thus, colored layers RC2 to RC7 were obtained.

R264: C.I. I. Pigment Red 264 (trade name: Irgazin Red L 4010 HD, manufactured by BASF)
R242: C.I. I. Pigment Red 242 (Brand name: Novoperm SCARlet 4RF, manufactured by CLARIANT)
O38: C.I. I. Pigment Orange 38 (trade name: Novoperm Red HF, manufactured by CLARIANT) C.I. I. Pigment Orange 38 has a wavelength of 520 nm when a spectral transmittance spectrum of a 2.5 μm coating film is measured at a P / V (red color material mass / solid content mass other than red color material) ratio = 0.2. The transmittance is 20% or less, and the transmittance at a wavelength of 640 nm is 70% or more, which corresponds to the red color material of the present invention.
R177: C.I. I. Pigment Red 177 (trade name: Chromophthal Red A2B, manufactured by BASF)
R179: C.I. I. Pigment Red 179 (Brand name: Paliogen Maroon L 3980, manufactured by BASF Dispersions & Pigments Asia Pacific)
R272: C.I. I. Pigment Red 272 (trade name: Irgazin Flame Red K 3800, manufactured by BASF)
Y150 derivative: C.I. I. Pigment Yellow 150 Derivative (Ni Complex) (trade name: LEVASCREEN YELLOW G01, LANXESS Co., Ltd.)
Byk-161: Trade name Disperbyk-161 (urethane-based dispersant, solid content 30% by mass, manufactured by Big Chemie)
6919: Trade name Disperbyk-LPN6919 (polymer having a structural unit represented by the general formula (I), amine value 120 mgKOH / g, solid content 60% by mass, manufactured by Big Chemie)

(Examples 24-41)
(1) Production of Color Material Dispersions R24 to R41 In Examples 24 to 41, as shown in Table 4 in Example 3 (1), the type and blending amount of color materials were changed, and the total amount Color material dispersions R24 to R41 were obtained in the same manner as (1) of Example 3 except that the amount of PGMEA was adjusted to 100 parts by mass.
(2) Production of Colored Resin Compositions R24 to R41 for Color Filter The above color material dispersions R24 to R41 were used in place of the color material dispersion R3 in (2) of Example 11, and the film thickness was 2.80 μm. Therefore, a colored resin composition for a color filter was prepared in the same manner as in (2) of Example 11 except that the amount of the alkali-soluble resin was adjusted so that the P / V ratio was the value shown in Table 4. R24 to R41 were obtained.
(3) Formation of colored layer In the same manner as (3) of Example 11 except that the colored resin compositions R24 to R41 were used in place of the colored resin composition R11 in (3) of Example 11. Thus, colored layers R24 to R41 were obtained.

(Example 42)
(1) Production of colorant dispersion
6.23 parts by mass of the dispersant c solution of Synthesis Example 3 as a dispersant, and diketopyrrolopyrrole pigment represented by the chemical formula (2) as a colorant (BrDPP, trade name: Irgaphor RED S 3621CF, manufactured by BASF) 14.0 parts by weight, 14.59 parts by weight of the alkali-soluble resin A solution obtained in Synthesis Example 8, 66.20 parts by weight of PGMEA, and 100 parts by weight of 2.0 mm zirconia beads in a mayonnaise bin, Shake with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour as preliminary crushing, then take out 2.0 mm zirconia beads with a particle size of 2.0 mm, add 200 parts by mass of zirconia beads with a particle size of 0.1 mm, and similarly As this crushing, dispersion was performed for 4 hours with a paint shaker to obtain a red color material dispersion r1.
In the red color material dispersion r1, instead of using 13.0 parts by mass of the diketopyrrolopyrrole pigment (BrDPP) represented by the chemical formula (2) as the color material, C.I. I. A red color material dispersion r2 was obtained in the same manner as the red color material dispersion r1 except that 13.0 parts by mass of Pigment Red 254 (trade name: Hostasper Red D2B-COF LV3781, manufactured by CLARIANT) was used.
In the red color material dispersion r1, instead of using 13.0 parts by mass of the diketopyrrolopyrrole pigment (BrDPP) represented by the chemical formula (2) as the color material, C.I. I. A red color material dispersion r3 was obtained in the same manner as the red color material dispersion r1 except that 13.0 parts by mass of Pigment Red 177 (trade name: Palogen Red L 4045, manufactured by BASF) was used.
Instead of using 13.0 parts by mass of the diketopyrrolopyrrole pigment (BrDPP) represented by the chemical formula (2) as a colorant in the red colorant dispersion r1, 13.0 parts by mass of Azo derivative 2 as a colorant is used. A yellow color material dispersion y was obtained in the same manner as in the red color material dispersion r1 except that a part of the red color material dispersion r1 was used.

