JP2018010210A - Coloring material dispersion liquid for color filter, photosensitive colored resin composition for color filter, color filter, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive colored resin composition for a color filter, from which a colored layer with improved contrast can be formed while suppressing occurrence of display failures.SOLUTION: The photosensitive colored resin composition for a color filter comprises a coloring material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photo-initiator, and a solvent. The colorant comprises C.I. Pigment Green 7, C.I. Pigment Green 58, and a yellow coloring material. The yellow coloring material comprises: at least one anion selected from the group consisting of mono, di, tri and tetra-anions of a specific azo compound and an azo compound having a tautomeric structure of the specific azo compound; at least two metal ions selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn; and a melamine derivative. The dispersant is a polymer having a specific structural unit.SELECTED DRAWING: None

Description

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

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

Many conventional display devices comply with sRGB (IEC 61966-2-1), which is an international standard for color space. However, there is a growing demand for display devices that support AdobeRGB having a wider color reproduction range than sRGB, in order to obtain a more realistic representation and to further improve color reproducibility. The AdobeRGB standard is a color space definition proposed by Adobe Systems. In AdobeRGB, the three primary colors are defined as follows for the chromaticity coordinates x and y in the XYZ color system. The AdobeRGB standard is characterized by having a wider color gamut in the green direction than the sRGB standard.
Red: x = 0.64; y = 0.34
Green: x = 0.21; y = 0.71
Blue: x = 0.15; y = 0.06

  There is also a need for a specification that conforms to the DCI (Digital Cinema Initiates) standard, which has a wider color gamut in the red and green directions than sRGB.

Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the formation of a color image of a liquid crystal display device, the light passing through the color filter is colored as it is into the color of each pixel constituting the color filter, and the light of those colors is synthesized to form a color image. As a light source at that time, in addition to a conventional cold cathode tube, an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used. In the organic light emitting display device, a color filter is used for color adjustment.
For this reason, there is a growing demand for color filters with higher brightness, higher contrast, and improved color reproducibility.

In the color filter, a region connecting three points of red, green, and blue pixels is a limit of colors that can be reproduced. In other words, a color filter having a larger triangle formed by three points of red, green, and blue pixels has a wider range of colors that the display device can reproduce on the screen.
In order to achieve a color space having a wide color reproduction gamut such as AdobeRGB or DCI, the green color of the color filter is particularly set to high chromaticity {(x = 0.18 to 0.30, y = 0). .55 to 0.75), more preferably (x = 0.18 to 0.30, y = 0.57 to 0.75), and even more preferably (x = 0.18 to 0.30, y = 0.61 to 0.75)} region.

Conventional green pigments widely used for green pixels include C.I. I. Pigment Green 58 (hereinafter sometimes abbreviated as PG58), C.I. I. Pigment green 36 (hereinafter sometimes abbreviated as PG36), C.I. I. Pigment Green 7 (hereinafter sometimes abbreviated as PG7).
However, when PG58 is used, the luminance increases, but when a green pixel included in the green chromaticity region of the high color density is manufactured, it is necessary to make the green pixel very thick, which causes a problem in mass productivity. In addition, since only the green pixels are thickened, it is difficult to maintain the color filter performance.
Further, when forming a green pixel so as to achieve the high color density green chromaticity region using PG 36, the green color included in the high color density green chromaticity region is not as high as that of PG58. In the case of manufacturing the pixel, it is necessary to increase the thickness of the green pixel, and there is a problem similar to that of PG58.
Further, when a green pixel is produced so as to achieve the high color density green chromaticity region using PG7, there has been a problem that the luminance and contrast of the green pixel are conventionally reduced.

  On the other hand, the green pixel has a problem that it tends to cause display defects. More specifically, the lateral electric field type liquid crystal display device is greatly affected by the electrical characteristics of the colored layer because the colored layer of the color filter is present in the liquid crystal driving electric field. When the PG 36 is used for the green pixel, the horizontal electric field type liquid crystal display device has various display defects such as liquid crystal orientation disorder due to the electrical characteristics of the green pixel and a burn-in phenomenon due to a shift in the switching threshold. Such a display defect occurs more prominently when PG58 is used for the green pixel, which is a problem.

In Patent Document 1, in a liquid crystal display device of a horizontal electric field mode, the electrical properties of the colored layer of the color filter do not adversely affect the switching performance of the liquid crystal, and it is sufficient that a protective layer made of a transparent resin is not provided. As a color filter that can ensure performance and can cope with high color reproducibility, it is disclosed that a colored layer that forms a green pixel includes a specific amount or less of PG36 and has a specific dielectric loss tangent (tan δ) value. Yes.
However, the technique disclosed in Patent Document 1 is insufficient in terms of wide color reproducibility and insufficient in terms of contrast even if display defects are reduced.

Japanese Patent Application Laid-Open No. 2004-228867 discloses C.I. for the purpose of enabling control of spectral characteristics required for a color filter for a solid-state imaging device, excellent color separation, and high transmittance. I. Pigment green 58 and C.I. I. Pigment Green 7 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, and C.I. I. A coloring composition for a solid-state imaging device containing at least one selected from the group consisting of CI Pigment Yellow 185 is disclosed.
However, the technique disclosed in Patent Document 2 has poor contrast and is insufficient for practical use.

On the other hand, Patent Document 3 includes, as a novel metal azo pigment, a dianion of a specific azo compound and an adduct of a metal azo compound composed of at least two metal ions of Zn ²⁺ and Ni ²⁺ and melamine or a derivative thereof, A metal azo pigment having a specific signal and no specific signal in an X-ray diffraction diagram is described.

JP 2009-162979 A JP2015-169880A JP 2014-12838 A

  The present invention has been made in view of the above circumstances, and is a color material dispersion that is excellent in color material dispersion stability and capable of forming a colored layer with improved contrast while suppressing the occurrence of display defects, and the color material Photosensitive colored resin composition for color filter capable of forming a colored layer having excellent color reproducibility with improved contrast while suppressing the occurrence of display defects, using the dispersion, and the photosensitive colored resin composition for color filter The use of the color filter improves the contrast while suppressing the occurrence of display defects and has excellent color reproducibility, and the use of the color filter improves the contrast while suppressing the occurrence of display defects. An object of the present invention is to provide a display device having excellent color reproducibility.

The color filter color material dispersion according to the present invention is a color filter color material dispersion containing a color material, a dispersant, and a solvent,
The color material is C.I. I. Pigment green 7, C.I. I. Pigment green 58, and yellow color material,
The yellow color material includes at least one anion selected from the group consisting of mono-, di-, tri-, and tetraanions of an azo compound represented by the following general formula (A) and an azo compound having a tautomer structure thereof: An ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (B): Including
The dispersant is a polymer having a structural unit represented by the following general formula (I).

The photosensitive colored resin composition for a color filter according to the present invention is a color filter photosensitive material containing a coloring material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. A colored resin composition comprising:
The color material is C.I. I. Pigment green 7, C.I. I. Pigment green 58, and yellow color material,
The yellow color material includes at least one anion selected from the group consisting of mono-, di-, tri-, and tetraanions of an azo compound represented by the following general formula (A) and an azo compound having a tautomer structure thereof: An ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (B): Including
The dispersant is a polymer having a structural unit represented by the following general formula (I).

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

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

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

  The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the photosensitive colored resin for color filter according to the present invention. It is a colored layer that is a cured product of the composition.

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

  According to the present invention, a colorant dispersion liquid that is excellent in colorant dispersion stability and suppresses the occurrence of display defects while being capable of forming a colored layer with improved contrast, and display defects using the colorant dispersion liquid. Occurrence of display defects using a photosensitive colored resin composition for a color filter capable of forming a colored layer having improved color reproducibility with improved generation while suppressing occurrence of the color filter A color filter with improved contrast and excellent color reproducibility while being suppressed, and a display device with improved contrast and excellent color reproducibility while suppressing the occurrence of display defects by using the color filter Can be provided.

