JP7094891B2 - Color material dispersion for color filters, colored resin compositions for color filters, color filters, and display devices - Google Patents

Description

The present invention relates to a color material dispersion liquid for a color filter, a colored resin composition for a color filter, 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 (mobile phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding more and more. Recently, organic light emitting display devices such as organic EL displays having high visibility due to self-luminous light have also attracted attention as next-generation image display devices. In terms of the performance of these image display devices, further improvement in image quality and reduction in power consumption such as improvement in contrast and color reproducibility are strongly desired.

Many of the conventional display devices comply with sRGB (IEC61966-2-1), which is an international standard for color spaces. However, in order to obtain an expression closer to the real thing, and because of the demand for further improvement in color reproducibility, it has AdobeRGB, which has a wider color reproduction range in the green direction, and AdobeRGB, which has a wider color reproduction range in the red and green directions, as compared with sRGB. DCI (Digital Cinema Initiatives) and BT (Roadcasting Service Television). There is an increasing demand for display devices compatible with 2020.

Here, the color filter used in the liquid crystal display device generally separates a transparent substrate, a colored layer formed on the transparent substrate and composed of coloring patterns of the three primary colors of red, green, and blue, and each coloring pattern. It has a light-shielding portion formed on the transparent substrate as described above.
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 them, the pigment dispersion method having excellent characteristics on average is most widely adopted from the viewpoints of spectral characteristics, durability, pattern shape, accuracy and the like.

On the other hand, as a peculiar problem of the liquid crystal display device, there is a problem of viewing angle dependence due to the refractive index anisotropy of the liquid crystal cell or the polarizing plate. This problem of viewing angle dependence is a problem that the color and contrast of the image visually recognized changes depending on whether the liquid crystal display device is viewed from the front or from an oblique direction. Such a problem of viewing angle characteristics has become more serious with the recent increase in the screen size of liquid crystal display devices.
In order to improve the problem of viewing angle dependence, 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 coloring layer, when the above retardation film is used, the difference in the phase difference of the coloring pattern of each color is compensated. There was a problem that it could not be done, and it was difficult to completely solve the problem of viewing angle dependence.

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

In Patent Document 1, C.I. I. A 1: 1 complex of Pigment Red 177 (hereinafter sometimes abbreviated as PG177) and nickel of azobarbituric acid, compatible isomers thereof, and other compounds in the crystal lattice of at least one of these compounds. A color filter using a combination of a pigment (CI pigment yellow 150 derivative (Ni complex)) consisting of at least one crystal selected from the group consisting of inserted crystals is disclosed. However, in order to express a deep red color using this pigment, it is necessary to use a pigment having a very high concentration, the phase difference value in the thickness direction becomes large, the contrast is lowered, and the plate-making property is deteriorated. There was a problem such as.

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

Japanese Unexamined Patent Publication No. 2010-144057 Japanese Unexamined Patent Publication No. 2014-12838

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

The color material dispersion liquid for a color filter according to the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent.
The color material contains a red color material and a yellow color material, and the color material contains a red color material and a yellow color material.
The yellow color material comprises at least one anion selected from the group consisting of mono, di, tri and tetra anions of an azo compound represented by the following general formula (A) and an azo compound having a tautomeric structure thereof. 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 the compound represented by the following general formula (B). Including,
The dispersant is a color material dispersion liquid 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 contains a red color material and a yellow color material, and the color material contains a red color material and a yellow color material.
The yellow color material comprises at least one anion selected from the group consisting of mono, di, tri and tetra anions of an azo compound represented by the following general formula (A) and an azo compound having a tautomeric structure thereof. 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 the 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).

（一般式（Ａ）中、Ｒ^ａはそれぞれ独立して、－ＯＨ、－ＮＨ_２、－ＮＨ－ＣＮ、アシルアミノ、アルキルアミノ又はアリールアミノであり、Ｒ^ｂはそれぞれ独立して、－ＯＨ又は－ＮＨ_２である。）

(In the general formula (A), Ra is independently -OH, -NH ₂ , -NH-CN, acylamino, alkylamino or arylamino, and R ^b is independently -OH ^or- , respectively. NH ₂ )

（一般式（Ｂ）中、Ｒ^ｃはそれぞれ独立して、水素原子又はアルキル基である。）

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

（一般式（Ｉ）中、Ｒ^１は水素原子又はメチル基、Ａは、２価の連結基、Ｒ^２及びＲ^３は、それぞれ独立して、水素原子、又はヘテロ原子を含んでもよい炭化水素基を表し、Ｒ^２及びＲ^３が互いに結合して環構造を形成してもよい。）

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, and R ² and R ³ are hydrocarbons which may independently contain a hydrogen atom or a hetero atom. Representing a group, R ² and R ³ may be bonded to each other to form a ring structure.)

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

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

According to the present invention, a color material dispersion for a color filter and a color material dispersion for a color filter that are excellent in color material dispersion stability and capable of forming a colored layer with improved contrast while reducing the phase difference value are used. However, the phase difference value is reduced by using a colored resin composition for a color filter capable of forming a colored layer having improved contrast and excellent color reproducibility while reducing the phase difference value, and the colored resin composition for the color filter. Provided is a color filter having improved contrast and excellent color reproducibility, and a display device having 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 material dispersion liquid for a color filter, the colored resin composition for a color filter, the color filter, and the display device according to the present invention will be described in detail in order.
In the present invention, the 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 refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acrylic represents each of acrylic and methacrylic, 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" as appropriate.

[Color material dispersion]
The color material dispersion liquid for a color filter according to the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent.
The color material contains a red color material and a yellow color material, and the color material contains a red color material and a yellow color material.
The yellow color material comprises at least one anion selected from the group consisting of mono, di, tri and tetra anions of an azo compound represented by the following general formula (A) and an azo compound having a tautomeric structure thereof. 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 the compound represented by the following general formula (B). Including,
The dispersant is a color material dispersion liquid for a color filter, which is a polymer having a structural unit represented by the following general formula (I).

（一般式（Ａ）中、Ｒ^ａはそれぞれ独立して、－ＯＨ、－ＮＨ_２、－ＮＨ－ＣＮ、アシルアミノ、アルキルアミノ又はアリールアミノであり、Ｒ^ｂはそれぞれ独立して、－ＯＨ又は－ＮＨ_２である。）

(In the general formula (A), Ra is independently -OH, -NH ₂ , -NH-CN, acylamino, alkylamino or arylamino, and R ^b is independently -OH ^or- , respectively. NH ₂ )

（一般式（Ｂ）中、Ｒ^ｃはそれぞれ独立して、水素原子又はアルキル基である。）

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

（一般式（Ｉ）中、Ｒ^１は水素原子又はメチル基、Ａは、２価の連結基、Ｒ^２及びＲ^３は、それぞれ独立して、水素原子、又はヘテロ原子を含んでもよい炭化水素基を表し、Ｒ^２及びＲ^３が互いに結合して環構造を形成してもよい。）

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, and R ² and R ³ are hydrocarbons which may independently contain a hydrogen atom or a hetero atom. Representing a group, R ² and R ³ may be bonded to each other to form a ring structure.)

Since the color material dispersion liquid of the present invention uses the specific color material in combination and a polymer having a structural unit represented by the general formula (I) as a dispersant in combination, the color material dispersion stability is improved. It is possible to form a colored layer having improved contrast while being excellent and reducing the retardation value.
Since most of the red color materials generally have an annular planar structure, they are easily crystallized when forming a colored layer as a color material dispersion liquid for a color filter. Therefore, the phase difference in the thickness direction in the obtained colored layer. The value tends to be large.
On the other hand, in the color material dispersion liquid of the present invention, the weight having a specific yellow color material containing two or more kinds of metal ions and a specific structural unit represented by the general formula (I) in the red color material. Since it is used in combination with a dispersant that is a coalescence, an interaction acts between the red color material and a specific yellow color material containing two or more types of metal ions, and crystals of the red color material and the yellow color material Growth is suppressed and atomization is possible, and since the red color material and the yellow color material are atomized and dispersed by the combination with the dispersant, the colored layer having improved contrast while reducing the retardation value. Is presumed to be able to form.
Conventionally, when the metal forming the metal complex containing the azo compound represented by the general formula (A) is one kind of coloring material, the crystallinity is high and it is difficult to atomize the metal, and it is difficult to improve the contrast. rice field. In addition, the phase difference value of the colored layer obtained in combination with the red color material tends to be high. On the other hand, in the present invention, a specific yellow color material containing two or more kinds of metal ions with respect to the anion of the azo compound represented by the general formula (A) is used. By containing two or more kinds of metal ions, the yellow color material not only suppresses the crystal growth of the yellow color material, but also suppresses the crystal growth of the red color material, and further, by combining the specific dispersant. It is presumed that the particles are atomized in the colorant dispersion.
Further, in the present invention, by combining the red color material with the specific yellow color material, the P / V ratio ((mass of the color material component in the composition) / (solid other than the color material component in the composition) Even if the fractional mass) ratio) is suppressed, red pixels included in the high color density red chromaticity region can be produced.
It is presumed that the phase difference 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 coloring material is suppressed. ..
Further, since the total content of the coloring material component in the colored resin composition can be suppressed, the content of the binder component can be relatively increased, so that the plate-making property is improved and the adhesion to the substrate is improved. It becomes possible to form a higher colored layer.

The color material dispersion liquid 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 colorant dispersion liquid of the present invention will be described in detail in order.

<Color material>
In the present invention, the coloring material includes a red coloring material and a yellow coloring material.
The yellow color material comprises at least one anion selected from the group consisting of mono, di, tri and tetra anions of an azo compound represented by the following general formula (A) and an azo compound having a tautomeric structure thereof. 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 the 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 the yellow color material, it is possible to suppress a decrease in luminance when combined with a red color material, and it is possible to suppress crystallization and atomize. Since the dispersibility is excellent when combined with a specific dispersant described later, the contrast can be improved and the phase difference value can be further reduced.

（一般式（Ａ）中、Ｒ^ａはそれぞれ独立して、－ＯＨ、－ＮＨ_２、－ＮＨ－ＣＮ、アシルアミノ、アルキルアミノ又はアリールアミノであり、Ｒ^ｂはそれぞれ独立して、－ＯＨ又は－ＮＨ_２である。）

(In the general formula (A), Ra is independently -OH, -NH ₂ , -NH-CN, acylamino, alkylamino or arylamino, and R ^b is independently -OH ^or- , respectively. NH ₂ )

Examples of the acyl group in the acylamino group in the general formula (A) include an alkylcarbonyl group, a phenylcarbonyl group, an alkylsulfonyl group, a phenylsulfonyl group, an alkyl, a phenyl, or a carbamoyl group and an alkyl which may be substituted with naphthyl. , 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 or more and 6 or less carbon atoms. Further, the alkyl group may be substituted with, for example, a halogen such as F, Cl, Br, -OH, -CN, -NH ₂ , and / or an alkoxy group having 1 or more and 6 or less carbon atoms. The phenyl group and naphthyl group are, for example, halogens such as F, Cl, Br, -OH, -CN, -NH ₂ , -NO ₂ , alkyl groups having 1 or more and 6 or less carbon atoms, and / or 1 carbon atoms. It may be substituted with an alkoxy group of 6 or more.
The alkyl group in the alkylamino group in the general formula (A) preferably has 1 or more carbon atoms and 6 or less carbon atoms. The alkyl group may be substituted with, for example, a halogen such as F, Cl, Br, -OH, -CN, -NH ₂ , and / or an alkoxy group having 1 or more and 6 or less carbon atoms.
Examples of the aryl group in the arylamino group in the general formula (A) include a phenyl group and a naphthyl group, and these aryl groups are, for example, halogens such as F, Cl and Br, −OH, and having 1 or more and 6 or less carbon atoms. It may be substituted with an alkyl group of, an alkoxy group having 1 or more and 6 or less carbon atoms, -NH ₂ , -NO ₂ and -CN.

In the azo compound represented by the general formula (A) and the azo compound having ^a tautomeric structure thereof, the Ra is independently -OH, -NH ₂ , -NH-CN, or an alkylamino. This is preferable from the viewpoint of producing ^a reddish hue, and the two Ras may be the same or different from each other.
In the general formula ( ^A ), the two Ras are, among other things, in terms of hue, when both are -OH, both are -NH-CN, or one is -OH and one is -NH-. The case of CN is even more preferable, and the case of both -OH is even more preferable.

Further, in the azo compound represented by the general formula (A) and the azo compound having a tautomeric structure thereof, it is more preferable that both of them are ^−OH from the viewpoint of hue.