(2) Production of colored resin composition R42 for color filter 1.65 parts by mass of red color material dispersion r1 obtained in (1) above, 3.57 parts by mass of red color material dispersion r2 and red color material 1.92 parts by mass of dispersion r3, 4.15 parts by mass of yellow color material dispersion y, 1.90 parts by mass of alkali-soluble resin A solution obtained in Synthesis Example 8, polyfunctional monomer (trade name Aronix M -403, manufactured by Toagosei Co., Ltd.), 0.60 parts by mass, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907) 0.09 parts by mass of BASF) and 0.04 parts of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name Irgacure 369, manufactured by BASF) Part, ethanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (photoinitiator: trade name Adeka Arcles NCI-831, manufactured by ADEKA) 0.02 part by mass, 0.07 part by mass of a fluorosurfactant (trade name MegaFuck F559, manufactured by DIC Corporation), 0.07 part by mass of a silane coupling agent (trade name KBM-503, manufactured by Shin-Etsu Silicone) , 0.05 parts by mass of a mercapto compound (pentaerythritol tetrakis (3-mercaptobutyrate)), 5.85 parts by mass of PGMEA, and 3.92 parts by mass of 3-methoxy-3-methyl-1-butyl acetate A colored resin composition R42 for filters was obtained.
(3) Formation of colored layer In (3) of Example 1, coloring was performed in the same manner as (3) of Example 1 except that the colored resin composition R42 was used instead of the colored resin composition R1. Layer R42 was obtained.
The obtained colored resin composition R42 for color filter has the same composition as the colored resin composition R3 for color filter of Example 3, and the evaluation results of the colored resin composition R42 for color filter and the colored layer R42 are as follows: It became the same as the evaluation result of colored resin composition R3 for color filters, and colored layer R3.

(Examples 43 to 48)
(1) Production of Colorant Dispersion R47 In Example 47, as shown in Table 5 in Example 1 (1), solid content was obtained by using Dispersant g solution instead of Dispersant a solution. Were changed to be the same part by mass, and a colorant dispersion R47 was obtained in the same manner as (1) of Example 1 except that the amount of PGMEA was adjusted so that the total amount was 100 parts by mass.
(2) Production of colored resin compositions R43 to R48 for color filter In Example 43, instead of using the alkali-soluble resin A solution in Example 3, the alkali-soluble resin B solution obtained in Synthesis Example 9 was used. Furthermore, as shown in Table 5 for the photoinitiator, instead of 0.04 parts by mass of IRG369, 0.02 parts by mass of oxime ester photoinitiator (trade name Irgacure OXE 01 (OXE01), manufactured by BASF) Example 2 (2) of Example 3 except that 0.04 parts by mass of NCI831 was used instead of 0.02 parts by mass of an oxime ester-based initiator (trade name Irgacure OXE 02 (OXE02), manufactured by BASF). Similarly, a colored resin composition R43 for color filters was obtained.
Further, in Example 44, instead of 0.03 part by mass of the antioxidant (trade name IRGANOX 1010 (1010), manufactured by BASF) in Example 11, the antioxidant (trade name ADK STAB AO-40 (AO- 40), manufactured by ADEKA) Except for using 0.03 parts by mass, a colored resin composition R44 for color filters was obtained in the same manner as (2) of Example 11.
In Example 45, instead of 0.03 part by mass of the antioxidant (trade name IRGANOX 1010 (1010), manufactured by BASF) in Example 11, the latent antioxidant (Compound a) of Synthesis Example 10 was used. A colored resin composition R45 for color filters was obtained in the same manner as (2) of Example 11 except that 0.03 part by mass was used.
In Example 46, instead of adding 0.03 part by mass of the antioxidant (trade name IRGANOX 1010 (1010), manufactured by BASF) in Example 11, an ultraviolet absorber (benzotriazole compound, trade name) A colored resin composition R46 for color filters was obtained in the same manner as (2) of Example 11 except that 0.03 parts by mass of TINUVIN 329 BASF) was added.
In Example 47, a colored resin composition for a color filter was obtained in the same manner as in (3) of Example 3 except that the color material dispersion R47 was used instead of the color material dispersion R3. R47 was obtained.
In Example 48, the colorant dispersion R47 was used instead of the colorant dispersion R3 in Example 43, and an antioxidant (trade name ADK STAB AO-40 (AO-40), manufactured by ADEKA) 0.03 A colored resin composition for a color filter in the same manner as in (2) of Example 43, except that part by mass and 0.03 part by mass of an ultraviolet absorber (benzotriazole-based compound, trade name: TINUVIN 329 BASF) were added. Product R48 was obtained.
(3) Formation of colored layer In the same manner as (3) of Example 1 except that the colored resin compositions R43 to R48 were used in place of the colored resin composition R1 in (1) of Example 1. As a result, colored layers R43 to R48 were obtained.