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 for color filter, the photosensitive colored resin composition for 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, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.
In addition, C.I. I. Pigment Green is “PG”, C.I. I. Pigment Blue “PB”, C.I. I. Pigment Yellow is abbreviated as “PY” where appropriate.

[Colorant dispersion]
The color material dispersion for a color filter according to the present invention is a color material dispersion for a color filter containing a color material, a pigment derivative, a dispersant, and a solvent,
The color material is C.I. I. Pigment green 7, C.I. I. Pigment green 58, and yellow color material,
The yellow color material includes at least one anion selected from the group consisting of mono-, di-, tri-, and tetraanions of an azo compound represented by the following general formula (A) and an azo compound having a tautomer structure thereof: An ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (B): Including
The dispersant is a polymer having a structural unit represented by the following general formula (I).

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

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

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

Since the color material dispersion of the present invention is used in combination with the specific color material and a polymer having a structural unit represented by the general formula (I) as a dispersant, the color material dispersion stability is improved. It is possible to form a colored layer with excellent contrast while suppressing occurrence of display defects.
Since PG7 used as a color material in the present invention exhibits a single color and bluish green color and has a relatively strong coloring power, PG7 in the color material is further combined by combining PG58 with the specific yellow color material. Even if the total content of PG58 and the P / V ratio ((color material component mass in the composition) / (solid content mass other than color material components in the composition) ratio) is suppressed, A green pixel included in the high color density green chromaticity region can be produced. Therefore, it is suitably used as a green color material dispersion.
It is presumed that the display defect is likely to occur in the green pixel due to the green color material having the phthalocyanine skeleton, but when the color material dispersion liquid of the present invention is used, the green pixel in the green color material having the phthalocyanine skeleton Since the content can be reduced and the P / V ratio can be reduced, it is estimated that a green pixel in which the occurrence of display defects is suppressed can be achieved.
In the present invention, the contrast is improved by using the specific yellow color material in combination with a dispersant that is a polymer having a structural unit represented by the general formula (I). When the metal forming the metal complex containing the azo compound represented by the general formula (A) is one kind of color material, it is difficult to atomize because of high crystallinity and it is difficult to improve the contrast. On the other hand, in this invention, the specific yellow color material containing 2 or more types of metal ions is used with respect to the anion of the azo compound represented by general formula (A). The yellow color material contains two or more kinds of metal ions, so that the crystal growth of the color material is suppressed and atomization is possible, and the dispersant is a polymer having a structural unit represented by the general formula (I) Therefore, it is presumed that a colored layer that is atomized in the colorant dispersion and improved in contrast can be formed.
Further, since PG7 is used in combination with PG58 and the specific yellow color material, and further in combination with a dispersant that is a polymer having a structural unit represented by the general formula (I), color material dispersion is achieved. Therefore, it is possible to create a color filter having a large triangle connecting three points of red, green, and blue pixels and having excellent color reproducibility while achieving improved contrast.

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

<Color material>
In the present invention, the color material is C.I. I. Pigment green 7, C.I. I. Pigment green 58, and yellow color material,
The yellow color material includes at least one anion selected from the group consisting of mono-, di-, tri-, and tetraanions of an azo compound represented by the following general formula (A) and an azo compound having a tautomer structure thereof: An ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (B): It is characterized by including.
In the present invention, since the specific yellow color material is used as the yellow color material, a decrease in luminance can be suppressed when PG7 and PG58 are combined, and crystallization can be suppressed and atomization can be achieved. Therefore, the contrast can be improved because of excellent dispersibility when combined with a specific dispersant described later.

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

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

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

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

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

In the yellow color material used in the present invention, the content ratio of at least two metals may be appropriately adjusted.
Among these, in the yellow color material used in the present invention, Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn Is preferably included in a molar ratio of 97: 3 to 10:90, and more preferably in a molar ratio of 90:10 to 10:90.
Among these, it is preferable that Ni: Zn is contained in a molar ratio of Ni: Zn of 90:10 to 10:90, and more preferably 80:20 to 20:80.
Alternatively, Ni and Cu are preferably included in a molar ratio of Ni: Cu of 97: 3 to 10:90, and more preferably 96: 4 to 20:80.

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

  As an aspect in which at least two kinds of metal ions are included in the yellow color material, there are a case where at least two kinds of metal ions are contained in a common crystal lattice, and a case where one kind of metal ion is included in another crystal lattice. An example is a case where crystals containing ions are aggregated. Among them, the case where at least two kinds of metal ions are contained in a common crystal lattice is preferable from the viewpoint of further improving the contrast. Whether the common crystal lattice includes at least two kinds of metal ions or whether another crystal lattice includes one type of metal ion each aggregated. For example, it can be appropriately determined using an 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 comprises a metal complex comprising an anion of an azo compound represented by the general formula (A) and an azo compound having a tautomeric structure thereof and a specific metal ion, and the following general formula (B The compound molecule | numerator with the compound represented by this is included. These intermolecular bonds can be formed, for example, by intermolecular interactions, by Lewis acid-base interactions, or by coordinate bonds. Alternatively, a structure such as an inclusion compound in which a guest molecule is incorporated in a lattice constituting a host molecule may be used. Alternatively, a mixed substitution crystal may be formed in which two substances form a joint crystal, and atoms of the second component are located at regular lattice positions of the first component.

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

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

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

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

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

  In the color material dispersion of the present invention, PG7 and PG58 are used as a color material in combination with the specific yellow color material, but other color materials as exemplified in the photosensitive colored resin composition described below. May be used in combination. As other color materials, for example, other green color materials, other yellow color materials, and orange color materials are preferably used.

  In the color material dispersion of the present invention, the content ratios of PG7, PG58, and the yellow color material, and the content ratio when other color materials are used are the same content ratios as those of the photosensitive colored resin composition described later. It is preferable. However, since the photosensitive coloring resin composition can be produced by mixing two or more kinds of coloring material dispersions as appropriate, it is not necessary to have the same content ratio as the photosensitive coloring resin composition described later. Used for.

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

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

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

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

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

Examples of the hydrocarbon group in the hydrocarbon group that may include a hetero atom in R ² and R ³ include an alkyl group, an aralkyl group, and an aryl group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group, and the like. 1-18 are preferable and, among them, a methyl group or an ethyl group is more preferable.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. 7-20 are preferable and, as for the carbon atom number of an aralkyl group, 7-14 are more preferable.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. 6-24 are preferable and, as for the carbon atom number of an aryl group, 6-12 are more preferable. The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.
The hydrocarbon group containing a hetero atom has a structure in which a carbon atom in the hydrocarbon group is replaced with a hetero atom. Examples of the hetero atom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.
Moreover, the hydrogen atom in a hydrocarbon group may be substituted by halogen atoms, such as a C1-C5 alkyl group, a fluorine atom, a chlorine atom, and a bromine atom.