Among 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. It is preferable to contain at least one kind, preferably to contain at least one kind selected from the group consisting of Ni, Cu, and Zn, and further preferably to contain at least Ni.
Further, it is preferable to contain Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn, and further, Ni. Further, it is preferable to include at least one metal selected from the group consisting of Zn, Cu, Al and Fe. Above all, the at least two kinds of 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 kinds of metals may be appropriately adjusted.
Among them, 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 at least one metal is preferably contained in a molar ratio of 97: 3 to 10:90 for Ni: the other at least one metal, and further, a molar ratio of 90:10 to 10:90. It is preferable to include it in a ratio.
Above all, from the viewpoint of reddish hue, it is preferable that Ni: Zn is contained in a molar ratio of 90:10 to 10:90, and more preferably in a molar ratio of 80:20 to 20:80. preferable.
Alternatively, from the viewpoint of reddish hue, Ni: Cu is preferably contained in a molar ratio of 97: 3 to 10:90, and more preferably contained in a molar ratio of 96: 4 to 20:80. preferable.
When the yellow color material has a reddish hue, it is easy to produce red pixels included in the red chromaticity region of the high color density 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 ions of the specific metal. 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 embodiment in which the ions of at least two kinds of metals are contained in the yellow color material, there are cases where ions of at least two kinds of metals are contained in a common crystal lattice and one kind of metal in another crystal lattice. The case where crystals containing ions are aggregated may be mentioned. Above all, it is preferable that ions of at least two kinds of metals are contained in the common crystal lattice from the viewpoint of further improving the contrast. It should be noted that whether the common crystal lattice contains at least two types of metal ions or the other crystal lattice contains crystals containing one type of metal ion is aggregated. For example, it can be appropriately determined by using the X-ray diffraction method with reference to Japanese Patent Application Laid-Open No. 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 is a metal complex composed of 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). ) Includes a complex molecule with the compound. Bonds between these molecules can be formed, for example, by intermolecular interactions, by Lewis acid-base interactions, or by coordinate bonds. Further, the structure may be such that the guest molecule is incorporated in the lattice constituting the host molecule, such as an inclusion compound. Alternatively, the two substances may form a co-crystal and form a mixed substitution crystal in which the atom of the second component is located at the position of the regular lattice of the first component.

（一般式（Ｂ）中、Ｒ^ｃはそれぞれ独立して、水素原子又はアルキル基である。）

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

The alkyl group in ^Rc is preferably an alkyl group having 1 or more and 6 or less carbon atoms, and more preferably an alkyl group having 1 or more and 4 or less carbon atoms. The alkyl group may be substituted with an —OH group.
Above all, 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 telecommunication structure thereof. It is preferably 5 mol or more and 300 mol or less, preferably 10 mol or more and 250 mol or less, and further preferably 100 mol or more and 200 mol or less.

Further, the yellow color material used in the present invention further includes urea and a substituted urea such as phenylurea and dodecylurea, and a polycondensate thereof with an aldehyde, particularly formaldehyde; a heterocycle such as barbituric acid and benzimidazole. Ron, benzimidazolone-5-sulfonic acid, 2,3-dihydroxyquinoxaline, 2,3-dihydroxyquinoxalin-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 and poly (meth) acrylic acid such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and methyl. -And modified cellulose such as ethyl hydroxyethyl cellulose may be contained.

The yellow color material used in the present invention can be prepared, for example, by referring to Japanese Patent Application Laid-Open No. 2014-12838.

On the other hand, the red color material used in the present invention has a P / V (amount of red color material / mass of solid content other than the red color material) ratio = 0.2, and has a spectral transmittance spectrum of a coating film having a film thickness of 2.5 μm. When the above is measured, a coloring material having a transmittance of 20% or less at a wavelength of 520 nm and a transmittance of 70% or more at a wavelength of 640 nm is used. The red color material used in the present invention includes C.I. I. A coloring material described as pigment orange is also included.

In order to make a red color material into a coating film and measure the color by itself, a suitable dispersant, a binder component and a solvent are mixed with the red color material to prepare a coating liquid, and the coating liquid is applied onto a transparent substrate. It may be dried and cured if necessary. As the binder component, a non-curable thermoplastic resin composition may be used as long as a transparent coating film capable of color measurement can be formed, or a photocurable (photosensitive) or thermosetting resin composition may be used. May be used. Further, in the colored resin composition of the present invention 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 can be formed as a color material and color measurement can be performed. can. Specifically, for example, the solid content used in the resin composition of Example 1 described later can be a solid content other than the red color material.
As a transparent coating film containing a dispersant and a binder component that can perform color measurement, for example, the transmittance of the spectral transmittance spectrum at 380 to 780 nm is 95% or more as a guideline with a film thickness of 2.0 μm. can do.
The spectral transmittance spectrum can be measured using a spectroscopic measuring device (for example, an Olympus microscopic device OSP-SP200). The measurement condition is a C light source.

The red color material used in the present invention is not particularly limited, and for example, diketopyrrolopyrrole pigments, naphthol azo pigments and other azo pigments, quinacridone pigments, dioxazine pigments, anthraquinone pigments, perinone pigments, etc. Examples thereof include perylene-based pigments and thioindigo-based pigments. The red color material used in the present invention is at least one selected from the group consisting of diketopyrrolopyrrole pigments, naphthol azo pigments, anthraquinone pigments, and perylene pigments from the viewpoint of suppressing the P / V ratio. It is preferable to contain seeds, and further, from the viewpoint of easily forming a hue having a high color density and high brightness, it is further preferable to contain at least one selected from the group consisting of diketopyrrolopyrrole pigments and anthraquinone pigments. preferable.

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

（一般式（１）中、Ａ^３及びＡ^４は、それぞれ独立に、ハロゲン原子、メチル基、エチル基、ｔｅｒｔ－ブチル基、フェニル基、Ｎ，Ｎ－ジメチルアミノ基、トリフルオロメチル基、又はシアノ基を表し、ｋ及びｋ’はそれぞれ独立に０以上５以下の整数を表し、ｋ及びｋ’がそれぞれ２以上の整数の場合、複数のＡ^３及びＡ^４は、それぞれ同じであっても異なっていてもよい。）

( ^In the general formula ( ¹ ), A3 and A4 are independently halogen atoms, methyl groups, ethyl groups, tert-butyl groups, phenyl groups, N, N-dimethylamino groups, trifluoromethyl groups, or Representing a cyano group, k and k'independently represent integers of 0 or more and 5 or less, respectively, and when k and k'are integers of 2 or more, even if a plurality of A3 and ^A4 are the same, ^respectively . It 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, diketopyrrolopyrrole pigment (BrDPP) represented by the following chemical formula (2), and the like can be mentioned.

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. Pigment Red 185 and the like.
Other azo pigments include C.I. I. Pigment Red 38, C.I. I. Pigment Red 41 and the like.

Examples of the anthraquinone pigment include C.I. I. Pigment Red 177, C.I. I. Pigment Red 168, C.I. I. Pigment Orange 51 and the like.

Examples of the perylene-based pigment include 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. Pigment Red 224 and the like.

As the red color material, C.I. I. Pigment Red 254, C.I. I. Pigment Red 264, C.I. I. Pigment Red 272, diketopyrrolopyrrole pigment (BrDPP) represented by the 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 kinds of red color materials selected from the group consisting of Pigment Red 179, and among them, C.I. I. Pigment Red 254, the diketopyrrolopyrrole pigment (BrDPP) represented by the chemical formula (2), and C.I. I. The combination with Pigment Red 177 is preferably used.
C. I. Pigment Red 254, the diketopyrrolopyrrole pigment (BrDPP) represented by the chemical formula (2), and C.I. I. The content ratio in combination with Pigment Red 177 may be appropriately adjusted according to the desired coloring material and is not particularly limited, but C.I. I. Pigment Red 254 is 10 parts by mass or more and 80 parts by mass or less, and the diketopyrrolopyrrole pigment (BrDPP) represented by the chemical formula (2) is 10 parts by mass or more and 70 parts by mass or less, and C.I. I. Pigment Red 177 is preferably 10 parts by mass or more and 60 parts by mass or less. If it is within the above range, the effect of the above combination is excellent. The content ratio of the red colorant is a preferable ratio when the colored resin composition described later is used, and a colored resin composition can be produced by appropriately mixing two or more kinds of colored material dispersions. Therefore, the colorant dispersion liquid itself is preferably used without having the same content ratio as the colored resin composition described later.

In the color material dispersion liquid of the present invention, the red color material and the specific yellow color material are used in combination as the color material, but other color materials as exemplified in the coloring resin composition described later are used in combination. You may. As the other coloring material, for example, another yellow coloring material, an orange coloring material not included in the red coloring material, or the like is preferably used, and among them, other as exemplified in the colored resin composition described later from the viewpoint of hue. The yellow color material of is preferably used.

In the color material dispersion liquid of the present invention, the content ratios of the red color material and the specific yellow color material, and the content ratio when other color materials are used are the same as the content ratios of the colored resin composition described later. It is preferable to do so. However, since the colored resin composition can be produced by appropriately mixing two or more kinds of the colored material dispersion liquid, it is preferably used even if the content ratio is not the same as that of the colored resin composition described later.

The average primary particle size of the coloring material used in the present invention is not particularly limited as long as it can develop a desired color when the coloring layer of the color filter is used, and varies depending on the type of coloring material used. Is preferably in the range of 10 nm or more and 100 nm or less, and more preferably 15 nm or more and 60 nm or less. When the average primary particle size of the coloring material is in the above range, the display device provided with the color filter manufactured by using the coloring material dispersion liquid of the present invention can have high contrast and high quality. ..

The average dispersed particle size of the coloring material in the coloring material dispersion liquid varies depending on the type of the coloring material used, but is preferably in the range of 10 nm or more and 100 nm, and preferably in the range of 15 nm or more and 60 nm or less. More preferred.
The average dispersed particle size of the colored material in the colored material dispersion is the dispersed particle size of the colored material particles dispersed in the dispersion medium containing at least a solvent, which is measured by a laser light scattering particle size distribution meter. Is. For the measurement of the particle size by the laser light scattering particle size distribution meter, the color material dispersion is appropriately diluted with the solvent used in the coloring material dispersion to a concentration that can be measured by the laser light scattering particle size distribution meter (for example, 1000 times). It 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 distributed particle size here is the volume average particle size.

In the color material dispersion liquid of the present invention, the content of the color material is not particularly limited. The content of the coloring 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 coloring material dispersion liquid from the viewpoint of dispersibility and dispersion stability. It is preferable to mix in a proportion of parts by mass or less.
In particular, when a coating film or a colored layer having a high colorant concentration is formed, 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 colorant dispersion liquid. It is preferable to mix in a ratio of 75 parts by mass or less.

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

In the general formula (I), A is a divalent linking group. Examples of the divalent linking group in A include an alkylene group having 1 or more and 10 or less carbon atoms, an arylene group, a -CONH- group, a -COO- group, and an ether group having 1 or more and 10 or less carbon atoms (-R'. -OR "-: R'and R" are independently alkylene groups) and combinations thereof.
Above all, 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 which may contain a hetero atom in R ² and R ³ include an alkyl group, an aralkyl group, an aryl group and the like.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group and the like, and the number of carbon atoms of the alkyl group is 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, a biphenylmethyl group and the like. The number of carbon atoms of 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, a xsilyl group and the like. 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 preferable 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 the carbon atom in the hydrocarbon group is replaced with the hetero atom. Examples of the heteroatom 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 or more and 5 or less carbon atoms, a fluorine atom, a chlorine atom and a bromine atom.

The fact that 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 via a nitrogen atom. Heteroatoms may be contained in the ring structure formed by R ² and R ³ . 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 or more and 5 or less carbon atoms, or a phenyl group, or R ² and R ³ are bonded to each other to form a pyrrolidine ring. , Piperidine ring, morpholin ring is preferably formed, and among them, at least one of R ² and R ³ is an alkyl group or a phenyl group having 1 or more and 5 or less carbon atoms, or R ² and R ³ are formed. Are preferably combined to form a pyrrolidine ring, a piperidine ring, and a morpholine ring.

Examples of the structural unit represented by the general formula (I) include alkyl group-substituted aminos such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. Examples thereof include group-containing (meth) acrylate, dimethylaminoethyl (meth) acrylamide, alkyl group-substituted amino group-containing (meth) acrylamide such as 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 a structural unit represented by the general formula (I) preferably contains a moiety having a solvent affinity from the viewpoint of improving dispersibility. As the solvent-affinitive moiety, among the monomers having an ethylenically unsaturated bond that can be polymerized with the monomer that induces the structural unit represented by the general formula (I), depending on the solvent so as to have solvent affinity. It is preferable to select and use it as appropriate. As a guide, it is preferable to introduce a solvent-affinity moiety 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.
The polymer used in the present invention is a block copolymer because it can improve the dispersibility and dispersion stability of the coloring material and the heat resistance of the resin composition, and can form a colored layer having high brightness and high contrast. Alternatively, a graft copolymer is preferable, and a block copolymer is particularly preferable. Hereinafter, particularly preferable block copolymers will be described in detail.

(Block copolymer)
Assuming that the block containing the structural unit represented by the general formula (I) is A block, the structural unit represented by the general formula (I) has basicity in the A block, and the adsorption site for the coloring material. Functions as. On the other hand, the B block that does not include the structural unit represented by the general formula (I) is made to function 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, or the like can be used. Among them, AB block copolymers or ABA block copolymers are preferable because they are excellent in dispersibility.

Examples of the structural unit constituting the B block include a monomer having an unsaturated double bond copolymerizable with the monomer for inducing the structural unit represented by the general formula (I), and among them, the following general formula. The structural unit represented by (II) is preferable.