[Evaluation methods]
<Evaluation of dispersibility of colorant dispersion>
For the colorant dispersions obtained in Examples and Comparative Examples, the viscosity immediately after preparation and after storage for 30 days at 25 ° C. are measured, the rate of change in viscosity is calculated from the viscosity before and after storage, and the viscosity stability is evaluated. did. The viscosity was measured at 25.0 ± 0.5 ° C. using a vibration viscometer. The results are shown in Tables 2-5.
(Viscosity stability evaluation criteria)
A: Change rate of viscosity before and after storage is less than 10% B: Change rate of viscosity before and after storage is 10% or more and less than 15% C: Change rate of viscosity before and after storage is 15% or more and less than 25% D: Before and after storage Viscosity change rate is 25% or more However, this is a value when the color material is 13 mass% with respect to the total mass including the solvent of the color material dispersion.
Even if the evaluation result is C, the color material dispersion can be used practically. However, if the evaluation result is B, the color material dispersion is better. If the evaluation result is A, the color material dispersion is excellent in dispersion stability. Are better.

<Optical performance evaluation, contrast evaluation>
The contrast, chromaticity (x, y), and luminance (Y) of the colored layers obtained in the examples and comparative examples were measured using a spectral characteristic measuring device LCF-1500M manufactured by Otsuka Electronics and a contrast measuring device CT-1B manufactured by Aisaka Electric. Measured.
(Contrast evaluation criteria)
・ Value when C is 0.570 to 0.600 with C light source AA: More than 10,000 A: 8000 to 10,000
B: 6000-7999
C: Less than 6000 · Value when C is 0.607 to 0.630 with C light source AA: Over 9000 A: 7000 to 9000
B: 5000-6999
C: Less than 5000 · Value when C is 0.650 to 0.693 with C light source AA: Exceeds 8000 A: 6000 to 8000
B: 4000-5999
C: Less than 4000

<Evaluation of phase difference>
The retardation of the colored layer was determined using the retardation in the thickness direction (Rth) calculated by the following formula as an index. Retardation (Rth) was measured using a retardation layer measuring apparatus (Axoscan ™ Mueller Matrix Polarimeter manufactured by AXOMETRICS). The measurement wavelength of the red colored layer was measured at 620 nm and 665 nm.
Rth = ((Nx + Ny) / 2−Nz) d
Nx: Refractive index in the in-plane slow axis direction Ny: Refractive index in the in-plane fast axis direction Nz: Refractive index in the thickness direction d: Film thickness (nm)

<Solvent resolubility evaluation>
The tip of a glass substrate having a width of 0.5 cm and a length of 10 cm was immersed in the colored resin composition for a color filter obtained in Examples and Comparative Examples, and applied to a 1 cm portion of the glass substrate. The pulled glass substrate was placed in a thermo-hygrostat so that the glass surface was horizontal, and dried at a temperature of 23 ° C. and a humidity of 80% RH for 10 minutes. Next, the glass substrate to which the dried coating film was adhered was immersed in PGMEA for 15 seconds. At this time, the redissolved state of the dried coating film was visually discriminated and evaluated.
(Solvent re-solubility evaluation criteria)
AA: The dried coating film was completely dissolved in 8 seconds or less. A: The dried coating film was completely dissolved. B: A flake of the dried coating film was formed in the solvent, and the solution was colored. C: The dried coating film was dissolved in the solvent. The flakes did not occur and the solution did not color. If the above evaluation criteria were AA, A or B, it was evaluated that the solvent resolubility was good and could be used practically without any problem, but the evaluation result was A and further AA. Is more effective.