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

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

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

In the polymer having the structural unit represented by the general formula (I), at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the following general formulas (1) to ( 3) The formation of a salt with one or more compounds selected from the group consisting of the compounds represented by 3) further improves the color material adsorbability at the salt forming site, and the color material dispersion stability and development. It is preferable from the viewpoint of excellent residue suppression and solvent resolubility.
In recent color filters, it is necessary to solve various problems in mass production of color filters in accordance with the technology for improving the colorant dispersibility in order to realize the demand for higher brightness and higher contrast. . That is, in order to increase the color material concentration in the resin composition, it is necessary to increase the amount of the dispersant, which causes problems such as generation of a development residue and a delay in development time. Furthermore, in the manufacturing process of a color filter, it is calculated | required that the solid content of the colored resin composition once dried is excellent in the property which melt | dissolves in a solvent again, and the re-solubility in a solvent. For example, if the photosensitive colored resin composition adheres to the tip of the die lip when coating with a die coater, a solidified product is generated by drying, but the solidified product dissolves in the photosensitive colored resin composition when coating is resumed. If it is not easy to do, a part of the solidified product on the die lip peels off and easily adheres to the colored layer of the color filter, which causes a foreign matter defect. In particular, when the colorant concentration of the colored resin composition is increased, the solvent re-solubility is likely to be insufficient, and the yield is reduced due to the occurrence of the foreign matter in the color filter manufacturing process.
On the other hand, 1 selected from the group consisting of at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) and compounds represented by the following general formulas (1) to (3) When the compound of the seed or more forms a salt, development residue suppression and solvent resolubility are improved.

(In General Formula (1), R ^a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or benzyl group, or —O—. R ^e is represented, and R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or benzyl group, or a carbon number having 1 to 4 carbon atoms. Represents a (meth) acryloyl group via an alkylene group. In the general formula (2), R ^b , R ^{b ′} and R ^{b ″} each independently have a hydrogen atom, an acidic group or an ester group thereof, and a substituent. A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or -O- It represents R ^{f, R f} is a also a good number of 1 to 20 carbon having substituent Via a chain, branched or cyclic alkyl group, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or an alkylene group having 1 to 4 carbon atoms (meth) Represents an acryloyl group, and X represents a chlorine atom, a bromine atom, or an iodine atom, In the general formula (3), R ^c and R ^d are each independently a hydrogen atom, a hydroxyl group, or a straight chain having 1 to 20 carbon atoms. Represents a branched or cyclic alkyl group, a vinyl group, an optionally substituted phenyl group or benzyl group, or —O—R ^e , where R ^e is a linear or branched chain having 1 to 20 carbon atoms. Or a cyclic alkyl group, a vinyl group, a phenyl group or benzyl group which may have a substituent, or a (meth) acryloyl group via an alkylene group having 1 to 4 carbon atoms, provided that R ^c and R ^d At least one of contains a carbon atom. )

In the general formulas (1) to (3), R ^a , R ^b , R ^{b ′} , R ^{b ″} , R ^c , R ^d , R ^e , and R ^f are linear or branched chains having 1 to 20 carbon atoms. Alternatively, the cyclic alkyl group may be linear or branched, and may contain a cyclic structure. Specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n- An undecyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a tetradecyl group, an octadecyl group, etc. are mentioned, Preferably a C1-C15 linear, branched or cyclic alkyl group is mentioned, More preferably, it is carbon number. 1-8 straight Examples include a chain, branched chain, or cyclic alkyl group.
In R ^a , R ^c , R ^d , and R ^e , examples of the substituent of the phenyl group or benzyl group that may have a substituent include an alkyl group having 1 to 5 carbon atoms and an acyl group. And an acyloxy group.

In R ^b , R ^{b ′} , R ^{b ″} , and R ^f , examples of the substituent of the phenyl group or benzyl group that may have a substituent include an acidic group or an ester group thereof, and those having 1 to 1 carbon atoms. 5 alkyl groups, acyl groups, acyloxy groups and the like.
In R ^b , R ^{b ′} , R ^{b ″} , and R ^f , as a substituent of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or a vinyl group Includes an acidic group or an ester group thereof, a phenyl group, an acyl group, an acyloxy group, and the like.
In R ^b , R ^{b ′} , R ^{b ″} , and R ^f , the acidic group refers to a group that exhibits acidity by releasing protons in water. Specific examples of the acidic group include a carboxy group (—COOH), A sulfo group (—SO ₃ H), a phosphono group (—P (═O) (OH) ₂ ), a phosphinico group (> P (═O) (OH)), a boronic acid group (—B (OH) ₂ ), A borinic acid group (> BOH) and the like, and an anion having a hydrogen atom dissociated such as a carboxylate group (—COO ⁻ ), and a salt of an alkali metal ion such as sodium ion or potassium ion It may be an acid salt formed.
Moreover, as an ester group of an acidic group, carboxylic acid ester (—COOR), sulfonic acid ester (—SO ₃ R), phosphoric acid ester (—P (═O) (OR) ₂ ), (> P (═O ) (OR)), boronic acid ester (—B (OR) ₂ ), borinic acid ester (> BOR) and the like. Among them, the acidic ester group is preferably a carboxylic acid ester (—COOR) from the viewpoint of dispersibility and dispersion stability. In addition, R here is a hydrocarbon group and is not particularly limited. However, from the viewpoint of dispersibility and dispersion stability, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group or an ethyl group is preferable. More preferably.

The compound of the general formula (2) includes a carboxy group, a boronic acid group, a borinic acid group, anions thereof, and alkali metal salts thereof from the viewpoints of dispersibility, dispersion stability, alkali developability, and development residue suppression. It is preferable to have one or more functional groups selected from these esters, and among them, it is more preferable to have a functional group selected from a carboxy group, a carboxylate group, a carboxylic acid group, and a carboxylic acid ester. .
When the compound of the general formula (2) has an acidic group and an ester group thereof (hereinafter referred to as an acidic group or the like), both the acidic group equivalent side and the halogen atom side hydrocarbon of the compound have terminal nitrogen. Although it is possible to form a salt with the site, it is presumed that the terminal nitrogen site and the halogen atom-side hydrocarbon form a salt more stably than when the terminal nitrogen site and an acidic group form a salt. And it is estimated that a dispersibility and dispersion stability improve because a coloring material adsorb | sucks to the salt formation site | part which exists stably.

  When the compound of the general formula (2) has the acidic group or the like, it may have two or more acidic groups or the like. When two or more acidic groups or the like are included, the plurality of acidic groups or the like may be the same or different. The number of the acidic groups and the like that the compound of the general formula (2) has is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.

R ^a in the general formula (1), at least one of R ^b , R ^{b ′} and R ^{b ″ in} the general formula (2), and at least one of R ^c and R ^d in the general formula (3) When one of them has an aromatic ring, the affinity with the skeleton of the coloring material described later is improved, the coloring material has excellent dispersibility and dispersion stability, and a colored composition having excellent contrast is obtained. It is preferable because it can be used.

  The molecular weight of the one or more compounds selected from the group consisting of the general formulas (1) to (3) is preferably 1000 or less, particularly 50 to 800, from the viewpoint of improving the colorant dispersibility. Is more preferable, it is preferable that it is 50-400, still more preferable is 80-350, and it is most preferable that it is 100-330.

Examples of the compound represented by the general formula (1) include benzene sulfonic acid, vinyl sulfonic acid, methane sulfonic acid, p-toluene sulfonic acid, monomethyl sulfuric acid, monoethyl sulfuric acid, mono n-propyl sulfuric acid and the like. A hydrate such as p-toluenesulfonic acid monohydrate may be used. Examples of the compound represented by the general formula (2) include methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, n-butyl chloride, hexyl chloride, octyl chloride, dodecyl chloride, Tetradecyl chloride, hexadecyl chloride, phenethyl chloride, benzyl chloride, benzyl bromide, benzyl iodide, chlorobenzene, α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethyl Examples include benzoic acid, 4-iodophenylbenzoic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, methyl α-bromophenylacetate, 3- (bromomethyl) phenylboronic acid, and the like. Examples of the compound represented by the general formula (3) include monobutyl phosphoric acid, dibutyl phosphoric acid, methyl phosphoric acid, dibenzyl phosphoric acid, diphenyl phosphoric acid, phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, and the like. .
The group consisting of phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, dibutyl phosphoric acid, benzyl chloride, benzyl bromide, vinyl sulfonic acid, and p-toluenesulfonic acid monohydrate because of particularly excellent dispersion stability It is preferable to use one or more selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, benzyl chloride, benzyl bromide, and p-toluenesulfonic acid monohydrate. preferable.
Moreover, it is represented by the general formula (2) having an acidic group and its ester group from the viewpoint that the effect of suppressing development residue is improved by combination with a block copolymer having excellent dispersion stability and having an acid value described later. Are also preferably used, among which α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, and 4-iodophenylbenzoic acid. One or more selected from the group is also preferably used.