（一般式（ＩＩ）中、Ａ’は、直接結合又は２価の連結基、Ｒ^４は、水素原子又はメチル基、Ｒ^５は、炭化水素基、－［ＣＨ（Ｒ^６）－ＣＨ（Ｒ^７）－Ｏ］_ｘ－Ｒ^８又は－［（ＣＨ_２）_ｙ－Ｏ］_ｚ－Ｒ^８で示される１価の基である。Ｒ^６及びＲ^７は、それぞれ独立に水素原子又はメチル基であり、Ｒ^８は、水素原子、炭化水素基、－ＣＨＯ、－ＣＨ_２ＣＨＯ、又は－ＣＨ_２ＣＯＯＲ^９で示される１価の基であり、Ｒ^９は水素原子又は炭素原子数１以上５以下のアルキル基である。
上記炭化水素基は、置換基を有していてもよい。
ｘは１以上３０以下の整数、ｙは１以上５以下の整数、ｚは１以上１８以下の整数を示す。）

(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, and-[CH (R ⁶ ) -CH (R). ⁷ ) -O] _x -R ⁸ or-[(CH ₂ ) _y -O] _z -R ⁸ is a monovalent group. R ⁶ and R ⁷ are independently hydrogen atoms or methyl groups, respectively. Yes, R ⁸ is a monovalent group represented by a hydrogen atom, a hydrocarbon group, -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 of.
The hydrocarbon group may have a substituent.
x is an integer of 1 or more and 30 or less, y is an integer of 1 or more and 5 or less, and z is an integer of 1 or more and 18 or less. )

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

The hydrocarbon group in R5 is preferably an alkyl group having ¹ or more and 18 or less carbon atoms, an alkenyl group having 2 or more and 18 or less carbon atoms, an aralkyl group, or an aryl group.
The alkyl group having 1 or more and 18 or less carbon atoms may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group. Examples thereof include 2-ethylhexyl group, 2-ethoxyethyl group, cyclopentyl group, cyclohexyl group, boronyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, adamantyl group, lower alkyl group substituted adamantyl group and the like.
The alkenyl group having 2 or more and 18 or less carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, a propenyl group and the like. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the obtained polymer, it is preferable that the double bond is at the end of the alkenyl group.
Examples of the substituent of the aliphatic hydrocarbon such as the alkyl group and the 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, a xylyl group and the like, 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.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent. The number of carbon atoms of 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 of the aromatic ring such as the aryl group and the aralkyl group include linear and branched alkyl groups having 1 or more and 4 or less carbon atoms, as well as alkenyl groups, nitro groups and halogen atoms.
The preferable number of carbon atoms does not include the number of carbon atoms of the substituent.

^In R5, 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 an integer of 1 or more and 4 or less, and particularly preferably 1 or more and 2 It is the following integer, and y is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 4 or less, and 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, and more preferably an integer of 1 or more and 2 or less.

The hydrocarbon group in R ⁸ can be the same as that shown in R ⁵ . Among them, the hydrocarbon group ⁱⁿ R8 is preferably an alkyl group having 1 or more carbon atoms and 18 or less carbon atoms from the viewpoint of excellent developability.
R ⁹ is a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms, and may be linear, branched, or cyclic.
Further, R5 in the structural unit represented by the general formula (II) may be the ^same as each other or may be different from each other.

The ^R5 is preferably selected so as to have excellent 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 solvent such as a glycol ether acetate-based solvent, an ether-based solvent, or an ester-based solvent is used, a methyl group, an ethyl group, an isobutyl group, an n-butyl group, a 2-ethylhexyl group, a benzyl group and the like are preferable.
Further, in the structural unit constituting the B block, as the above R5,-[CH (R ⁶ ) -CH (R ⁷ ) -O] _x -R ⁸ or-[ ⁽ CH ₂ ) _y -O] _z- It is preferable to contain the one having ^R8 from the viewpoint of excellent developability and excellent suppression of development residue.

Further, the 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 impaired, and the block copolymer may be used together. After synthesizing the polymer, the substituent may be added by reacting with the compound having the above substituent.

In the present invention, the glass transition temperature (Tg) of the block portion having a solvent affinity for the block copolymer may be appropriately selected. From the viewpoint of heat resistance, the glass transition temperature (Tg) of the solvent-affinitive block portion is preferably 80 ° C. or higher, and more preferably 100 ° C. or higher.
The glass transition temperature (Tg) of the block portion of the solvent affinity in the present invention can be calculated by the following formula. Similarly, the glass transition temperature of the color material-affinity block portion and the block copolymer can be calculated.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that the solvent-friendly block portion is copolymerized with n monomer components from i = 1 to n. 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 of i = 1 to n. As the value (Tgi) of the homopolymer glass transition temperature of each monomer, the value of Polymer Handbook (3rd Edition) (J. Brandrup, E. H. Immergut (Wiley-Interscience, 1989)) may be adopted. can.

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

The solvent-affinity block portion may be selected so as to function as a solvent-affinity site, and the repeating unit constituting the solvent-affinity block portion may consist of one type or two or more types. May include repeating units of.

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

The acid value of the dispersant used in the present invention is preferably 1 mgKOH / g or more as a lower limit from the viewpoint of the effect of suppressing the development residue. Above all, the acid value of the dispersant is more preferably 2 mgKOH / g or more because the effect of suppressing the development residue is more excellent. On the other hand, the acid value of the dispersant is preferably 0 mgKOH / g from the viewpoint of dispersibility and dispersion stability. Further, the acid value of the dispersant used in the present invention is 18 mgKOH / g or less as the upper limit of the acid value of the dispersant from the viewpoint of preventing deterioration of development adhesion and solvent resolubility. preferable. Above all, the acid value of the dispersant is more preferably 12 mgKOH / g or less, and even more preferably 8 mgKOH / g or less, from the viewpoint of improving development adhesion and solvent resolubility.
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 adhesion and the solvent resolubility are improved.

Further, in the present invention, the glass transition temperature of the dispersant is preferably 30 ° C. or higher from the viewpoint of improving the development adhesion. That is, regardless of whether the dispersant is a pre-salt block copolymer or a salt-type block copolymer, the glass transition temperature thereof is preferably 30 ° C. or higher. If the glass transition temperature of the dispersant is low, it is particularly close to the developer temperature (usually about 23 ° C.), and there is a risk that the development adhesion will decrease. It is presumed that this is because when the glass transition temperature is close to the developer temperature, the movement of the dispersant becomes large during development, and as a result, the development adhesion deteriorates. When the glass transition temperature is 30 ° C. or higher, the molecular motion of the dispersant during development is suppressed, and it is presumed 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 weighing.
The glass transition temperature of the dispersant in the present invention is based on JIS K7121 and can be determined by measuring by differential scanning calorimetry (DSC).

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

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

As the carboxy group-containing monomer, a monomer copolymerizable with a monomer having a structural unit represented by the general formula (I) and containing 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. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic acid anhydride, ω-carboxy-polycaprolactone. Mono (meth) acrylate and the like can also be used. Further, as a precursor of the carboxy group, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used. Among them, (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, and in particular. Although not limited, it is preferably 0.05% by mass or more and 4.5% by mass or less, and 0.07% by mass or more and 3.7% by mass or less, based on the total mass of all the constituent units of the block copolymer. It is more preferable to have.
When the content ratio of the structural unit derived from the carboxy group-containing monomer is at least the above lower limit value, the effect of suppressing the development residue is exhibited, and when it is at least the above upper limit value, the development adhesion is deteriorated and the solvent resolubility is deteriorated. It can prevent deterioration.
The structural unit derived from the carboxy group-containing monomer may have the above-mentioned specific acid value, may be composed of one kind, or may contain two or more kinds of structural units.

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

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

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

The method for producing the block copolymer is not particularly limited. The block copolymer can be produced by a known method, but it is particularly preferable to produce it by the 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 can be improved. Examples of the living polymerization method include a living anion polymerization method such as a living radical polymerization method and a group transfer polymerization method, and a living cationic polymerization method. A copolymer can be produced by sequentially polymerizing the monomers by these methods. For example, a block copolymer can be produced by first producing the A block and polymerizing the constituent units constituting the B block with the A block. Further, in the above production method, the order of polymerization of the A block and the B block can be reversed. It is also possible to manufacture the A block and the B block separately, and then couple the A block and the B block.

A specific example of a block copolymer having a block portion containing a structural unit represented by the general formula (I) and a block portion having solvent affinity is described in, for example, Japanese Patent No. 4911253. Block copolymers can be mentioned as suitable.

In the present invention, from the viewpoint of dispersibility and dispersion stability of the coloring material, at least a part of the amino groups in the polymer containing the structural unit represented by the general formula (I), an organic acid compound and the like. It is also preferable to use a polymer obtained by forming a salt from a halogenated hydrocarbon as a dispersant (hereinafter, such a polymer may be referred to as a salt-type polymer).
Above all, the dispersibility of the coloring material is that the polymer containing the repeating unit having a tertiary amine is a block copolymer and the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid. It is preferable from the viewpoint of excellent dispersion stability. As a specific example of the organic acid compound used for such a dispersant, for example, the organic acid compound described in JP-A-2012-236882 can be mentioned as a suitable one.
Further, the halogenated hydrocarbon is preferably at least one of allyl halide such as allyl bromide and benzyl chloride and aralkyl halide, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

In the colorant dispersion liquid of the present invention, at least one of the polymers having the structural unit represented by the general formula (I) is used as the dispersant, and the content thereof is the type of the colorant to be used and further described later. It is appropriately selected according to the solid content concentration and the like in the colored resin composition for a color filter.
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 liquid from the viewpoint of dispersibility and dispersion stability. It is preferable to mix in a proportion of parts by mass 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 liquid. More preferably, it is blended in a ratio of 5 parts by mass or more and 20 parts by mass or less.
In the present invention, the solid content is all other than the above-mentioned solvent, and includes monomers and the like 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. The solvent can be used alone or in combination of two or more.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, i-propyl alcohol and methoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate and methoxypropion. Ester solvents such as methyl meth, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, n-butyl butyrate, clohexanol acetate; acetone, Ketone solvents such as methyl ethyl ketone, cyclohexanone, 2-heptanone; glycol ether acetate such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate Solvents: Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA); Diacets such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl Glycol ether solvents such as ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether; N, N-dimethyl Aprotonic amide solvents such as formamide, N, N-dimethylacetamide, N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated carbides such as benzene, toluene, xylene and naphthalene. Hydrogen-based solvents; saturated hydrocarbon-based solvents such as N-heptane, N-hexane, and N-octane; organic solvents such as aromatic hydrocarbons such as toluene and xylene can be mentioned. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferably used in terms of the solubility of other components. Among them, the 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), and 3-methoxy. Solubility and coating of other components 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 viewpoint of aptitude.

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

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

As the second solvent (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. The second solvent may be used alone or in combination of two or more.

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

When a mixed solvent is used, the content of the solvent having an alcoholic hydroxyl group is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less in the total solvent. Further, 0.1% by mass or more is preferable, 0.3% by mass or more is more preferable, and 1% by mass or more is further preferable.
Within the above range, the solubility of the dispersant tends to be good, and the dispersion of the dispersant in the first solvent is not hindered, so that the dispersion stability tends to be good.

When the first solvent is a solvent having a boiling point of less than 150 ° C., if a solvent having a boiling point of 150 ° C. or higher is used as the second solvent, uneven drying is less likely to occur, foreign matter is less likely to occur, and solvent resolubility is likely to be improved. ..
Examples of solvents having a boiling point of 150 ° C. or higher include diethylene glycol ethylmethyl ether (boiling point 179 ° C.), 3-methoxy-3-methyl-1-butyl acetate (boiling point 188 ° C.), diethylene glycol ethylmethyl ether (boiling point 179 ° C.), 3. -Methoxybutyl acetate (boiling point 172 ° C.) and the like can be mentioned.

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

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

In the color material dispersion liquid of the present invention, it is preferable that the solvent as described above is usually in the range of 55% by mass or more and 95% by mass or less with respect to the total amount of the color material dispersion liquid containing the solvent, particularly 65. It is preferably in the range of mass% or more and 90% by mass or less, and more preferably in the range of 70% by mass or more and 88% by mass. If the amount of solvent is too small, the viscosity increases and the dispersibility tends to decrease. Further, if the amount of the solvent is too large, the concentration of the coloring material decreases, and it may be difficult to achieve the target chromaticity coordinates.

<Other ingredients>
The color material dispersion liquid of the present invention may further contain a dispersion auxiliary resin and other components, if necessary, as long as the effects of the present invention are not impaired.
Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified in the 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, which may have the effect of stabilizing the dispersion and reducing the amount of the dispersant due to the effect of stabilizing the dispersion.
Other components include, for example, a surfactant for improving wettability, a silane coupling agent for improving adhesion, a defoaming agent, an anti-repellent agent, an antioxidant, an anti-aggregation agent, and an ultraviolet absorber. And so on.

The colored material dispersion liquid 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 liquid is P / V (mass of the color material component in the composition) / (color material in the composition) prepared in advance in the stage before preparing the color resin composition for a color filter described later. It is a color material dispersion having a high solid content mass ratio other than the components. Specifically, the ratio (mass of color material component in composition) / (mass of solid content other than color material component in composition) is usually 1.0 or more. By mixing the color material dispersion liquid and each component described later, a colored resin composition for a color filter having excellent dispersibility can be prepared.

[Manufacturing method of color material dispersion]
In the present invention, the method for producing the color material dispersion liquid is not particularly limited as long as the color material is a method for obtaining the color material dispersion liquid dispersed in the solvent by the dispersant. Above all, one of the following two manufacturing methods is preferable from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

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

Further, in the case of using a dispersant which is a salt-type block copolymer, a second method for producing a colorant dispersion liquid according to the present invention is a solvent, the block copolymer, the organic acid compound, or a halogenated hydrocarbon. While mixing hydrogen and a coloring material to form a salt of at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I), the organic acid compound and the halogenated hydrocarbon. It has a step of dispersing the coloring material. Even when the coloring materials are dispersed while forming such a salt, two or more kinds of coloring materials may be co-dispersed, or two or more kinds of colors may be dispersed or co-dispersed after one or more kinds of coloring materials are dispersed or co-dispersed. The color material dispersion liquid of the present invention may be obtained by mixing the material dispersion liquid.