<Development residue evaluation>
The colored resin compositions for color filters obtained in the examples and comparative examples were respectively applied to a spin coater on a 100 mm × 100 mm glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) with a thickness of 0.7 mm. After being applied, it was dried at 60 ° C. for 3 minutes using a hot plate to form a colored layer having a thickness of 2.5 μm. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. After observing the unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer by visual observation, the glass substrate is thoroughly wiped with a lens cleaner (trade name Toraysee MK Clean Cloth, manufactured by Toray Industries, Inc.), The coloring degree of the lens cleaner was visually observed.
(Development residue evaluation criteria)
AA: Even in the same evaluation with a colored layer having a thickness of 3.5 μm, no development residue was visually confirmed and the lens cleaner was not colored at all. A: No development residue was visually confirmed, and the lens cleaner was completely colored. B: Development residue was not visually confirmed, and the color of the lens cleaner was slightly confirmed. C: Development residue was visually confirmed, and the color of the lens cleaner was confirmed. D: Development residue was visually confirmed. When the above evaluation criteria are AA, A, B, or C, it can be used practically, but if the evaluation result is B, further A, and further AA, the effect is more excellent. ing.

<Development resistance evaluation>
The colored resin compositions for color filters obtained in Examples and Comparative Examples were each applied on a glass substrate having a thickness of 0.7 mm (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater. After heating and drying on an 80 ° C. hot plate for 3 minutes, ultraviolet rays of 40 mJ / cm ² were irradiated using an ultrahigh pressure mercury lamp. The film thickness at this point is measured and set to T1 (μm). Thereafter, shower development was performed using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. The film thickness after development is measured and set to T2 (μm). T2 / T1 × 100 (%) was calculated.
(Development resistance evaluation criteria)
AA: 98% or more A: 95% or more and less than 98% B: 90% or more and less than 95% C: less than 90% Although the evaluation results are AA, A, and B, they can be used practically. AA is more effective.

<Water stain evaluation>
The color filter colored resin composition obtained in each example and each comparative example was formed on a glass substrate (NH Techno Glass Co., Ltd., “NA35”) with a thickness of 1 after post-baking using a spin coater. After coating with a film thickness to form a colored layer of .6 μm, it is dried at 60 ° C. for 3 minutes using a hot plate, and irradiated with ultraviolet light of 60 mJ / cm ² using an ultrahigh pressure mercury lamp without using a photomask. As a result, a colored layer was formed on the glass substrate. Next, spin development is performed using 0.05 wt% potassium (KOH) as a developer, the developer is subjected to an indirect solution for 60 seconds and then washed with pure water, and the washed substrate is rotated for 10 seconds to remove water. Immediately after centrifugation, the contact angle of pure water was measured as described below to evaluate water stain.
The contact angle of pure water was measured by dropping 1.0 μL of pure water on the surface of the colored layer immediately after removing the water by centrifugation, and determining the static contact angle 10 seconds after the landing according to the θ / 2 method. Measured. The measuring device was measured using a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd.
(Water stain evaluation criteria)
AA: Contact angle of 80 degrees or more A: Contact angle of 75 degrees or more and less than 80 degrees B: Contact angle of 65 degrees or more and less than 75 degrees C: Contact angle of 50 degrees or more and less than 65 degrees D: Contact angle of less than 50 degrees Water stain evaluation standard is AA If it is A or B, it can be used practically, but if the evaluation result is A and further AA, the effect is more excellent.