In the polymer having the structural unit represented by the general formula (I), the content of one or more compounds selected from the group consisting of the general formulas (1) to (3) is represented by the general formula (I). Since the terminal structural unit represented by the structural unit represented by the salt forms a salt with the structural unit represented by the general formula (I), One or more compounds selected from the group consisting of 1) to (3) are preferably 0.01 mol or more, more preferably 0.1 mol or more, and 0.2 mol or more. Is more preferably 0.3 mol or more. If it is at least the above lower limit value, the effect of improving the colorant dispersibility due to salt formation can be easily obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, further preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. When it is not more than the above upper limit value, it can be excellent in development adhesion and solvent re-solubility.
In addition, the 1 or more types of compound selected from the group which consists of said general formula (1)-(3) may be used individually by 1 type, and may combine 2 or more types. When combining 2 or more types, it is preferable that the total content is in the above range.

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

[Block copolymer]
When the block containing the structural unit represented by the general formula (I) is an A block, the structural unit represented by the general formula (I) is basic and the A block has an adsorption site for a coloring material. Function as. Further, at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) and one or more compounds selected from the group consisting of the general formulas (1) to (3) are salts. In this case, the salt forming part functions as a stronger adsorption site for the coloring material. On the other hand, the B block not containing the structural unit represented by the general formula (I) functions as a block having solvent affinity. Therefore, the block copolymer used in the present invention functions as a color material dispersant by sharing the function between the color material, the adsorbing A block and the solvent B affinity block.

{A block}
The A block is a block including the structural unit represented by the general formula (I), but since the structural unit represented by the general formula (I) is as described above, description thereof is omitted here.
In the A block including the structural unit represented by the general formula (I), it is preferable that three or more structural units represented by the general formula (I) are included. Especially, from the point which improves a dispersibility and dispersion stability, it is preferable to contain 3-100 pieces, It is more preferable to contain 3-50 pieces, Furthermore, it is more preferable to contain 3-30 pieces.
The structural unit represented by the general formula (I) only needs to function as a coloring material adsorption site, and may be composed of one kind or may contain two or more kinds of structural units.

The A block may have a structural unit other than the structural unit represented by the general formula (I) as long as the object of the present invention is achieved, and may share the structural unit represented by the general formula (I). Any polymerizable structural unit can be contained. For example, as the structural unit other than the structural unit represented by the general formula (I) that may be contained in the basic block portion, specifically, for example, a structural unit represented by the general formula (II) described later, etc. Is mentioned.
In the A block in the block copolymer before salt formation, the content of the structural unit represented by the general formula (I) is 50 to 100% by mass with respect to the total mass of all the structural units of the A block. Is preferable, more preferably 80 to 100% by mass, and most preferably 100% by mass. This is because as the proportion of the structural unit represented by the general formula (I) is higher, the adsorptive power to the coloring material is improved, and the dispersibility and dispersion stability of the block copolymer are improved. In addition, the content rate of the said structural unit is computed from the preparation mass at the time of synthesize | combining A block which has a structural unit represented by general formula (I).

Further, the content ratio of the structural unit represented by the general formula (I) in the block copolymer before salt formation is such that all the structural units of the block copolymer are obtained from the viewpoint of good dispersibility and dispersion stability. The total mass is preferably 5 to 60% by mass, and more preferably 10 to 50% by mass. In addition, the content rate of each structural unit in the said block copolymer is computed from the preparation mass at the time of synthesize | combining the block copolymer before salt formation.
In addition, the structural unit represented by general formula (I) should just have affinity with a color material, may consist of 1 type, and may contain 2 or more types of structural units. Good.

{B block}
B block is a block which does not contain the structural unit represented by the said general formula (I). As the B block, among monomers having an unsaturated double bond that can be copolymerized with the monomer that derives the structural unit represented by the general formula (I), an appropriate solvent is used depending on the solvent. It is preferable to select and use. As a guideline, it is preferable to introduce the B block so that the solubility of the copolymer at 23 ° C. is 20 (g / 100 g solvent) or more with respect to the solvent used in combination.

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

(In General Formula (II), A ′ is a direct bond or a divalent linking group, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ⁸ is a monovalent group, and R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group. R ⁸ is a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or a carbon atom having 1 to 5 carbon atoms. It is an alkyl group.
The hydrocarbon group may have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

In the general formula (II), A ′ is a direct bond or a divalent linking group. The direct bond means that A ′ has no atom, that is, C (carbon atom) in the general formula (II) and R ⁵ are bonded without interposing another atom. As a bivalent coupling group, it can be set to the same thing as A in general formula (I). Among these, A ′ is preferably a divalent linking group containing a direct bond, a —CONH— group, or a —COO— group from the viewpoint of solubility in an organic solvent.

In the general formula (II), R ⁵ is a hydrocarbon group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ^8. Indicates.
The hydrocarbon group for R ⁵ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, 2 -Ethylhexyl group, 2-ethoxyethyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like can be mentioned.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, and a propenyl group. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the polymer obtained, it is preferable that there is a double bond at the terminal of the alkenyl group.
Examples of the aliphatic hydrocarbon substituent such as an alkyl group or an alkenyl group include a nitro group and a halogen atom.

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

In the above R ⁵ , x is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2, and y is an integer of 1-5, preferably an integer of 1-4, more preferably. Is 2 or 3. z is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2.

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

The R ⁵ is preferably selected so as to be excellent in compatibility with a solvent described later. Specifically, for example, the solvent is generally used as a solvent for a colored resin composition for a color filter. In the case of using a commonly used solvent such as glycol ether acetate, ether or ester, a methyl group, an ethyl group, an isobutyl group, an n-butyl group, a 2-ethylhexyl group, a benzyl group or the like is preferable.

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

  The number of structural units constituting the B block is not particularly limited, but is 10 to 300 from the viewpoint that the solvent affinity site and the color material adsorption site effectively act to improve the dispersibility of the color material. Preferably, it is 10 to 100, more preferably 10 to 70.

  In the B block in the block copolymer, the content ratio of the structural unit represented by the general formula (II) is based on the total mass of all the structural units of the B block from the viewpoint of improving the solvent affinity and the colorant dispersibility. On the other hand, it is preferable that it is 50-100 mass%, and it is more preferable that it is 70-100 mass%. In addition, the content rate of the said structural unit is computed from the preparation mass at the time of synthesize | combining B block.

  Moreover, the content ratio of the structural unit represented by the general formula (II) in the block copolymer before salt formation improves the color material dispersibility and dispersion stability. It is preferable that it is 40-95 mass% with respect to the total mass of a unit, and it is more preferable that it is 50-90 mass%. In addition, the content rate of the said structural unit is computed from the preparation mass at the time of synthesize | combining the block copolymer before salt formation.

  In the B block, the structural unit may be appropriately selected so as to function as a solvophilic moiety, and the structural unit represented by the general formula (II) may be composed of one kind, or two or more kinds. The structural unit may be included. Two or more structural units included in the B block may be randomly arranged in the block.