In the first manufacturing method and the second manufacturing method, the coloring material can be dispersed by using a conventionally known disperser.
Specific examples of the disperser include a roll mill such as a two-roll and three-roll mill, a ball mill such as a ball mill and a vibrating ball mill, a paint conditioner, a continuous disc type bead mill, and a bead mill such as a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter used is preferably 0.03 mm or more and 3.0 mm or less, and more preferably 0.05 or more and 2.0 mm or less.

[Colored resin composition for color filters]
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 contains a red color material and a yellow color material, and the color material contains a red color material and a yellow color material.
The yellow color material comprises at least one anion selected from the group consisting of mono, di, tri and tetra anions of the azo compound represented by the general formula (A) and the azo compound having a tautomeric structure thereof. 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 the 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 liquid of the present invention, and as described in the section of the color material dispersion liquid of the present invention, the phase difference. It is possible to form a colored layer having high brightness and high contrast and excellent color reproducibility while reducing the value.

The colored resin composition for a color filter of the present invention contains at least a coloring material, 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. It may be. Hereinafter, each component contained in the colored resin composition for a color filter of the present invention will be described, but the red color material, the specific yellow color material, the dispersant, and the solvent, which are essential components of the color materials, will be described above. Since it is the same as that described in the colorant dispersion liquid of the present invention, the description thereof is omitted here.

<Color material>
The coloring material in the coloring resin composition for a color filter of the present invention contains a red coloring material and the specific yellow coloring material as essential components, but in order to adjust the color tone, another coloring material is used in combination. May be good.
It is not particularly limited as long as it can develop a desired color when the colored layer of the color filter is formed, and various organic pigments, inorganic pigments, and dispersible dyes are mixed alone or in combination of two or more. Can be used. Among them, organic pigments are preferably used because they have high color development and high heat resistance. Examples of the organic pigment include compounds classified as Pigments in the color index (CI; published by The Society of Dyers and Colorists), specifically, the following color index (CI). .) Examples include those with numbers.
Further, as the dispersible dye, a dye that can be dispersed by adding various substituents to the dye or by insolubilizing the dye in a solvent by using a known rake formation (chloride forming) method, or a dye having low solubility. Examples thereof include dyes that can be dispersed by using them 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.
As the dispersible dye, a conventionally known dye can be appropriately selected. 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 the dye dissolved in 10 g of the solvent (or the mixed solvent) is 10 mg or less, it can be determined that the dye can be dispersed in the solvent (or the mixed solvent).

As the other color material, among them, another yellow color material and an orange color material not included in the red color material are preferably used.
Examples of other coloring materials include, but are not limited to, the following.
As another yellow color material, 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, Examples thereof include 155, 156, 166, 167, 168, 175, 180, and 185.

In the colored resin composition for a color filter of the present invention, the content ratio of the red color material to the entire color material may be appropriately adjusted according to a desired chromaticity, and is not particularly limited.
Above all, from the viewpoint of widening the color reproducibility and increasing the contrast while reducing the phase difference value, it is preferable to contain 35% by mass or more and 99% by mass or less of the red color material with respect to the total amount of the color material. It is more preferably contained in an amount of 4% by mass or more and 98% by mass or less, and even more preferably 45% by mass or more and 97% by mass or less.

In addition, 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 reducing the phase difference value. It is more preferable that it is 2% by mass or more and 60% by mass or less, and even more preferably 3% by mass or more and 55% by mass or less.
More preferred.

In the colored resin composition for a color filter of the present invention, the azo compound represented by the general formula (A) in the yellow color material and the azo compound having a telecommunication structure thereof are composed of mono, di, tri and tetra anion. 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, and the general. The total content with the compound represented by the formula (B) (the specific yellow color material) may be appropriately adjusted according to a desired chromaticity, and is not particularly limited. Above all, 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 widening the color reproducibility and increasing the contrast while reducing the phase difference value. It 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 more preferably 25% by mass or more and 100% by mass or less. Even more preferable.

Further, in the colored resin composition for a color filter of the present invention, the red color material and other color materials other than the yellow color material are further contained in the color material as long as the effect of the present invention is not impaired. 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 amount of the coloring material. Is more preferable, and 80% by mass or more and 100% by mass or less is even more preferable.

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

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

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

(Alkali-soluble resin)
The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected and used from those that act as a binder resin and are soluble in the alkali developer used for pattern formation.
In the present invention, the alkali-soluble resin can be referred to as having an acid value of 40 mgKOH / g or more as a guide.
The preferable alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group, and specifically, acrylic such as an acrylic copolymer having a carboxy group and a styrene-acrylic copolymer having a carboxy group. Examples thereof include based resins and epoxy (meth) acrylate resins having a carboxy group. Among these, those having a carboxy group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain are particularly preferable. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. Further, two or more kinds of acrylic resins such as these acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be mixed and used.

Acrylic resins such as an acrylic copolymer having a structural unit having a carboxyl group and a styrene-acrylic copolymer having a carboxy group are, 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. Be done. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic acid anhydride, ω-carboxy-polycaprolactone. Mono (meth) acrylate and the like can also be used. Further, as a precursor of the carboxyl group, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used. Of these, (meth) acrylic acid is particularly preferable in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin preferably has a hydrocarbon ring further from the viewpoint of excellent adhesion of the colored layer. By having a hydrocarbon ring, which is a bulky group, in the alkali-soluble resin, shrinkage during curing is suppressed, peeling from the substrate is alleviated, and substrate adhesion is improved. Further, the present inventors have found that the solvent resistance of the obtained colored layer, particularly the swelling of the colored layer, is suppressed by using the alkali-soluble resin having a hydrocarbon ring. Although the action is unclear, the inclusion of a bulky hydrocarbon ring in the colored layer suppresses the movement of molecules in the colored layer, resulting in higher strength of the coating film and suppression of swelling due to the solvent. It is presumed to be.
Examples of such a hydrocarbon ring include an aliphatic hydrocarbon ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, and a combination thereof. May have a substituent such as an alkyl group, a carbonyl group, a 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 may be contained as a divalent or higher valent group.

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

When the hydrocarbon ring contains an aliphatic hydrocarbon ring, it is preferable because the heat resistance and adhesion of the colored layer are improved and the brightness of the obtained colored layer is improved.
Further, when the cardo structure is included, it is particularly preferable because the curability of the colored layer is improved and the solvent resistance (suppression of NMP swelling) is improved.

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

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

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

［一般式（ＩＩＩ）において、Ｒ^Ｍは、置換されていてもよい炭化水素環である。］

[In general formula (III), ^RM is a optionally substituted hydrocarbon ring. ]

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

Specific examples of the hydrocarbon ring that may be substituted in the ^RM of the general formula (III) include the same examples as those of the specific example of the hydrocarbon ring.
For example, an aliphatic hydrocarbon ring such as a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a methoxyphenyl group, a benzyl group, a hydroxyphenyl group, Examples include an aromatic hydrocarbon ring such as a naphthyl group, and a group in which a part of these groups is substituted with a substituent.

In the alkali-soluble resin used in the present invention, it is easier to adjust the amount of each structural unit by using an acrylic copolymer having a structural unit having a hydrocarbon ring in addition to the structural unit having a carboxy group. It is preferable because it is easy to increase the amount of the structural unit having the hydrocarbon ring to improve the function of the structural unit.
The acrylic copolymer having the structural unit having a carboxy group and the above-mentioned hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer". 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. Examples thereof include (meth) acrylate and styrene, and cyclocarbonate (meth) acrylate, dicyclopentanyl (meth) acrylate, and adamantyl (adamantyl) are used because the cross-sectional shape of the colored layer after development has a great effect of being maintained even in heat treatment. It is preferable to use at least one selected from meta) acrylate, benzyl (meth) acrylate, and styrene.

The alkali-soluble resin used in the present invention also preferably has an ethylenic double bond in the side chain. In the case of having an ethylenically double bond, the alkali-soluble resins or the alkali-soluble resin and the polyfunctional monomer may form a cross-linking 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 to improve the development resistance, and the heat shrinkage of the cured film is suppressed to improve the adhesion to the substrate.
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 adding a compound having an epoxy group and an ethylenic double bond in the molecule, for example, glycidyl (meth) acrylate, to the carboxyl group of the alkali-soluble resin, and introducing an ethylenic double bond into the side chain. Alternatively, a method in which a structural unit having a hydroxyl group is introduced into a copolymer, a compound having an isocyanate group and an ethylenic double bond is added to the molecule, and an ethylenic double bond is introduced into a side chain. And so on.

The alkali-soluble resin of the present invention may further contain other structural units such as methyl (meth) acrylate and ethyl (meth) acrylate, which are structural units having an ester group. 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 solubility in a solvent and further improves solvent resolubility.

The alkali-soluble resin in the present invention is preferably an acrylic resin such as an acrylic copolymer having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, and a styrene-acrylic copolymer. 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 charging amount of each structural unit.

The amount of the carboxyl group-containing ethylenically unsaturated monomer charged is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount of the monomers, from the viewpoint of obtaining a good pattern. On the other hand, the amount of the carboxyl group-containing ethylenically unsaturated monomer charged is preferably 50% by mass or less, preferably 40% by mass or less, based on the total amount of the monomers, from the viewpoint of suppressing the film roughness of the pattern surface after development. It is more preferable to have.
When the proportion of the carboxyl group-containing ethylenically unsaturated monomer is at least the above 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 above upper limit. If it is as follows, there is a tendency that the formed pattern is less likely to fall off from the substrate or the surface of the pattern is roughened during development with an alkaline developer.

Further, in an acrylic resin such as an acrylic copolymer having a structural unit having an ethylenic double bond and a styrene-acrylic copolymer, which are more preferably used as an alkali-soluble resin, an epoxy group and an ethylenic double bond are used. 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, based on 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 significantly deteriorated, and if it exceeds 50,000, it may be difficult to form a pattern during development with an alkaline developer.
The weight average molecular weight (Mw) of the carboxy group-containing copolymer can be measured by a Shodex GPC system-21H (Shodex GPC System-21H) using polystyrene as a standard material and THF as an eluent.

The epoxy (meth) acrylate resin having a carboxy group is not particularly limited, but is an epoxy (meth) obtained by reacting a reaction product of an epoxy compound with an unsaturated group-containing monocarboxylic acid with an acid anhydride. Epoxy compounds are suitable.
The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known ones and used. The epoxy (meth) acrylate resin having a carboxy group may be used alone or in combination of two or more.

It is preferable to select and use an alkali-soluble resin having an acid value of 50 mgKOH / g or more from the viewpoint of developability (solubility) in an alkaline aqueous solution used for a developing solution. 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) in an alkaline aqueous solution used for a developing solution and adhesion to a substrate. It is preferably 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.

When the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated bond equivalent has the effect of improving the film strength of the cured film, improving the development resistance, and excellent adhesion to the substrate. From the point of view, 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. Further, if it is 100 or more, the ratio of other structural units such as the structural unit having a carboxy group and the structural unit having a hydrocarbon ring can be relatively increased, so that the developability and heat resistance are excellent. There is.
Here, the ethylenically unsaturated bond equivalent is the weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following mathematical formula (1).

Formula (1)
Ethylene unsaturated bond equivalent (g / mol) = W (g) / M (mol)
(In the 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 ethylenically double bonds contained in 1 g of an alkali-soluble resin in accordance with the test method for iodine value as described in JIS K 0070: 1992. It may be calculated.

The alkali-soluble resin used in the colored resin composition for a color filter may be used alone or in combination of two or more, and the content thereof is not particularly limited, but is used for a color filter. The alkali-soluble resin is preferably in the range of 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 40% by mass or less with respect to the total solid content of the colored resin composition. When the content of the alkali-soluble resin is at least the above lower limit value, sufficient alkali developability can be easily obtained, and when the content of the alkali-soluble resin is at least the above upper limit value, the film is roughened or the pattern is chipped during development. Is easy to suppress.

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

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

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

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

In the present invention, the initiator preferably contains an oxime ester-based photoinitiator from the viewpoint of improving sensitivity. By using the oxime ester-based photoinitiator, it is easy to suppress the variation in the line width in the plane when forming the fine line pattern. Further, by using the oxime ester-based photoinitiator, the development resistance tends to be improved and the effect of suppressing the generation of water stains tends to be enhanced. In addition, water stain means that when a component that enhances alkaline developability is used, traces of water stain are generated after alkaline development and rinsing with pure water. Such water stains disappear after post-baking, so there is no problem as a product, but there is a problem that it is detected as unevenness abnormality in the visual inspection of the patterning surface after development, and it is not possible to distinguish between normal products and abnormal products. Occurs. Therefore, if the inspection sensitivity of the inspection device is lowered in the visual inspection, the yield of the final color filter product is lowered as a result, which becomes a problem.
The oxime ester-based photoinitiator preferably has an aromatic ring, and has a condensed ring containing an aromatic ring, from the viewpoint of reducing contamination of the colored resin composition for a color filter by decomposition products and contamination of the apparatus. It is more preferable to have a fused ring containing a benzene ring and a hetero ring.
Oxime ester-based photoinitiators include 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime), JP-A-2000-80068, JP-A-2001-233842, JP-A-2010-527339, JP-A-2010-527338, It can be appropriately selected from the oxime ester-based photoinitiators described in JP-A-2013-041153 and the like. Commercially available products include Irgacure OXE-02 (manufactured by BASF) having a carbazole skeleton, ADEKA ARCLUS NCI-831 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changshu Strong Electronics New Materials Co., Ltd.), and ADEKA having a diphenylsulfide skeleton. Arcles NCI-930 (manufactured by ADEKA), TR-PBG-345, TR-PBG-3057 (above, manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.) Irgacure OXE-01 (manufactured by BASF), TR-PBG with fluorene skeleton 365 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.) may be used. In particular, it is preferable to use an oxime ester-based photoinitiator having a diphenylsulfide skeleton or a fluorene skeleton from the viewpoint of brightness. Further, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.
Further, it is preferable to use two or more kinds of oxime ester-based photoinitiators in combination because the brightness and development resistance are easily improved and the effect of suppressing the generation of water stains is high. In particular, the combined use of two types of oxime ester-based photoinitiators having a diphenyl sulfide skeleton or the combined use of an oxime ester-based photoinitiator having a diphenyl sulfide skeleton and an oxime ester-based photoinitiator having a fluorene skeleton has high brightness and heat resistance. It is preferable because of its high property. Further, the combined use of the oxime ester-based photoinitiator having a carbazole skeleton and the oxime ester-based photoinitiator having a fluorene skeleton or the oxime ester-based photoinitiator having a diphenyl sulfide is excellent in sensitivity and the effect of suppressing the occurrence of water stains. Is preferable.