<SiN adhesion evaluation>
The colored resin composition for color filter obtained in each example and each comparative example was applied on a SiN substrate (manufactured by Foresight Co., Ltd.) using a spin coater, and then at 80 ° C. using a hot plate. The film is dried for 3 minutes, irradiated with 60 mJ / cm ² ultraviolet rays using an ultra-high pressure mercury lamp, and further post-baked for 30 minutes in a clean oven at 230 ° C., so that the film thickness after curing becomes 2.10 μm. The colored layer was formed by adjusting the thickness.
The obtained colored layer was subjected to a cross-cut test in accordance with JIS K 5600-5-6, and after repeating the peeling operation with the tape 5 times, the presence or absence of peeling of the coating film was observed and evaluated according to the following evaluation criteria. did.
(SiN adhesion evaluation criteria)
AA: There is no peeling of the eyes of any lattice
A: Although there is a small peeling of the coating film at the intersection of the cuts, the exclusive area of the peeling is less than 5%. B: The coating film is peeled off at the intersections along the cut line. Exclusive area of peeling is 5% or more and less than 15%
C: The coating film is partially or totally peeled along the cut line. Exclusive area of peeling is 15% or more and less than 35%

[Summary of results]
From the results in the table, Examples 1 to 41 in which the red color material is combined with the specific yellow color material, and further, the dispersant is a polymer having a structural unit represented by the general formula (I). The colorant dispersions No. 47 and No. 47 were found to have good viscosity stability. On the other hand, it was revealed that the color material dispersion of Comparative Example 1 in which a red color material is combined with a conventional yellow color material and a urethane-based dispersant has poor viscosity stability. Further, it was revealed that even when the specific yellow color material was combined with the red color material, the color material dispersion of Comparative Example 2 in which the urethane-based dispersant was combined had poor viscosity stability.
In addition, the colorant dispersions of Comparative Examples 3 to 7 in which a conventional yellow color material is combined with a red color material may use a dispersant that is a polymer having a structural unit represented by the general formula (I). It was shown that the viscosity stability was poor.

In addition, for the color filter of Examples 1 to 48, the red color material is combined with the specific yellow color material, and further, the dispersant is a polymer having a structural unit represented by the general formula (I). The colored resin composition has good colorant dispersion stability, and it has been clarified that the colored layer using the colored resin composition is excellent in contrast while the retardation value is reduced. In addition, each of the colored layers using the colored resin compositions of Examples 1 to 48 has excellent adhesion to SiN, and among them, the colored resin compositions of Examples 11, 44, 45, 46, and 48 were used. It was also revealed that the colored layer has excellent adhesion to SiN. Further, the adhesion of Example 10 to SiN was A, which was close to AA, and was good.
On the other hand, Comparative Examples 1 and 3 to 7 in which color materials different from the Examples are combined are inferior in contrast and large in phase difference value as compared with Examples having the same chromaticity coordinates (x, y). It was.
Further, even when the specific yellow color material is combined with the red color material, the comparative example 2 in which the urethane-based dispersant is combined is inferior in contrast to the example of the same chromaticity coordinate (x, y). The phase difference value was large.
Further, in Comparative Examples 1, 3 to 7, the P / V ratio in the colored resin composition tends to be larger and the adhesion to SiN is inferior as compared with Examples having the same chromaticity coordinates (x, y). It was.
Furthermore, Comparative Example 1 was inferior in terms of solvent resolubility, development residue suppression, development resistance, and water stain as compared with Examples having the same chromaticity coordinates (x, y).

Among the examples, the alkali-soluble resin includes both a maleimide structure having a hydrocarbon ring and a styrene structure, and in the example in which an antioxidant is added, a colored layer having improved development residue and brightness is formed. It was revealed that
Further, it has been clarified that when two types of oxime ester photoinitiators are used in combination with an antioxidant, a colored layer having improved development resistance and luminance is formed. Among them, it is preferable to use an oxime ester photoinitiator having a fluorene skeleton and an oxime ester photoinitiator having diphenyl sulfide in terms of excellent luminance, and it has an oxime ester photoinitiator having a carbazole skeleton and diphenyl sulfide. The combined use of an oxime ester photoinitiator was preferred in that the effect of suppressing water stain was increased.