The dispersant is at least one of the following block copolymer (P1) and the following salt-type block copolymer (P2),
P1: a block copolymer containing an A block containing the structural unit represented by the general formula (I) and a B block containing a structural unit derived from a carboxy group-containing monomer;
P2: From the group consisting of compounds represented by the following general formulas (1) to (3) and at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer A salt-type block copolymer in which one or more selected compounds form a salt;
The acid value of the dispersant is 1 mgKOH / g or more and 18 mgKOH / g or less, and the glass transition temperature of the dispersant is 30 ° C. or more, while the colorant dispersion stability is excellent and the occurrence of development residue is suppressed. It is preferable from the viewpoint that it has excellent solvent re-solubility and has high development adhesiveness when it is a colored resin composition.
When the colorant concentration is increased and the dispersant content is increased, the amount of the binder is relatively decreased. Therefore, the colored resin layer is easily peeled off from the base substrate during development. When the dispersant contains a B block containing a structural unit derived from a carboxy group-containing monomer and has the specific acid value and glass transition temperature, the development adhesion is improved. If the acid value is too high, the developability is excellent, but it is presumed that the polarity is too high and peeling easily occurs during development.

(Constitutional unit derived from carboxy group-containing monomer)
As the carboxy group-containing monomer used in the present invention, a monomer containing an unsaturated double bond and a carboxy group that can be copolymerized with a monomer that derives the structural unit represented by formula (I) 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, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use acid anhydride group containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

In the block copolymer before salt formation, the content ratio of the structural unit derived from the carboxy group-containing monomer may be appropriately set so that the acid value of the block copolymer is within the range of the specific acid value. Although not limited, it is preferable that it is 0.05-4.5 mass% with respect to the total mass of all the structural units of a block copolymer, and it is more preferable that it is 0.07-3.7 mass%.
Since the content ratio of the structural unit derived from the carboxy group-containing monomer is not less than the lower limit value, the effect of suppressing the development residue is expressed, and since it is not more than the upper limit value, the development adhesiveness is deteriorated and the solvent resolubility is reduced. Deterioration can be prevented.
In addition, the structural unit derived from a carboxy group containing monomer should just become said specific acid value, may consist of 1 type, and may contain 2 or more types of structural units.

Moreover, in this invention, it is preferable from the point which improves the development adhesiveness that the structural unit derived from a hydroxyl-containing monomer is contained in B block of a block copolymer. In the case where a structural unit derived from a hydroxyl group-containing monomer is included, it tends to interact with glass, metal or the like usually used as a substrate, so that it is considered that the development adhesion is improved. When the structural unit derived from a hydroxyl group-containing monomer is contained in the B block, the development speed is further improved.
Here, the hydroxyl group means an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.

As the structural unit derived from a hydroxyl group-containing monomer, a monomer containing an unsaturated double bond and a hydroxyl group that can be copolymerized with a monomer that derives the structural unit represented by formula (I) can be used. Examples of such monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerin mono (meth). Examples thereof include acrylate, polyethylene glycol mono (meth) acrylate, ε-caprolactone 1-mol adduct of 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like.
From the viewpoint of improving developability, it is more preferable to have a primary hydroxyl group than to have a secondary hydroxyl group. The primary hydroxyl group refers to a hydroxyl group in which the carbon atom to which the hydroxyl group is bonded is a primary carbon atom, and the secondary hydroxyl group refers to a hydroxyl group in which the carbon atom to which the hydroxyl group is bonded is a secondary carbon atom.
As will be described later, 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. It is preferable to use a hydroxyl group-containing monomer that is 0 ° C. or higher, and it is preferable to use a hydroxyl group-containing monomer that is 10 ° C. or higher.
From the viewpoint of improving the development adhesiveness, it is preferable that one or more selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate.

  In the block copolymer before salt formation, the content ratio of the structural unit derived from the hydroxyl group-containing monomer is preferably 1% by mass or more based on the total mass of all the structural units of the block copolymer. More preferably, it is more preferably 3% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more. When it is at least the above lower limit, the development adhesiveness can be made preferable. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. If it is not more than the above upper limit, it can be made preferable from the viewpoint of increasing the introduction ratio of other useful monomers. In addition, the content rate of the said structural unit is computed from the preparation mass at the time of synthesize | combining the block copolymer before salt formation.

Moreover, in this invention, it is preferable from the point which the solvent resolubility improves that the structural unit derived from an aromatic group containing monomer is contained in B block. In the case where a structural unit derived from an aromatic group-containing monomer is included, compatibility with the solvent and other components is likely to be improved, so that it is considered that the solvent resolubility is improved.
As the structural unit derived from the aromatic group-containing monomer, a monomer containing an unsaturated double bond and an aromatic group that can be copolymerized with the monomer that derives the structural unit represented by the general formula (I) can be used. . Examples of such a monomer include acrylates such as benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and phenoxyethyl (meth) acrylate, styrenes such as styrene, and vinyl ethers such as phenyl vinyl ether. Kind.
As will be described later, the glass transition temperature of the dispersant used in the present invention is set to a specific value or more, and from the viewpoint of improving the development adhesion, among others, the value of the glass transition temperature of each monomer homopolymer (Tgi) is It is preferable to use an aromatic group-containing monomer having a temperature of 0 ° C. or higher, and it is preferable to use an aromatic group-containing monomer having a temperature of 10 ° C. or higher.
From the point that the solvent resolubility is easily improved, among them, at least one selected from the group consisting of benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and phenoxyethyl (meth) acrylate It is preferable that there is one, and more preferable is one or more selected from the group consisting of benzyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate.

  In addition, in the block copolymer before salt formation, the content ratio of the structural unit derived from the aromatic group-containing monomer is based on the total mass of all the structural units of the block copolymer from the viewpoint of improving solvent resolubility. It is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more. Solvent resolubility can be made preferable as it is more than the said lower limit. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. If it is not more than the above upper limit, it can be made preferable from the viewpoint of increasing the introduction ratio of other useful monomers.

  Among them, the B block having solvophilic properties is composed of (i) a structural unit derived from a hydroxyl group-containing monomer and a structural unit derived from an aromatic group-containing monomer, and (ii) a structural unit derived from a hydroxyl group and an aromatic group-containing monomer. The inclusion of at least one kind is preferred from the viewpoint of improving the development adhesion and solvent re-solubility.

(I) When the structural unit derived from a hydroxyl group-containing monomer and the structural unit derived from an aromatic group-containing monomer are included, the structural unit derived from a hydroxyl group-containing monomer with respect to 1 part by mass of the structural unit derived from the aromatic group-containing monomer Is preferably contained in an amount of 0.15 parts by mass or more, more preferably 0.5 parts by mass or more. It is because it can be set as the thing excellent in image development adhesiveness as it is more than the said lower limit. Similarly, the structural unit derived from the hydroxyl group-containing monomer is preferably contained in an amount of 15 parts by mass or less, more preferably 7 parts by mass or less, with respect to 1 part by mass of the structural unit of the aromatic group-containing monomer. It is because it can be excellent in solvent resolubility that it is below the above-mentioned upper limit. Among them, the glass transition temperature value (Tgi) of the homopolymer is 10 parts per 1 part by mass of the structural unit derived from the aromatic group-containing monomer having a glass transition temperature value (Tgi) of the homopolymer of 10 ° C. or more. It is particularly preferable that the structural unit derived from a hydroxyl group-containing monomer having a temperature of not lower than ° C. is contained in the above range. It is because the development adhesiveness can be further improved by containing at the above lower limit or more, and the solvent resolubility can be further improved by containing at the above upper limit or less.