Further, it is preferable to use an oxime ester-based photoinitiator in combination with a photoinitiator having a tertiary amine structure from the viewpoint of suppressing water stains and improving sensitivity. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure which is an oxygen quencher in the molecule, the radicals generated from the initiator are not easily deactivated by oxygen, and the sensitivity can be improved. be. Examples of commercially available photoinitiators having a tertiary amine structure include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (for example, Irgacure 907, manufactured by BASF). 2-Benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (eg, Irgacure 369, manufactured by BASF), 4,4'-bis (diethylamino) benzophenone (eg, Hycure ABP, etc.) Kawaguchi Pharmaceutical Co., Ltd.).
In addition, it is preferable to combine the oxime ester-based photoinitiator with the thioxanthone-based initiator from the viewpoints of adjusting the sensitivity, suppressing water stains, and improving the development resistance. It is preferable to combine an initiator in that the brightness and development resistance are improved, the sensitivity can be easily adjusted, the effect of suppressing the occurrence of water stains is high, and the development resistance is improved.

The content of the photoinitiator used in the colored resin composition for a color filter of the present invention is usually about 0.01 part 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. It is 60 parts by mass or less. When this content is at least the above lower limit value, photocuring is sufficiently advanced and the exposed portion is suppressed from elution during development, while when it is at least the above upper limit value, the yellowing of the obtained colored layer is weakened and the brightness is increased. It is possible to suppress the decrease.
Further, as the photoinitiator used in the colored resin composition for a color filter of the present invention, the total content of two or more kinds of oxime ester-based photoinitiators is based on the total solid content of the colored resin composition for a color filter. The point that the combined effect of these photoinitiators is sufficiently exhibited when the content is in the range of 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. It is preferable from the above.

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 or more and 97% by mass or less 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 mass% or more and 96% by mass or less. When it is at least the above lower limit value, a colored layer having excellent hardness and adhesion to the substrate can be obtained. Further, when it is not more than the above upper limit value, the developability is excellent and the generation of minute wrinkles due to heat shrinkage is suppressed.

<Arbitrary additive component>
The colored resin composition for a color filter may contain various additives, if necessary.
Additives include, for example, antioxidants, mercapto compounds, polymerization inhibitors, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, UV absorbers, adhesion promoters. And so on.

It is preferable that the colored resin composition for a color filter of the present invention further contains an antioxidant because the heat resistance is improved, the fading of the coloring material is suppressed, and the brightness is improved. Further, it is preferable that the colored resin composition for a color filter 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 ones. Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like, and have heat resistance. From this point of view, it is preferable to use a hindered phenolic antioxidant.

A hindered phenolic antioxidant is a structure containing at least one phenol structure in which a substituent having 4 or more carbon atoms is substituted at at least one of the 2- and 6-positions of the hydroxyl group of the phenol structure. It means an antioxidant having.
Specific examples of the hindered phenol-based antioxidant include dibutyl hydroxytoluene (BHT) and 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) mecitylene (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, manufactured by 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: Irga) Knox MD1024, manufactured by BASF), octyl 3- (4-hydroxy-3,5-diisopropylphenyl) propionate (trade name: Irganox 1135, manufactured by BASF), 4,6-bis (octylthiomethyl) -o-cresol (Product name: Irganox 1520L, manufactured by BASF), N, N'-hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide] (trade name: Irganox 1098, 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-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: ADK STAB AO-80, Adeca) , Bis (3-tert-butyl-4-hydroxy-5-methylbenzenepropionic acid) Ethylenebis (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-triazi N-2,4,6 (1H, 3H, 5H) -trion (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- Dethyl 4-hydroxybenzylphosphonate (trade name: Irgamod 195, manufactured by BASF), 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl acrylate ( Product name: Sumilyzer GM, manufactured by Sumitomo Chemical Co., Ltd., 4,4'-thiobis (6-tert-butyl-m-cresol) (Product name: Sumilyzer WX-R, manufactured by Sumitomo Chemical Co., Ltd.), 6,6'-di-tert -Butyl-4,4'-butylideneji-m-cresol (trade name: Adecastab AO-40, manufactured by ADEKA) and the like can be mentioned. 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. ..
Further, a hindered phenolic antioxidant having a molecular weight of 1000 or less and a molecular weight of 280 equivalents or less per phenolic hydroxyl group, and further having a molecular weight of 500 or less and a molecular weight of 200 equivalents or less per phenolic hydroxyl group. Is preferable because it is possible to form a colored layer having improved brightness and contrast while reducing the retardation value. Since such antioxidants have high fluidity and many active points per weight, radical traps suppress the aggregation of colorants due to rapid curing shrinkage during exposure and post-baking, and resin and the like. It is presumed that the above effect is likely to be obtained by suppressing yellowing. Examples of such an antioxidant include 6,6'-di-tert-butyl-4,4'-butylidenge-m-cresol (trade name: ADEKA STAB AO-40, manufactured by ADEKA) and the like.

Further, in the present invention, it is preferable to use a latent antioxidant as the antioxidant because it is possible to form a colored layer having improved contrast while reducing the phase difference value. When a latent antioxidant is used, the radical trapping effect is particularly high during post-baking, so it is presumed that the above effect is likely to be obtained by suppressing color material aggregation due to rapid curing shrinkage during post-baking. Will be done. In the present invention, the latent antioxidant is a compound having a protecting group that can be desorbed by heating, and is a compound that exhibits an antioxidant function when the protecting group is desorbed. Of these, those that facilitate the removal of protecting groups by heating at 150 ° C. or higher are preferable. For example, potential antioxidants as described in WO 2014/021023.
Examples of the latent antioxidant preferably used in the present invention include a latent hindered phenolic antioxidant in which the phenolic hydroxyl group of the hindered phenolic antioxidant is protected by a protecting group that can be desorbed by heating. .. Examples of the latent hindered phenolic antioxidant include the phenolic hydroxyl group of the hindered phenolic antioxidant, acid anhydride, acid anhydride, Bocification reagent, alkyl halide compound, silyl chloride compound, and allyl ether compound. The reaction product with is mentioned. As the latent hindered phenolic antioxidant, among them, a structure in which hydrogen of the phenol group of the hindered phenolic antioxidant is replaced with a carbamate-based protecting group such as 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, and for example, JP-A-57-11375, JP-A-3-173843, JP-A-6-128195, JP-A-7-206771, JP-A-7-252191, Special Table. Obtained by reacting a phenolic compound produced by the method described in each publication of 2004-501128 with an acid anhydride, a acid anhydride, a chloride reagent, an alkyl halide compound, a silyl chloride compound, an allyl ether compound, or the like. Can be done. Further, a commercially available product may be used.

The colored resin composition for a color filter of the present invention is preferably contained as a colored resin composition in combination with the oxime ester-based photoinitiator and an antioxidant because the brightness is improved by a synergistic effect.

The content of the antioxidant is preferably 0.05 parts by mass or more and 10.00 parts by mass or less, preferably 0.10 parts by mass, based on 100 parts by mass of the total solid content in the colored resin composition. It is more preferable that the amount is 5.00 parts by mass or more and 5.00 parts by mass or less. If it is at least the above lower limit value, it is excellent in heat resistance and light resistance. On the other hand, if it is not more than the above upper limit value, the colored resin composition of the present invention can be a highly sensitive photosensitive resin composition.

When the antioxidant is used in combination with the oxime ester-based photoinitiator, the 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-based 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 further preferably 5 parts by mass or more and 45 parts by mass or less. If it is within the above range, the effect of the above combination is excellent.

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 generation of water stains.
Further, when the colored resin composition for a color filter of the present invention is contained as a photosensitive colored resin composition in combination with the oxime ester-based photoinitiator and a mercapto compound, development resistance is improved and water stains occur. It is preferable from the viewpoint that the suppressing effect is further improved, the linearity is further improved when the fine line pattern is formed, and the ability to form the fine line pattern according to the design of the mask line width is improved. In addition, "improved linearity" means that the unevenness of the end portion of the colored layer formed in the developing step after applying the coloring composition is small, and the colored layer is formed in a linear or substantially linear shape.

The mercapto compound can function as a chain transfer agent, and has the property of receiving radicals from slow-reacting radicals to accelerate the reaction and improve curability.
Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzoimidazole, and 3-mercaptopropionic acid. , 3-Methyl mercaptopropionate, Ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis (3-mercaptobutylyloxy) butane, 1,3,5-tris (3-mercaptobutyloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethyl propionate (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), Examples thereof include pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) and the like.
The mercapto compound may be used alone or in combination of two or more, and among them, one or more selected from the group consisting of polyfunctional mercapto compounds having two or more mercapto groups in one molecule may be used. This is preferable because the crosslink density is high and the effect of suppressing water stains is improved.
Further, a secondary mercapto compound having a secondary mercapto group in which the carbon atom to which the mercapto group is bonded is a secondary carbon atom is preferable because a good water stain suppressing effect can be easily maintained even after long-term storage. Further, it is more preferable that the polyfunctional secondary mercapto compound has two or more secondary mercapto groups in one molecule.

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

Further, it is preferable that the colored resin composition for a color filter of the present invention further contains an ultraviolet absorber because it is possible to form a colored layer having improved contrast while reducing the phase difference value. It is presumed that the effect of improving these characteristics is due to the suppression of color material aggregation due to rapid curing shrinkage in the exposure process. The ultraviolet absorber may be appropriately selected from conventionally known ones. Specific examples of the ultraviolet absorber include benzotriazole-based compounds, benzophenone-based compounds, triazine-based compounds and the like. Above all, it is preferable to use a benzotriazole-based compound from the viewpoint that a colored layer having improved contrast can be formed while the retardation value is reduced.

Examples of the benzotriazole-based compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, and octyl-3 [3-]. t-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-t-butyl-4-hydroxy-5- (5-) Chloro-2H-benzotriazole-2-yl) phenyl] propionate mixture, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3- (3-) t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5) '-T-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H-benzotriazole-2-yl)-(1,1-dimethylethyl)-(1,1-dimethylethyl) ) -4-Hydroxy, C7-9 side chain and linear alkyl ester compound, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2 -(2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol and the like, but are limited thereto. It is not something that is done.
Examples of commercially available products include BASF's "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", and "TINUVIN 384-2". , "TINUVIN 900", "TINUVIN 928", "TINUVIN 99-2", "TINUVIN 1130" and the like.

As the benzotriazole-based compound, the benzotriazole-based compound represented by the following general formula (IV) is preferable from the viewpoint that a colored layer having improved contrast can be formed while the phase difference value is reduced.

（一般式（ＩＶ）中、Ｒ^１１及びＲ^１２はそれぞれ独立して、水素原子又はフェニル基で置換されていても良い炭素数１～２０のアルキル基、Ｘは、水素原子又は塩素原子を表す。）

(In the general formula (IV), R ¹¹ and R ¹² each independently represent 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 the 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 hydrogen. It is preferably an atom, a t-butyl group, a t-amyl group, or an α, α-dimethylbenzyl group.

The content of the ultraviolet absorber used in the colored resin composition for a color filter is not particularly limited, but the amount of the ultraviolet absorber is 0.05 part by mass or more with respect to 100 parts by mass of the total solid content in the 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 at least the above lower limit value, it is excellent in heat resistance and light resistance. On the other hand, if it is not more than the above upper limit value, the colored resin composition of the present invention can be a highly sensitive photosensitive resin composition.

The colored resin composition for a color filter of the present invention is preferably contained as a colored resin composition in combination with the oxime ester-based photoinitiator and an ultraviolet absorber because the brightness is improved by a synergistic effect.

When the ultraviolet absorber is used in combination with the oxime ester-based 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-based 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 further preferably 5 parts by mass or more and 45 parts by mass or less. If it is within the above range, the effect of the above combination is excellent.

Specific examples of the surfactant and the plasticizer include those described in JP2013-029832A.

Examples of the silane coupling agent 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 Co., Ltd.) 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, and is 0. . More preferably, it is 1 part by mass or more and 5.0 parts by mass or less. When it is at least the above lower limit value and at least the above upper limit value, the adhesion of SiN is excellent.