Further, Example 44 using a hindered phenol-based antioxidant having a molecular weight of 500 or less and a molecular weight per phenolic hydroxyl group of 200 equivalents or less is colored with improved brightness while reducing the retardation value. A layer was formed. In Example 44, the contrast was A close to AA, and a colored layer with improved contrast was obtained.
In Example 45 using the latent antioxidant, a phase difference value was reduced, and a colored layer having a contrast of A, which was close to AA, and an improved contrast was obtained.
Further, in Example 46 using the ultraviolet absorber, a colored layer having a reduced retardation value, a contrast A close to AA, and an improved contrast was obtained.
In addition, a hinder having an oxime ester photoinitiator having a carbazole skeleton and an oxime ester photoinitiator having diphenyl sulfide, having a molecular weight of 500 or less and a molecular weight per phenolic hydroxyl group of 200 equivalents or less. In Example 48 using a combination of a dophenol-based antioxidant and an ultraviolet absorber, a colored layer with improved brightness and improved water stain suppression effect was formed while the retardation value was reduced. In Example 48, the contrast was A close to AA, and a colored layer with improved contrast was obtained.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Counter substrate 30 Liquid crystal layer 40 Liquid crystal display device 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 emitting display device

Claims

A color material dispersion containing a color material, a dispersant, and a solvent,
The color material includes a red color material and a yellow color material,
The yellow color material includes at least one anion selected from the group consisting of mono-, di-, tri-, and tetraanions of an azo compound represented by the following general formula (A) and an azo compound having a tautomer structure thereof: An ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (B): Including
A color material dispersion for a color filter, wherein the dispersant is a polymer having a structural unit represented by the following general formula (I).

(In the general formula (A), each R a is independently —OH, —NH 2 , —NH—CN, acylamino, alkylamino, or arylamino, and each R b is independently —OH or — NH 2. )

(In the general formula (B), each R c is independently a hydrogen atom or an alkyl group.)

(In the general formula (I), R 1 is a hydrogen atom or a methyl group, A is a divalent linking group, R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon that may contain a hetero atom. Represents a group, and R 2 and R 3 may combine with each other to form a ring structure.)
The color material for a color filter according to claim 1, wherein the red color material includes at least one selected from the group consisting of a diketopyrrolopyrrole pigment, a naphthol azo pigment, an anthraquinone pigment, and a perylene pigment. Dispersion.
Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn as at least two kinds of metals in the yellow color material The color material dispersion for a color filter according to claim 1, comprising:
The color material dispersion for a color filter according to any one of claims 1 to 3, wherein at least two kinds of metals in the yellow color material are Ni and Zn, or Ni and Cu.
A colored resin composition for a color filter containing a coloring material, a dispersant, a binder component, and a solvent,
The color material includes a red color material and a yellow color material,
The yellow color material includes at least one anion selected from the group consisting of mono-, di-, tri-, and tetraanions of an azo compound represented by the following general formula (A) and an azo compound having a tautomer structure thereof: An ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (B): Including
A colored resin composition for a color filter, wherein the dispersant is a polymer having a structural unit represented by the following general formula (I).

(In the general formula (A), each R a is independently —OH, —NH 2 , —NH—CN, acylamino, alkylamino, or arylamino, and each R b is independently —OH or — NH 2. )

(In the general formula (B), each R c is independently a hydrogen atom or an alkyl group.)

(In the general formula (I), R 1 is a hydrogen atom or a methyl group, A is a divalent linking group, R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon that may contain a hetero atom. Represents a group, and R 2 and R 3 may combine with each other to form a ring structure.)
The colored resin for a color filter according to claim 5, wherein the red color material includes at least one selected from the group consisting of a diketopyrrolopyrrole pigment, a naphthol azo pigment, an anthraquinone pigment, and a perylene pigment. Composition.
Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn as at least two kinds of metals in the yellow color material A colored resin composition for a color filter according to claim 5 or 6.
The colored resin composition for a color filter according to any one of claims 5 to 7, wherein at least two kinds of metals in the yellow color material are Ni and Zn, or Ni and Cu.
The color filter for a color filter according to any one of claims 5 to 8, wherein the binder component comprises an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and the photoinitiator is an oxime initiator. Colored resin composition.
The colored resin composition for a color filter according to any one of claims 5 to 9, further comprising an antioxidant.
A cured film can be formed with chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source in the range of x = 0.550 to 0.700 and y = 0.290 to 0.450. The colored resin composition for a color filter according to any one of claims 5 to 10.
A color filter comprising at least 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 5 to 11. A color filter, which is a cured product.
A display device comprising the color filter according to claim 12.