Examples of (ii) hydroxyl group and aromatic group-containing monomer in the structural unit derived from the hydroxyl group and aromatic group-containing monomer include 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl- Examples include 2-hydroxyethyl-phthalic acid. 2-Hydroxy-3-phenoxypropyl (meth) acrylate has a homopolymer having a glass transition temperature value (Tgi) of 10 ° C. or higher, an effect obtained from a structural unit derived from a hydroxyl group-containing monomer, and aromaticity. It is preferably used since any of the effects obtained from the structural unit derived from the group-containing monomer can be obtained. That is, it is preferable in terms of improving development adhesion, development speed, and solvent resolubility.
(Ii) When a structural unit derived from a hydroxyl group and aromatic group-containing monomer is included, the development adhesion, development speed, and solvent resolubility can be improved by one structural unit. There is also an advantage that the introduction ratio can be increased.

  Further, as described later, the glass transition temperature of the dispersant used in the present invention is set to a specific value or more, and the glass transition temperature value (Tgi) of the monomer homopolymer is 10 from the viewpoint of improving the development adhesion. It is preferable that the monomer having a temperature of 0 ° C. or higher is 75% by mass or more, and more preferably 85% by mass or more in the B block.

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

Further, the amine value of the block copolymer before salt formation is not particularly limited, but from the viewpoint of colorant dispersibility and dispersion stability, the lower limit is preferably 40 mgKOH / g or more, and 50 mgKOH / g or more. It is more preferable that it is 60 mgKOH / g or more. Moreover, as an upper limit, it is more preferable that it is 130 mgKOH / g or less, and it is still more preferable that it is 120 mgKOH / g or less. If it is more than the said lower limit, dispersion stability is more excellent. Moreover, if it is below the said upper limit, it is excellent in compatibility with another component and solvent resolubility becomes favorable.
In the present invention, the amine value of the block copolymer before salt formation refers to potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize 1 g of the solid content of the block copolymer before salt formation. This is a value measured by the method described in JIS K 7237.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 to 20000, and preferably 2000 to 15000 from the viewpoint of improving the colorant dispersibility and dispersion stability. More preferably, it is more preferably 3000-12000.
Here, the weight average molecular weight is determined as a standard polystyrene conversion value by (Mw) and gel permeation chromatography (GPC).
In the present invention, the weight average molecular weight Mw of the block copolymer is determined as a standard polystyrene conversion value by GPC (gel permeation chromatography). For the measurement, HLC-8120GPC manufactured by Tosoh Corporation was used, the elution solvent was N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide was added, and the polystyrene standard for calibration curve was Mw377400, 210500, 96000, 50400. , 20650, 10850, 5460, 2930, 1300, 580 (Easy PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Corporation), and TSK-GEL ALPHA-M × 2 (Tosoh Corporation) (Made by Co., Ltd.). The macromonomer, salt-type block copolymer, and graft copolymer that are the raw materials for the block copolymer are also subjected to the above conditions.

  In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, and the like can be used. Among these, an AB block copolymer or an ABA block copolymer is preferable in terms of excellent dispersibility.

  The manufacturing method of the said block copolymer is not specifically limited. Although a block copolymer can be produced by a known method, it is preferable to produce it by a living polymerization method. This is because chain transfer and deactivation are unlikely to occur, a copolymer having a uniform molecular weight can be produced, and dispersibility and the like can be improved. Examples of the living polymerization method include a living anionic polymerization method such as a living radical polymerization method and a group transfer polymerization method, and a living cation polymerization method. A copolymer can be produced by sequentially polymerizing monomers by these methods. For example, a block copolymer can be produced by first producing the A block and polymerizing the structural units constituting the B block into the A block. In the above production method, the order of polymerization of the A block and the B block can be reversed. Also, the A block and the B block can be manufactured separately, and then the A block and the B block can be coupled.

Moreover, as a preparation method of a salt type block copolymer, the said general formula (1)-(3) is used in the solvent which melt | dissolved thru | or disperse | distributed the polymer which has a structural unit represented by the said general formula (I). Examples thereof include a method of adding one or more compounds selected from the group consisting of stirring and further heating if necessary.
In addition, from the nitrogen part of the terminal which the structural unit represented by the said general formula (I) of the polymer which has a structural unit represented by the said general formula (I), and the said general formula (1)-(3) The fact that one or more compounds selected from the group form a salt and the proportion thereof can be confirmed by a known method such as NMR.

The amine value of the obtained salt-type block copolymer has a value that is smaller by the amount of salt formation than the block copolymer before salt formation. However, since the salt formation site is the same as the terminal nitrogen site corresponding to the amino group, or rather becomes a strengthened color material adsorption site, the color material dispersibility and color material dispersion stability tend to be improved by salt formation. is there. In addition, like the amino group, if the salt forming site is too much, the solvent resolubility is adversely affected. Therefore, in the present invention, the amine value of the block copolymer before salt formation can be used as an index for improving the colorant dispersion stability and solvent resolubility. The amine value of the obtained salt-type block copolymer (P2) is preferably from 0 mgKOH / g to 130 mgKOH / g, and more preferably from 0 mgKOH / g to 120 mgKOH / g.
If it is below the above upper limit, the compatibility with other components is excellent, and the solvent resolubility becomes good.

In addition, the amine value of the salt type block copolymer salt-formed by the compound represented by the general formula (2) among the salt type block copolymers is measured by the method described in JIS K 7237. Can be a value. In the compound of the general formula (2), since the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the halogen atom side hydrocarbon form a salt, the salt is also formed by the measurement method. This is because the amine value can be measured without any change.
On the other hand, among the salt-type block copolymers, the amine value of the salt-type block copolymer that is salt-formed by the compound represented by the general formula (1) or (3) It calculates | requires by calculating as follows from the amine titer of a block copolymer. In the compound represented by the general formula (1) or (3), the terminal nitrogen site and the acidic group of the structural unit represented by the general formula (I) form a salt. This is because when the amine value of the copolymer is measured by the method described in JIS K 7237, the state of salt formation is changed and an accurate value cannot be measured.
First, the amine value of the block copolymer before salt formation is determined by the method described above. Next, using 13C-NMR, the group consisting of the general formula (1) or (3) with respect to the terminal nitrogen moiety of the structural unit represented by the general formula (I) of the salt block copolymer The reaction rate of one or more compounds selected from (the ratio of the nitrogen moiety at the terminal of the salt formation) is measured. The terminal nitrogen moiety of the structural unit represented by the general formula (I) formed by salt formation of one or more compounds selected from the group consisting of the general formula (1) or (3) has an amine value of 0. (The amine value of the block copolymer before salt formation (P1) measured by the method described in JIS K 7237) × (the ratio of the nitrogen sites at the terminals where the salt is formed as calculated from the 13C-NMR spectrum) (%) / 100) is calculated by subtracting the amine value consumed by salt formation from the amine value of the block copolymer before salt formation.
Amine value of salt-type block copolymer = {Amine value of block copolymer before salt formation measured by the method described in JIS K 7237}-{Block before salt formation measured by the method described in JIS K 7237 Amine value of copolymer} × {Nitrogen moiety ratio (%) / 100} at the terminal of salt formation calculated from 13C-NMR spectrum

The acid value of the dispersant used in the present invention is preferably 1 mg KOH / g or more as a lower limit from the viewpoint that a development residue suppressing effect is exhibited. Among them, the acid value of the dispersant is more preferably 2 mgKOH / g or more from the viewpoint of more excellent development residue suppression effect. In addition, the acid value of the dispersant used in the present invention is preferably 18 mgKOH / g or less as the upper limit from the viewpoint of preventing the deterioration of the development adhesion and the solvent resolubility. Among these, the acid value of the dispersant is more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less, from the viewpoint of improving the development adhesion and the 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. The upper limit of the acid value of the block copolymer before salt formation is preferably 18 mgKOH / g or less, more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less. . This is because the development adhesiveness and the solvent resolubility are improved.