<Mixing ratio of each component in the colored resin composition for color filter>
The total content of the coloring material shall be 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 the color filter. Is preferable. When it is at least the above lower limit value, the colored layer when the colored resin composition for a color filter is applied to a predetermined film thickness (usually 1.0 μm or more and 5.0 μm or less) has a sufficient color density. Further, when it is not more than the above upper limit value, it is possible to obtain a colored layer having excellent storage stability, sufficient hardness, and adhesion to a substrate. In particular, when a colored layer having a high color material concentration is formed, the content of the color material is 15% by mass or more and 65% by mass or less, more preferably 25, with respect to the total solid content of the coloring resin composition for a color filter. It is preferable to mix in a proportion of mass% or more and 60% by mass or less.
The content of the dispersant is not particularly limited as long as it can uniformly disperse the coloring material, but is, for example, 1 with respect to the total solid content of the colored resin composition for a color filter. It can be used in an amount of% by mass or more and 40% by mass or less. Further, it is preferable to blend in a proportion of 2% by mass or more and 30% by mass or less, and particularly preferably in a proportion of 3% by mass or more and 25% by mass or less with respect to the total solid content of the colored resin composition for a color filter. .. When it is at least the above lower limit, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the colored resin composition for a color filter is excellent. Further, when it is not more than the above upper limit value, the developability is good. In particular, when forming a colored layer having a high colorant concentration, the content of the dispersant is 2% by mass or more and 25% by mass or less, more preferably 3 with respect to the total solid content of the colored resin composition for a color filter. It is preferable to mix in a proportion of mass% or more and 20% by mass or less.
Further, the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. It is usually preferably in the range of 55% by mass or more and 95% by mass or less 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 or more and 88% by mass or less. It is more preferable to have. When the content of the solvent is within the above range, the coatability can be made excellent.

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

<Cured film of colored resin composition for color filter>
The colored resin composition for a color filter has chromaticity coordinates of x = 0.550 to 0.700 and y = 0.290 to 0.450 in the XYZ color system of JIS Z8701 measured using a C light source. It is preferable that a cured film in the range of 1 can be formed.
Above all, from the viewpoint of improving color reproducibility, the chromaticity coordinates in the XYZ color system of JIS Z8701 measured using the C light source are x = 0.570 to 0.693 and y = 0.300 to 0. It is preferable that a cured film in the range of .426 can be formed, and further, it is possible to form a cured film in the range of x = 0.600 to 0.690 and y = 0.300 to 0.348. 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 has x in the chromaticity coordinates in the XYZ color system of JIS Z8701 measured by a C light source with a single pixel. It is preferable to be able to display a color space in the range of = 0.570 to 0.693, y = 0.300 to 0.426 and a stimulus value Y of 9.0 ≦ Y, and further, x = 0.600 to 0.690. , Y = 0.300 to 0.348 and it is more preferable to be able to display a color space in which the stimulus value Y is in the range of 9.5 ≦ Y. The thickness of the cured film here is the film after the colored resin composition for a color filter is applied, dried, exposed to cure the polyfunctional monomer, and then post-baked in a clean oven at 230 ° C. for 30 minutes. It means thickness.
In the chromaticity coordinates in the XYZ color system of JIS Z8701 measured with a C light source with a single pixel and a film thickness of 2.8 μm or less, x = 0.570 to 0.693, y = 0.300. As a good blending ratio or combination for displaying a color space in the range of ~ 0.426 and a stimulus value Y of 9.0 ≦ Y, the red color material is 45.0% by mass or more 98 with respect to the total amount of the color material. It is preferable that the content is 0.0% by mass or less, the specific yellow color material is 2.0% by mass or more and 55.0% by mass or less, and the red color material is 50.0% by mass or more and 95.0% by 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 said. Is preferably 10.0% by mass or more and 45.0% by mass or less.

<Manufacturing method of 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, and for example, the color material dispersion of the present invention contains an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and if necessary. It can be obtained by adding other components and mixing using a known mixing means. Alternatively, the dispersant is used to prepare a color material dispersion liquid for each color material, and each color material dispersion liquid, a binder component, and if necessary, other components are mixed by a known mixing means. It can be obtained by mixing.

[Color filter]
The color filter according to the present invention is a color filter including at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a colored resin composition for a color filter according to the present invention. It has a colored layer which is a cured product of.

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

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

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

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

(Shading part)
The light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate described later, and can be the same as that used as a light-shielding portion in a general color filter.
The pattern shape of the light-shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. The light-shielding portion may be a metal thin film such as chromium obtained by a sputtering method, a vacuum vapor deposition method, or the like. Alternatively, the light-shielding portion 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 the resin binder. In the case of a resin layer containing light-shielding particles, 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 a photosensitive resist, etc. be.

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

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

The transparent substrate in the color filter of the present invention may be any base material transparent to visible light, and is not particularly limited, and a transparent substrate used for a general color filter can be used. Specifically, a transparent rigid material having no flexibility such as quartz glass, non-alkali glass, or synthetic quartz plate, or a transparent flexible material having flexibility such as a transparent resin film, an optical resin plate, or flexible glass. The material is mentioned.
The thickness of the transparent substrate is not particularly limited, but for example, one having a thickness of 100 μm or more and 1 mm or less can be used depending on the use of the color filter of the present invention.
In addition to the substrate, the light-shielding portion, and the colored layer, the color filter of the present invention has, for example, an overcoat layer, a transparent electrode layer, an alignment film, alignment protrusions, columnar spacers, and the like. May be good.

[Display device]
The display device according to the present invention is characterized by having 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, and examples thereof include 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 display disorder due to the electrical characteristics of green pixels and a burn-in phenomenon due to a switching threshold deviation are suppressed. Therefore, the liquid crystal display is displayed. The device is preferably selected.

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

The drive method of the liquid crystal display device of the present invention is not particularly limited, and a drive method generally used for the liquid crystal display device can be adopted. Examples of such a drive system include a TN system, an IPS system, an OCB system, an MVA system, and the like. In the present invention, any of these methods can be suitably used.
Further, as the facing substrate, it can be appropriately selected and used according to the drive method and the like of the liquid crystal display device of the present invention.

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

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

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

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
The acid value of the block copolymer before salt formation was determined by a method according to the method described in JIS K 0070.
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 above-mentioned measuring method of the present invention.
The glass transition temperature (Tg) of the block copolymer before and after salt formation is measured by differential scanning calorimetry (DSC) (EXSTAR DSC 7020, manufactured by SII Nanotechnology) by a method according to the method described in JIS K7121. Was measured using.

(Production Example 1 Preparation of Azo Derivative 1)
23.1 g of diazobarbituric acid and 19.2 g of barbituric acid were introduced into 550 g of distilled water. Then, it was adjusted to azobarbituric acid (0.3 mol) using an aqueous potassium hydroxide solution, and mixed with 750 g of distilled water. 5 g of 30% hydrochloric acid was added dropwise. Then, 38.7 g of melamine was introduced. Then, 0.57 mol of nickel chloride solution and 0.03 mol of copper chloride solution were mixed and added, and the mixture was 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 (Ni: Cu = 95: 5 (molar ratio) azo pigment).

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

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

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

(Synthesis Example 1: Preparation of Dispersant a)
Add 250 parts by mass of THF and 0.6 parts by mass of lithium chloride to a 500 mL round bottom 4-port separable flask equipped with a cooling tube, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer to sufficiently replace nitrogen. rice field. After cooling the reaction flask to −60 ° C., 4.9 parts by mass of butyl lithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. 1-ethoxyethyl methacrylate (EEMA) 3.3 parts by mass, 2-hydroxyethyl methacrylate (HEMA) 18.2 parts by mass, 2-ethylhexyl methacrylate (EHMA) 4.2 parts by mass, methacrylic acid for B block monomer 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 A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to obtain a solid content of 30% by mass. 32.5 parts by mass of water was added, the temperature was raised to 100 ° C., and the mixture was reacted for 7 hours to deprotect the constituent units derived from EEMA to obtain constituent units derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, purified by filtration and vacuum drying, and is a structural unit derived from an 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 B block having a pro-solvent property was obtained. When the block copolymer A-1 thus obtained was confirmed by GPC (gel permeation chromatography), the weight average molecular weight Mw was 8100. The amine value was 110 mgKOH / g.
In a 100 mL round bottom flask, 29.35 parts by mass of block copolymer A-1 is dissolved in 29.35 parts by mass of PGMEA, and 1.59 parts by mass of phenylphosphonic acid (manufactured by Tokyo Kasei) (phenylphosphonic acid is block-weighted). 0.1 mol) was added to 1 mol of the DMMA unit of the coalesced 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.
In an NMR sample tube, put 1 g of a solution containing 9 parts by mass of salt-type block copolymer A-1 (solid matter after reprecipitation) and 91 parts by mass of chloroform-D1 NMR, and put ¹³ C-NMR spectrum into nuclear magnetic resonance. The measurement was performed using a resonator (manufactured by JEOL Ltd., FT NMR, JNM-AL400) under the conditions of room temperature and 10000 integrations. Of the obtained spectral data, the integrated value of the carbon atom peak adjacent to the unsalted nitrogen atom and the carbon atom peak adjacent to the salt-formed nitrogen atom at the terminal nitrogen moiety (amino group). From the ratio, calculate the ratio of the number of amino groups formed by salt to the total number of amino groups, which is not different from the theoretical salt formation ratio (two acidic groups of total phenylphosphonic acid are the DMMA of block copolymer A-1). It was confirmed that it formed a salt with the nitrogen site at the end).
The amine value after salt formation was calculated as 88 mgKOH / g by subtracting the amine value (22 mgKOH / g) for 0.20 mol of the DMMA unit from the amine value of 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, the pre-salt formation block copolymers A-2 to A-4 and the salt-type block copolymer A-2 are the same as in Synthesis Example 1, except that the content is changed to the content shown in Table 1. (Dispersant b) to A-4 (Dispersant d) solutions were synthesized. In addition, 1-ethoxyethyl methacrylate (EEMA) was used in 2.8 parts by mass in Synthesis Example 2, 2.2 parts by mass in Synthesis Example 3, and 1.1 parts by mass in Synthesis Example 4. 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-port separable flask was depressurized, dried, and then replaced with Ar (argon).
While Ar-flowing, 100 g of dehydrated THF, 2.0 g of methyltrimethylsilyldimethylketenacetal, 0.15 ml of a 1 M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), and 0.2 g of mesitylene were added. Using a dropping funnel, 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 methacrylic acid. 35.7 parts by mass of methyl (MMA) was added dropwise over 45 minutes. Since heat was generated as the reaction proceeded, 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 LiBr10 mM) was 8,350, and the amine value was 95 mgKOH / g.
Block copolymer A-5 is dissolved in 29.35 parts by mass of PGMEA in a 100 mL round bottom flask, and 3.17 parts by mass of phenylphosphonic acid (PPA, manufactured by Tokyo Kasei) (phenylphosphonic acid blocks). 0.20 mol) is added to 1 mol of the DMMA unit of the copolymer A-5, and the mixture is stirred at a reaction temperature of 30 ° C. for 20 hours to obtain a salt-type block copolymer A-5 (dispersant e) solution. rice field. 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, benzyl chloride (manufactured by Tokyo Kasei) was used in place of phenylphosphonic acid in an amount of 3.80 parts by mass (0.3 mol with respect to 1 mol of DMMA unit in which benzyl chloride is block copolymer A-5). A solution of the salt-type block copolymer A-6 (dispersant f) was synthesized in the same manner as in Synthesis Example 5. 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 (BzMA). Instead of 35.7 parts by mass of MMA), 7.6 parts by mass of n-butyl methacrylate (BMA), 32.9 parts by mass of methyl methacrylate (MMA), and PME-1000 (methoxypolyethylene glycol monomethacrylate (polyethylene glycol)). Chain repeat number n≈23), trade name Blemmer PME-1000, manufactured by Nichiyu) 39.9 parts by mass, dimethylaminoethyl methacrylate (DMMA) replaced by 26.7 parts by mass, 19.6 parts by mass. A solution of the block copolymer A-7 before salt formation and the salt-type block copolymer A-7 (dispersant g) was obtained in the same manner as in Synthesis Example 5 except that it was used. 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 is dropped into a polymerization tank containing 150 parts by mass of PGMEA at 100 ° C. over 3 hours. did. After completion of the 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 were added to the obtained polymer solution, and the mixture was heated at 110 ° C. for 10 hours for reaction. Air was bubbled into the solution. The obtained alkali-soluble resin A is a resin in which a side chain having an ethylenic double bond is introduced into a 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 by a Shodex GPC system-21H (Shodex GPC System-21H) 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)
In Synthesis Example 8, instead of using 40 parts by mass of BzMA as the comonomer species at the time of polymerization, 20 parts by mass of styrene and 20 parts by mass of N-phenylmaleimide (Tokyo Kasei Kogyo 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 12000.

(Synthesis Example 10: Synthesis of Latent Antioxidant (Compound a))
0.01 mol of phenol compound represented by the following chemical formula (3), 0.05 mol of di-tert-butyl dicarbonate and 30 g of pyridine are mixed, and 0.025 mol of 4-dimethylaminopyridine is added at room temperature under a nitrogen atmosphere, and 60 The mixture was stirred at ° C. for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, 200 g of chloroform was added, and oil-water separation was performed. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and 100 g of methanol was added to the residue for crystallization. The obtained white powdery crystals were dried under reduced pressure at 60 ° C. for 3 hours 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 Coloring Material Dispersion Liquid R1 As a dispersant, 6.23 parts by mass of the dispersant a solution of Synthesis Example 1 was used, and as a red color material, a diketopyrrolopyrrole pigment (BrDPP, commercial product) represented by the following chemical formula (2). Name Irgaphor RED S 3621CF, manufactured by BASF) in 2.57 parts by mass, C.I. I. Pigment Red 254 (trade name: Hostaperm Red D2B-COF LV3781, manufactured by CLARIANT) in an amount of 3.86 parts by mass, C.I. I. Pigment Red 177 (trade name: Cromophtal Red A2B, manufactured by BASF) was 2.08 parts by mass, and the Azo derivative 2 obtained in Production Example 2 as a yellow color material was 4.49 parts by mass, and the alkali solubility obtained in Synthesis Example 8. Put 14.59 parts by mass of resin A solution, 66.12 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm in a mayonnaise bottle, and use a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for preliminary crushing. 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 disperse for 4 hours with a paint shaker as the main crushing in the same manner. A dispersion R1 was obtained.

(2) Production of Colored Resin Composition R1 for Color Filter 11.29 parts by mass of the coloring material dispersion R1 obtained in (1) above, and 1.90 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 8. , Multifunctional monomer (trade name: Aronix M-403, manufactured by Toa Synthetic Co., Ltd.) in an amount of 0.60 parts by mass, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one. (Photoinitiator: trade name Irgacure 907 (IRG907), manufactured by BASF) 0.09 part by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: Product name Irgacure 369 (IRG369), manufactured by BASF) 0.04 parts by mass, Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O) -Acetyloxime) (photoinitiator: trade name Adeca Arcurus NCI-831 (NCI831), manufactured by ADEKA) by 0.02 parts by mass, fluorine-based surfactant (brand name Megafuck F559, manufactured by DIC Co., Ltd.) 0.07 parts by mass, silane coupling agent (trade name KBM-503, manufactured by Shinetsu Silicone) 0.07 parts by mass, mercapto compound (pentaerythritol tetrakis (3-mercaptobutyrate)) 0.05 parts by mass, PGMEA 5 parts .85 parts by mass and 3.92 parts by mass of 3-methoxy-3-methyl-1-butyl acetate were added to obtain a colored resin composition R1 for a color filter.
(3) Formation of Colored Layer The colored resin composition R1 obtained in (2) above is placed on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a thickness of 100 mm × 100 mm. After applying with a spin coater, dry at 80 ° C. for 3 minutes using a hot plate, irradiate with ultraviolet rays of 60 mJ / cm ² using an ultra-high pressure mercury lamp, and post-bake in a clean oven at 230 ° C. for 30 minutes. As a result, 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 Coloring Material Dispersion Liquids R2 to R9 and RC1 In Examples 2 to 6 and Comparative Example 1, in (1) of Example 1, instead of the dispersant a solution, respectively, as shown in Table 2. , The same as (1) of Example 1 except that the type and amount of the dispersant were changed so that the solid content was the same by mass and the amount of PGMEA was adjusted so that the total was 100 parts by mass. Color material dispersions R2 to R6 were obtained.
Further, in Examples 7 to 9, the same as in (1) of Example (3) except that the type and amount of the coloring material used were changed as shown in Table 2 in (1) of Example 3. The color material dispersion liquids R7 to R9 were obtained.
Further, in Comparative Example 1, in (1) of Example 1, instead of the dispersant a solution, the type and amount of the dispersant used are set so that the solid content is the same mass part. The color material dispersion liquid RC1 was obtained in the same manner as in (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 the color material were further changed. rice field.
(2) Production of Colored Resin Compositions R2 to R11 and RC1 for Color Filters In Examples 2 to 9 and Comparative Example 1, the color material dispersion liquid R1 in (2) of Example 1 is shown in Table 2, respectively. As described above, using the color material dispersions R2 to R9 and RC1, the amount of the alkali-soluble resin was adjusted so that the P / V ratios would be the values shown in Table 2 in order to make the film thickness 2.10 μm. Colored resin compositions R2 to R9 and RC1 for color filters were obtained in the same manner as in (2) of Example 1 except for the adjustment.
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 further, an antioxidant (trade name IRGANOX1010 (1010)) was used. , BASF) A colored resin composition R10 for a color filter was obtained in the same manner as in (2) of Example 3 except that 0.03 part by mass 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-based photoinitiator (trade name TR-PBG-365 (trade name TR-PBG-365) PBG365), manufactured by Changzhou Strong Electronics New Materials Co., Ltd.) was used in 0.04 parts by mass, and instead of 0.02 parts by mass of NCI831, an oxime ester-based initiator (trade name TR-PBG-3057 (PBG3057), Changzhou Strong Electronics) was used. 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 part by mass of (manufactured by Shin Material Co., Ltd.) was used.
(3) Formation of Colored Layer In (3) of Example 1, the above-mentioned colored resin compositions R2 to R11 and RC1 are used instead of the colored resin composition R1, respectively, except that the colored resin compositions are different from (3) of Example 1. In the same manner, 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, manufactured by LANXESS Co., Ltd.)
Byk-161: Product 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 Coloring Material Dispersion Liquids R12 to R23 In Examples 12 to 23, as shown in Table 3 in Example 3 (1), the types and blending amounts of the coloring materials were changed, and the total was increased. Color material dispersions R12 to R23 were obtained in the same manner as in (1) of Example 3 except that the amount of PGMEA was adjusted to 100 parts by mass.
(2) Production of Colored Resin Compositions R12 to R23 for Color Filters The above colored material dispersions R12 to R23 are used instead of the colorant dispersions R3 in (2) of Example 11, respectively, and the film thickness is 2.50 μm. The colored resin composition for a color filter is the same as in (2) of Example 11 except that the amount of the alkali-soluble resin is adjusted so that the P / V ratio becomes the value shown in Table 3 respectively. R12 to R23 were obtained.
(3) Formation of Colored Layer The same procedure as in (3) of Example 11 except that the colored resin compositions R12 to R23 were used instead of the colored resin composition R11 in (3) of Example 11. The colored layers R12 to R23 were obtained.

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

Ｒ２６４：Ｃ．Ｉ．ピグメントレッド２６４（商品名：Ｉｒｇａｚｉｎ Ｒｅｄ Ｌ ４０１０ ＨＤ、ＢＡＳＦ製）
Ｒ２４２：Ｃ．Ｉ．ピグメントレッド２４２（商品名：Ｎｏｖｏｐｅｒｍ Ｓｃａｒｌｅｔ ４ＲＦ、ＣＬＡＲＩＡＮＴ製）
Ｏ３８：Ｃ．Ｉ．ピグメントオレンジ３８（商品名：Ｎｏｖｏｐｅｒｍ Ｒｅｄ ＨＦ、ＣＬＡＲＩＡＮＴ製）Ｃ．Ｉ．ピグメントオレンジ３８は、Ｐ／Ｖ（赤色色材質量／赤色色材以外の固形分質量）比＝０．２で２．５μｍの塗膜の分光透過率スペクトルを測定した場合に、５２０ｎｍの波長の透過率が２０％以下であり、且つ６４０ｎｍの波長の透過率が７０％以上であり、本発明の赤色色材に相当。
Ｒ１７７：Ｃ．Ｉ．ピグメントレッド１７７（商品名：Ｃｒｏｍｏｐｈｔａｌ Ｒｅｄ Ａ２Ｂ、ＢＡＳＦ製）
Ｒ１７９：Ｃ．Ｉ．ピグメントレッド１７９（商品名：Ｐａｌｉｏｇｅｎ Ｍａｒｏｏｎ Ｌ ３９８０、ＢＡＳＦ Ｄｉｓｐｅｒｓｉｏｎｓ ＆ Ｐｉｇｍｅｎｔｓ Ａｓｉａ Ｐａｃｉｆｉｃ製）
Ｒ２７２：Ｃ．Ｉ．ピグメントレッド２７２（商品名：Ｉｒｇａｚｉｎ Ｆｌａｍｅ Ｒｅｄ Ｋ ３８００、ＢＡＳＦ製）
Ｙ１５０誘導体：Ｃ．Ｉ．ピグメントイエロー１５０誘導体（Ｎｉ錯体）（商品名：ＬＥＶＡＳＣＲＥＥＮ ＹＥＬＬＯＷ Ｇ０１、ランクセス株式会社製）
Ｂｙｋ－１６１：商品名Ｄｉｓｐｅｒｂｙｋ－１６１（ウレタン系分散剤、固形分３０質量％、ビックケミー製）
６９１９：商品名Ｄｉｓｐｅｒｂｙｋ－ＬＰＮ６９１９（一般式（Ｉ）で表される構成単位を有する重合体、アミン価１２０ｍｇＫＯＨ／ｇ、固形分６０質量％、ビックケミー製）

R264: C.I. I. Pigment Red 264 (Product name: Irgazin Red L 4010 HD, manufactured by BASF)
R242: C.I. I. Pigment Red 242 (Product name: Novoperm Scallet 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 the spectral transmittance spectrum of a coating film of 2.5 μm is measured at a P / V (amount of red color material / mass of solid content 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 (Product name: Cromophtal Red A2B, manufactured by BASF)
R179: C.I. I. Pigment Red 179 (Product Name: Pariogen Maroon L 3980, BASF Dispersions & Pigments Asia Pacific)
R272: C.I. I. Pigment Red 272 (Product 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, manufactured by LANXESS Co., Ltd.)
Byk-161: Product 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 to 41)
(1) Production of Coloring Material Dispersion Liquids R24 to R41 In Examples 24 to 41, as shown in Table 4, in Example 3 (1), the types and blending amounts of the coloring materials were changed, and the total was Color material dispersions R24 to R41 were obtained in the same manner as in (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 Filters The above colored material dispersions R24 to R41 are used instead of the colorant dispersions R3 in (2) of Example 11, respectively, and the film thickness is 2.80 μm. The colored resin composition for a color filter is the same as in (2) of Example 11 except that the amount of the alkali-soluble resin is adjusted so that the P / V ratio becomes the value shown in Table 4 respectively. R24 to R41 were obtained.
(3) Formation of Colored Layer The same procedure as in (3) of Example 11 except that the colored resin compositions R24 to R41 were used instead of the colored resin composition R11 in (3) of Example 11. The colored layers R24 to R41 were obtained.

(Example 42)
(1) Manufacture of color material dispersion liquid
As a dispersant, 6.23 parts by mass of the dispersant c solution of Synthesis Example 3 was used, and as a coloring material, a diketopyrrolopyrrole pigment represented by the chemical formula (2) (BrDPP, trade name: Irgaphor RED S 3621CF, manufactured by BASF). 13.0 parts by mass, the alkali-soluble resin A solution obtained in Synthesis Example 8 by 14.59 parts by mass, PGMEA by 66.20 parts by mass, and a particle size of 2.0 mm zirconia beads by 100 parts by mass in a mayonnaise bottle. As a preliminary crush, shake with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour, then take out zirconia beads having a particle size of 2.0 mm, add 200 parts by mass of zirconia beads having a particle size of 0.1 mm, and do the same. As the main crushing, dispersion was carried out with a paint shaker for 4 hours to obtain a red color material dispersion liquid r1.
In the red color material dispersion liquid 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. Pigment Red 254 (trade name: Hostaperm Red D2B-COF LV3781, manufactured by CLARIANT) was obtained in the same manner as the red color material dispersion liquid r1 except that 13.0 parts by mass was used to obtain a red color material dispersion liquid r2.
In the red color material dispersion liquid 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. Pigment Red 177 (trade name: Pariogen Red L 4045, manufactured by BASF) was used in the same manner as the red color material dispersion liquid r1 except that 13.0 parts by mass was used to obtain a red color material dispersion liquid r3.
In the red color material dispersion liquid r1, instead of using 13.0 parts by mass of the diketopyrrolopyrrole pigment (BrDPP) represented by the chemical formula (2) as the color material, 13.0 mass by mass of the Azo derivative 2 as the color material. The yellow color material dispersion liquid y was obtained in the same manner as in the red color material dispersion liquid r1 except that the part 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, red color material The dispersion liquid r3 is 1.92 parts by mass, the yellow color material dispersion liquid y is 4.15 parts by mass, the alkali-soluble resin A solution obtained in Synthesis Example 8 is 1.90 parts by mass, and the polyfunctional monomer (trade name: Aronix M). -403, manufactured by Toa Synthetic Co., Ltd.) by 0.60 parts by mass, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907, (BASF) by 0.09 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name Irgacure 369, manufactured by BASF) by 0.04 mass Part, Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (photoinitiator: trade name Adecaarclus NCI- 831, 0.02 parts by mass of ADEKA), 0.07 parts by mass of fluorine-based surfactant (trade name Megafuck F559, manufactured by DIC Co., Ltd.), silane coupling agent (trade name KBM-503, Shinetsu) (Made of silicone) 0.07 parts by mass, mercapto compound (pentaerythritol tetrakis (3-mercaptobutyrate)) 0.05 parts by mass, PGMEA 5.85 parts by mass, 3-methoxy-3-methyl-1-butyl acetate By adding 3.92 parts by mass, a colored resin composition R42 for a color filter was obtained.
(3) Formation of Colored Layer Coloring is performed in the same manner as in (3) of Example 1 except that the colored resin composition R42 is used instead of the colored resin composition R1 in (3) of Example 1. Layer R42 was obtained.
The obtained colored resin composition R42 for a color filter has the same composition as the colored resin composition R3 for a color filter of Example 3, and the evaluation results of the colored resin composition R42 for a color filter and the colored layer R42 are as follows. The results were the same as the evaluation results of the colored resin composition R3 for the color filter and the colored layer R3.