As described above, the acid value of the block copolymer before salt formation represents the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid content of the block copolymer. It is a value measured by the method described in K0070.
Further, the acid value of the salt type block copolymer in which the salt type block copolymer is salted with the compound represented by the general formula (2) is also a value measured by the method described in JIS K 0070. It is. In the compound of the general formula (2), the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the halogen atom-side hydrocarbon form a salt. This is because it can be measured without change.
On the other hand, when the salt-type block copolymer is a salt-type block copolymer that is salt-formed by the compound represented by the general formula (1) or (3), an acidic group used for salt formation The acid value is calculated by removing. This is because the acidic group used for salt formation does not function as an acidic group that increases the acid value of the dispersant. Therefore, in this application, the acid value of the salt type block copolymer salt-formed with the compound represented by the general formula (1) or (3) is calculated by a value obtained by the following formula. When the acid value of the salt-type block copolymer salt-formed by the compound represented by the general formula (1) or (3) is measured by the method described in JIS K 0070, it changes to a salt-forming state. This is because an accurate value cannot be measured.

Acid value of salt-type block copolymer = {total acid value of the compound represented by the general formula (1) or (3) used for salt formation−acid value consumed by salt formation} + block before salt formation Here, the total acid value of the compound represented by the general formula (1) or (3) used for the salt formation can be measured by the method described in JIS K 0070. it can. On the other hand, the acid value consumed by salt formation is calculated from the salt formation ratio obtained by NMR.
Specifically, the acid value consumed by salt formation is determined by, for example, measuring a 13C-NMR spectrum using a nuclear magnetic resonance apparatus, and in the obtained spectrum data, nitrogen that is not salt-formed at the terminal nitrogen site. From the ratio of the integrated value of the carbon atom peak adjacent to the atom and the carbon atom peak adjacent to the salt formed nitrogen atom, the ratio of the number of terminal nitrogen sites formed to the salt to the total number of terminal nitrogen sites is calculated. . {Amine number of the block copolymer before salt formation measured by the method described in JIS K 7237} × {Nitrogen moiety ratio (%) / 100} of the terminal salt formed as calculated from the 13C-NMR spectrum The consumed amine value is calculated, and this value is the same as the acid value consumed by salt formation.
However, when 1 mol or less of the compound represented by the general formula (1) is salt-formed with respect to 1 mol of the terminal nitrogen moiety of the structural unit represented by the general formula (I), the acidic group is 1 When the salt of the compound represented by the general formula (3) having 1 mol or less is formed, or the compound represented by the general formula (3) having two acidic groups is salted by 0.5 mol or less. When forming, if the total amount of acidic groups forms a salt with the terminal nitrogen moiety of the structural unit represented by the general formula (I), in the salt-type block copolymer after the salt formation, the acidic group Since does not affect the acid value, it can have the same acid value as the block copolymer before salt formation.
On the other hand, when the compound represented by the general formula (3) having two acidic groups is added in a mole number exceeding the above, there is an acidic group that is not salt-formed in the dispersant even after the salt is formed. Therefore, as shown in the above formula, the acid value of the acidic group that has not formed a salt is added to the acid value of the block copolymer before the salt formation to calculate the acid value of the dispersant.

Moreover, in this invention, it is preferable that the glass transition temperature of a dispersing agent is 30 degreeC or more from the point which image development adhesiveness improves. That is, whether the dispersant is a block copolymer before salt formation or a salt block copolymer, the glass transition temperature is preferably 30 ° C. or higher. If the glass transition temperature of the dispersant is low, the developer adhesion may be lowered, particularly if it is equal to or lower than the developer temperature (usually about 23 ° C.). This is presumed that when the glass transition temperature is equal to or lower than the developer temperature, the movement of the dispersant increases during development, resulting in deterioration in development adhesion. If the glass transition temperature is higher than the developer temperature, the molecular motion of the dispersant during development is suppressed, so that 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 precision weighing.
The glass transition temperature of the dispersant in the present invention can be determined by measuring by differential scanning calorimetry (DSC) according to JIS K7121.

However, the glass transition temperature (Tg) of the block copolymer not forming salt can be calculated by the following formula and used as an index.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the block copolymer. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. As the glass transition temperature value (Tgi) of the homopolymer of each monomer, the value of Polymer Handbook (3rd Edition) (by J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.
Since the glass transition temperature by the said calculated value becomes a value substantially the same as the measured value by said DSC, it can be used as the parameter | index of the glass transition temperature of the block copolymer which is not salt-forming.

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

[solvent]
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the colorant dispersion and can dissolve or disperse them. A solvent can be used individually or in combination of 2 or more types.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, i-propyl alcohol and methoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate and methoxypropion. Ester solvents such as methyl acid, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, n-butyl butyrate, clohexanol acetate; acetone, Ketone solvents such as methyl ethyl ketone, cyclohexanone, 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoate Glycol ether acetate solvents such as -3-methyl-1-butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate; carbitol acetates such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA) Solvents: diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol Ethyl methyl ether, propylene glycol monomer Glycol ether solvents such as ether and dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; tetrahydrofuran and the like Cyclic ether solvents such as: unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane; aromatic hydrocarbons such as toluene and xylene Organic solvents such as Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used from the viewpoint of solubility of other components. Among them, as a solvent used in the present invention, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, butyl carbitol acetate (BCA), 3-methoxy One or more selected from the group consisting of -3-methyl-1-butyl acetate, ethyl lactate, methyl 2-hydroxypropionate, and 3-methoxybutyl acetate, solubility of other components and coating It is preferable from the point of aptitude.

  Moreover, it is also preferable to use the mixed solvent containing 2 or more types of solvents from viewpoints, such as developability and solvent re-dissolution property.

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

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

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

In the case of using a mixed solvent, the content of the solvent having an alcoholic hydroxyl group is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less in the total solvent. Moreover, 0.1 mass% or more is preferable, 0.3 mass% or more is more preferable, and 1 mass% or more is still more preferable.
Within the above range, the solubility of the dispersant tends to be good, and since the dissolution of the dispersant in the first solvent is not hindered, the dispersion stability tends to be good.

When the first solvent is a solvent having a boiling point of less than 150 ° C., use of a solvent having a boiling point of 150 ° C. or more as the second solvent makes it difficult for drying unevenness to occur, hardly causes foreign matter, and tends to improve the solvent resolubility. .
Examples of solvents having a boiling point of 150 ° C. or higher include diethylene glycol ethyl methyl ether (boiling point 179 ° C.), 3-methoxy-3-methyl-1-butyl acetate (boiling point 188 ° C.), diethylene glycol ethyl methyl ether (boiling point 179 ° C.), 3 -Methoxybutyl acetate (boiling point 172 ° C.) and the like.

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

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

  In the color material dispersion of the present invention, the solvent as described above is usually preferably in the range of 55 to 95% by mass, particularly 65 to 90% by mass with respect to the total amount of the color material dispersion containing the solvent. % Is preferably within the range of 70% to 88% by mass. When there is too little solvent, a viscosity will rise and a dispersibility will fall easily. Moreover, when there are too many solvents, color material density | concentration will fall and it may be difficult to achieve to a target chromaticity coordinate.

<Dye derivative>
In the present invention, it is preferable to use a pigment derivative in combination with the specific colorant and the specific dispersant from the viewpoint of improving contrast.
A dye derivative is a compound having a role of adding various functions to a dye by adding a functional group to the dye skeleton. The dye derivative preferably has a dye skeleton of a coloring material such as various pigments used in a colored layer of a color filter.

  Examples of the coloring material skeleton used in the color filter coloring layer include an azo skeleton, anthraquinone skeleton, triphenylmethane skeleton, xanthene skeleton, cyanine skeleton, naphthoquinone skeleton, quinoneimine skeleton, methine skeleton, quinophthalone skeleton, and phthalocyanine. Examples include a skeleton, a diketopyrrolopyrrole skeleton, and a dioxazine skeleton.