(Examples 43 to 48)
(1) Production of Coloring Material Dispersion Liquid R47 In Example 47, as shown in Table 5, in Example 1 (1), a dispersant g solution was used instead of the dispersant a solution, and the solid content was solid. The color material dispersion liquid R47 was obtained in the same manner as in (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. Further, as shown in Table 5, the photoinitiator is 0.02 part by mass of an oxime ester-based photoinitiator (trade name: Irgacure OXE 01 (OXE01), manufactured by BASF) instead of 0.04 part by mass of IRG369. Except for using 0.04 part by mass of NCI831 instead of 0.02 part by mass of an oxime ester-based initiator (trade name: Irgacure OXE 02 (OXE02), manufactured by BASF), the same as (2) of Example 3. Similarly, a colored resin composition R43 for a color filter was obtained.
Further, in Example 44, in Example 11, instead of 0.03 parts by mass of the antioxidant (trade name IRGANOX1010 (1010), manufactured by BASF), the antioxidant (trade name Adeka Stub AO-40 (AO-)). 40), ADEKA) A colored resin composition R44 for a color filter was obtained in the same manner as in (2) of Example 11 except that 0.03 parts by mass was used.
Further, in Example 45, instead of 0.03 parts by mass of the antioxidant (trade name IRGANOX1010 (1010), manufactured by BASF) in Example 11, the latent antioxidant (compound a) of Synthesis Example 10 was used. A colored resin composition R45 for a color filter was obtained in the same manner as in (2) of Example 11 except that 0.03 part by mass was used.
Further, in Example 46, instead of adding 0.03 part by mass of an antioxidant (trade name IRGANOX1010 (1010), manufactured by BASF) in Example 11, an ultraviolet absorber (benzotriazole-based compound, trade name). TINUVIN 329 (manufactured by BASF) A colored resin composition R46 for a color filter was obtained in the same manner as in (2) of Example 11 except that 0.03 part by mass was added.
In Example 47, the colored resin composition for a color filter is the same as in Example 3 (2), except that the color material dispersion liquid R47 is used instead of the color material dispersion liquid R3 in Example 3. Obtained R47.
In Example 48, in Example 43, a color material dispersion R47 is used instead of the color material dispersion R3, and an antioxidant (trade name: ADEKA STAB AO-40 (AO-40), manufactured by ADEKA) 0.03. Colored resin composition for color filter in the same manner as in (2) of Example 43 except that 0.03 part by mass and an ultraviolet absorber (benzotriazole-based compound, trade name: TINUVIN 329, manufactured by BASF) were added. I got the thing R48.
(3) Formation of Colored Layer The same procedure as in (3) of Example 1 except that the colored resin compositions R43 to R48 were used instead of the colored resin composition R1 in (3) of Example 1. The colored layers R43 to R48 were obtained.

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

<Optical performance evaluation, contrast evaluation>
The contrast, chromaticity (x, y), and luminance (Y) of the colored layers obtained in Examples and Comparative Examples were measured using the Otsuka Electronics spectral characteristic measuring device LCF-1500M and the Tsubosaka Electric contrast measuring device CT-1B. Was measured.
(Contrast evaluation standard)
-Value when x is 0.570 to 0.600 with C light source AA: Exceeds 10000 A: 8000 to 10000
B: 6000-7999
C: Less than 6000 ・ Value when x is 0.607 to 0.630 with C light source AA: Exceeds 9000 A: 7000 to 9000
B: 5000-6999
C: Less than 5000 ・ Value when x 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 phase difference of the colored layer was indexed by the retardation (Rth) in the thickness direction calculated by the following formula. The retardation (Rth) was measured using a retardation layer measuring device (AxoscanTM Mueller Matrix Polarimator manufactured by AXOMETRICS). The measurement wavelengths of the red colored layer were measured at 620 nm and 665 nm.
Rth = ((Nx + Ny) /2-Nz) d
Nx: Refractive index in the in-plane slow phase axial direction Ny: Refractive index in the in-plane advancing phase axial 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 dipped in the colored resin composition for a color filter obtained in Examples and Comparative Examples, and applied to a 1 cm long portion of the glass substrate. The pulled-up glass substrate was placed in a constant temperature and humidity chamber 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 attached was immersed in PGMEA for 15 seconds. At this time, the redissolved state of the dry coating film was visually discriminated and evaluated.
(Solvent resolubility evaluation criteria)
AA: The dry coating was completely dissolved in 8 seconds or less A: The dry coating was completely dissolved B: Fragments of the dry coating were formed in the solvent and the solution was colored C: The dry coating was completely dissolved in the solvent If the above evaluation criteria are AA, A or B, the solvent resolubility is evaluated to be good and the solution can be used without any problem in practical use, but the evaluation result is A or AA. It is more effective than the solvent.

<Evaluation of development residue>
The colored resin compositions for color filters obtained in Examples and Comparative Examples were placed on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a thickness of 100 mm × 100 mm, respectively, with a spin coater. After coating using, a colored layer having a thickness of 2.5 μm was formed by drying at 60 ° C. for 3 minutes using a hot plate. The glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer. After visually observing the unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer, wipe it off sufficiently with a lens cleaner (manufactured by Toray Industries, Inc., trade name: Toray Industries Wiping Cloth) soaked in ethanol. The degree of coloring of the lens cleaner was visually observed.
(Development residue evaluation criteria)
AA: No development residue was visually confirmed and the lens cleaner was not colored in the same evaluation using a colored layer having a thickness of 3.5 μm. A: No development residue was visually confirmed and the lens cleaner was completely colored. No B: No development residue was visually confirmed and the lens cleaner was slightly colored. C: The development residue was slightly confirmed visually and the lens cleaner was slightly colored. D: The development residue was visually confirmed. If 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 even more AA, the effect is better. ing.

<Development resistance evaluation>
The colored resin compositions for color filters obtained in Examples and Comparative Examples were applied onto a glass substrate (manufactured by NH Techno Glass Co., Ltd., “NA35”) having a thickness of 0.7 mm using a spin coater. After heat-drying on a hot plate at 80 ° C. for 3 minutes, ultraviolet rays of 40 mJ / cm ² were irradiated using an ultra-high pressure mercury lamp. The film thickness at this point is measured and set to T1 (μm). Then, shower development was carried out using a 0.05 mass% potassium hydroxide aqueous 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% If the evaluation results are AA, A, B, it can be practically used, but the above evaluation criteria are A, and further. If it is AA, the effect is more excellent.

<Water stain evaluation>
The colored resin composition for a color filter obtained in each Example and each Comparative Example was placed on a glass substrate (manufactured by NH Technoglass Co., Ltd., “NA35”) in a thickness 1 after post-baking using a spin coater. After applying with a film thickness to form a colored layer of .6 μm, dry at 60 ° C. for 3 minutes using a hot plate, and irradiate the entire surface with ultraviolet rays 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 using 0.05 wt% potassium (KOH) as a developing solution, indirect solution in the developing solution for 60 seconds, and then washing with pure water for development treatment. The washed substrate is rotated for 10 seconds to add water. Immediately after centrifugal removal, the contact angle of pure water was measured as shown below to evaluate water stains.
To measure the contact angle of pure water, a droplet of 1.0 μL of pure water is dropped on the surface of the colored layer immediately after the water is centrifugally removed, and the static contact angle 10 seconds after the droplet is applied is determined according to the θ / 2 method. I measured it. 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 80 degrees or more A: Contact angle 75 degrees or more and less than 80 degrees B: Contact angle 65 degrees or more and less than 75 degrees C: Contact angle 50 degrees or more and less than 65 degrees D: Contact angle less than 50 degrees Water stain evaluation standard is AA , A or B 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 a color filter obtained in each Example and each Comparative Example was applied onto 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 ultraviolet rays of 60 mJ / cm ² using an ultra-high pressure mercury lamp, and further post-baked in a clean oven at 230 ° C. for 30 minutes so that the film thickness after curing becomes 2.10 μm. The thickness was adjusted to form a colored layer.
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 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 standard)
AA: No peeling of any grid
A: Although there is a small peeling of the coating film at the intersection of the cut, the area occupied by the peeling is less than 5%. B: The coating film is peeled off at the intersection along the line of the cut. Occupied area of peeling is 5% or more and less than 15%
C: The coating film is partially or completely peeled off along the cut line. Occupied area of peeling is 15% or more and less than 35%

[Summary of results]
From the results in the table, Examples 1 to 41 combine the red color material with the specific yellow color material, and further combine with a dispersant which is a polymer having a structural unit represented by the general formula (I). , And 47 colorant dispersions were found to have good viscosity stability. On the other hand, it was clarified that the color material dispersion liquid of Comparative Example 1 in which the conventional yellow color material and the urethane-based dispersant were combined with the red color material had poor viscosity stability. Further, it was clarified that the color material dispersion liquid of Comparative Example 2 in which the urethane-based dispersant was combined had poor viscosity stability even when the red color material was combined with the specific yellow color material.
Further, the color material dispersion liquids of Comparative Examples 3 to 7 in which the conventional yellow color material is combined with the red color material may use a dispersant which is a polymer having a structural unit represented by the general formula (I). It was shown to be inferior in viscosity stability.

Further, for the color filters of Examples 1 to 48 in which the red color material is combined with the specific yellow color material, and further, a dispersant which is a polymer having a structural unit represented by the general formula (I) is combined. It was clarified that the colored resin composition had good colorant dispersion stability, and that the colored layer using the colored resin composition had excellent contrast while reducing the phase difference value. Further, the colored layers using the colored resin compositions of Examples 1 to 48 are excellent in adhesion to SiN, respectively, and among them, the colored resin compositions of Examples 11, 44, 45, 46, and 48 were used. It was also clarified that the colored layer has excellent adhesion to SiN. Further, the adhesion to SiN of Example 10 was A, which was close to AA, which was good.
On the other hand, in Comparative Examples 1, 3 to 7, in which different color materials from the examples are combined, the contrast is inferior and the phase difference value is large as compared with the examples having the same chromaticity coordinates (x, y). Was there.
Further, even if the specific yellow color material is combined with the red color material, the contrast of Comparative Example 2 in which the urethane-based dispersant is combined is inferior to that of the example having the same chromaticity coordinates (x, y). , The phase difference value was large.
Further, in Comparative Examples 1 and 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 the examples having the same chromaticity coordinates (x, y). Was there.
Further, Comparative Example 1 was inferior in terms of solvent resolubility, suppression of development residue, development resistance, and water stain as compared with Examples having the same chromaticity coordinates (x, y).

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

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

1 Substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposite 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 emission display device

Claims (13)

A color material dispersion liquid containing a color material, a dispersant, and a solvent.
The color material contains a red color material and a yellow color material, and the color material contains a red color material and a yellow color material.
The yellow color material comprises at least one anion selected from the group consisting of mono, di, tri and tetra anions of an azo compound represented by the following general formula (A) and an azo compound having a tautomeric structure thereof. 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 the compound represented by the following general formula (B). Including,
A color material dispersion for red pixels of 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), Ra is independently -OH, -NH ₂ , -NH-CN, acylamino, alkylamino or arylamino, and R ^b is independently -OH ^or- , respectively. NH ₂ )

(In the general formula (B), 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, and R ² and R ³ are hydrocarbons which may independently contain a hydrogen atom or a hetero atom. Representing a group, R ² and R ³ may be bonded to each other to form a ring structure.) The red pixel of the color filter according to claim 1, wherein the red color material contains at least one selected from the group consisting of a diketopyrrolopyrrole pigment, a naphthol azo pigment, an anthraquinone pigment, and a perylene pigment. Color material dispersion for use. As at least two kinds of metals in the yellow color material, Ni and at least one kind of metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn are used. The color material dispersion liquid for red pixels of the color filter according to claim 1 or 2, which comprises. The color material dispersion liquid for red pixels of the 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 red pixels of a color filter containing a coloring material, a dispersant, a binder component, and a solvent.
The color material contains a red color material and a yellow color material, and the color material contains a red color material and a yellow color material.
The yellow color material comprises at least one anion selected from the group consisting of mono, di, tri and tetra anions of an azo compound represented by the following general formula (A) and an azo compound having a tautomeric structure thereof. 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 the compound represented by the following general formula (B). Including,
A colored resin composition for red pixels of 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), Ra is independently -OH, -NH ₂ , -NH-CN, acylamino, alkylamino or arylamino, and R ^b is independently -OH ^or- , respectively. NH ₂ )

(In the general formula (B), 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, and R ² and R ³ are hydrocarbons which may independently contain a hydrogen atom or a hetero atom. Representing a group, R ² and R ³ may be bonded to each other to form a ring structure.) The red pixel of the color filter according to claim 5, wherein the red color material contains at least one selected from the group consisting of a diketopyrrolopyrrole pigment, a naphthol azo pigment, an anthraquinone pigment, and a perylene pigment. Colored resin composition for. As at least two kinds of metals in the yellow color material, Ni and at least one kind of metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn are used. The colored resin composition for red pixels of the color filter according to claim 5 or 6, which comprises. The colored resin composition for a red pixel of the 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 according to any one of claims 5 to 8, wherein the binder component contains an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and the photoinitiator is an oxime initiator . Colored resin composition for red pixels . The colored resin composition for red pixels of the color filter according to any one of claims 5 to 9, further comprising an antioxidant. It is possible to form a cured film in which the chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source are in the range of x = 0.550 to 0.700 and y = 0.290 to 0.450. The colored resin composition for red pixels of the color filter according to any one of claims 5 to 10. A color filter including at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a colored resin for red pixels of the color filter according to any one of claims 5 to 11. A color filter characterized by being a cured product of the composition. A display device comprising the color filter according to claim 12.

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