Since it is combined with PG7, PG58 and the specific yellow color material to form a green colored layer, the pigment skeleton of the pigment derivative includes a pigment derivative having a pigment skeleton of a yellow color material and a pigment having a pigment skeleton of a green color material. It is preferably a derivative or a pigment derivative having a pigment skeleton of a blue color material.
As the dye derivative, a dye derivative further having at least one of an acidic group and basic in the dye skeleton is preferably used.
In the present invention, among these, a pigment derivative having an acidic group is preferably used because it is used in combination with the dispersant having the basic group. Examples of the acidic group include a carboxylic acid group, a carboxylic acid salt, a sulfonic acid group, a sulfonamide group, and a sulfonic acid salt. Among these, from the group consisting of a sulfonic acid group, a sulfonamide group, and a sulfonic acid salt. It is preferable that at least one selected.

As the dye derivative used in the present invention, a dye derivative having a yellow dye skeleton and a dye derivative having a phthalocyanine skeleton are preferably used from the viewpoint of hue, and among them, a PY138 derivative and a copper phthalocyanine derivative are preferable. Further, at least one of a sulfonated derivative of PY138 and a sulfonated derivative of copper phthalocyanine is more preferably used. The dye derivative has a high affinity to the specific colorant and easily adsorbs the dye skeleton, and the sulfonated portion has a high affinity to the nitrogen moiety contained in the dispersant, and thus adsorbs easily. By including a specific pigment derivative, the colorant dispersibility and colorant dispersion stability are improved, the contrast is improved, and the generation of development residues is suppressed, while the solvent resolubility is improved.
This is because the specific colorant is firmly adsorbed to the nitrogen site contained in the structural unit represented by the general formula (I) via the dye derivative, and is surrounded by the dispersant. It is presumed that the toner is easily adsorbed by the dispersing agent during development and the coloring material is not left on the substrate, and the generation of the residue is easily suppressed. Similarly, it is presumed that the specific color material firmly adsorbed on the nitrogen site and surrounded by the dispersant is likely to flow while adsorbed to the dispersant when dissolved again.

(Sulfonated derivative of PY138)
Examples of the sulfonated derivative of PY138 include a structure represented by the following chemical formula (S) in which at least one selected from the group consisting of a sulfonic acid group, a sulfonamide group, and a sulfonate is bonded to PY138. .

(In the chemical formula (S), Z represents a sulfonic acid group, —SO ₂ NH— (CH ₂ ) _{m ′} —NR′R ″, —SO ₂ NH— (CH ₂ ) _{m ′} —COOH, —SO ₂ NH— (CH ₂ ) _{m ′} —SO ₃ H, and one selected from the group consisting of sulfonates, R ′ and R ″ are each independently a hydrogen atom, substituted with 1 to 20 carbon atoms. M represents a saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group, or a heterocyclic ring that may further contain nitrogen, oxygen, or sulfur atoms together with an adjacent nitrogen atom, m Each independently represents an integer of 1 to 6. n ′ represents the number of substituents and represents an integer of 1 to 4.)

Typical examples of the amine component (— (CH ₂ ) _{m ′} —NR′R ″) introduced as a substituent represented by —SO ₂ NH— (CH ₂ ) _{m ′} —NR′R ″ are as follows: , Piperidinomethyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl, diethylaminopropyl, dibutylaminopropyl, piperidinoethyl, pipecolinoethyl, morpholinoethyl, piperidinopropyl, pipecolinopropyl, diethylaminohexyl, diethylaminoethoxypropyl, diethylaminobutyl, dimethylaminoamyl , N-N-methyl-lauryl-aminopropyl, 2-ethylhexylaminoethyl, stearylaminoethyl, oleylaminoethyl and the like.

Further, p-dimethylaminoethylsulfamoylphenyl, p-diethylaminoethylsulfamoylphenyl, p-dimethylaminopropylsulfamoylphenyl, p-diethylaminoethylcarbamoylphenyl and the like seem to be bonded to the —SO ₂ NH— group. It may be a sulfonamido group.

  When there is a sulfonic acid group that does not form a salt, the colorant adsorbing power of the dispersant can be improved by interaction with the salt-forming site of the salt-type dispersant described later, so that the contrast is improved. From the point of view, it is preferable.

Among them, in the case of the sulfonamide group represented by —SO ₂ NH— (CH ₂ ) _{m ′} —NR′R ″ and a sulfonic acid salt-formed with an amino group containing a long-chain alkyl group having 3 or more carbon atoms In the case of a salt, it is preferable from the viewpoint of good solvent resolubility.

The substituents are preferably used, sulfonic acid _{group, -SO 2 NHC 2 H 4 COOH} , -SO 3 - N (CH 3) 2 (C 18 H 37) 2 +, -SO 2 NHC 3 H 6 N ( C ₂ H ₅ ) _{2 and the} like.

  In the chemical formula (S), the number of substituents n ′ is preferably 1 to 2, and more preferably 1 from the viewpoint of high affinity with the nitrogen moiety of the dispersant.

  The sulfonated derivative of PY138 can be produced, for example, by introducing PY138 into concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or a mixture thereof to perform a sulfonation reaction. After the sulfonation reaction, the reaction solution is diluted with a large amount of water or is preferably neutralized with an aqueous amine solution when producing an amine salt. The resulting suspension is filtered and then washed with an aqueous washing solution. And dry. By appropriately selecting the amine of the aqueous amine solution to be used, the amine salt of sulfonic acid can be appropriately introduced as designed. In the production of sulfonic acid amide, thionyl chloride is allowed to act on the sulfonated product of PY138 obtained by the above-mentioned method to form sulfonic acid chloride, which is then mixed with an amine to appropriately form the sulfonated amide as designed. Can be introduced.

  When sulfonation is performed by the above method, the amount of sulfonic acid groups or sulfonamide groups introduced per molecule can be controlled by adjusting the reaction solution concentration, reaction temperature, reaction time, and the like.

  As the sulfonated derivative of PY138, one kind can be used alone, or two or more kinds can be mixed and used. For example, two or more kinds of sulfonated derivatives having different types, substitution positions, or substitution numbers of sulfonic acid groups and / or sulfonamide groups may be used.

  In the present invention, the sulfonated derivative of PY138 is preferably contained in an amount of 1 to 15% by mass, more preferably 2 to 10% by mass, based on the total content of the yellow color material. More preferably, 8% by mass is contained. By using it in such a content, it becomes possible to produce a colored layer that achieves the demand for high brightness and high contrast without greatly changing the hue.

(Sulfonated derivatives of copper phthalocyanine)
The sulfonated derivative of copper phthalocyanine is a structure represented by the following formula (S ′) in which at least one selected from the group consisting of a sulfonic acid group, a sulfonamide group, and a sulfonate is bonded to copper phthalocyanine. Is mentioned.
Formula (S ′): CuPc— (Z) _{n ′}
(In the formula (S ′), CuPc is a copper phthalocyanine structure residue, Z is a sulfonic acid group, —SO ₂ NH— (CH ₂ ) _{m ′} —NR′R ″, —SO ₂ NH— (CH ₂ ) M _′ —COOH, —SO ₂ NH— (CH ₂ ) _{m ′} —SO ₃ H, and one selected from the group consisting of sulfonates, and R ′ and R ″ are each independently a hydrogen atom. A saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms which may be substituted, or further containing a nitrogen, oxygen or sulfur atom together with the adjacent nitrogen atom (It represents what formed a good heterocyclic ring, and m ′ is each independently an integer of 1 to 6. n ′ represents the number of substituents and represents an integer of 1 to 4.)

The copper phthalocyanine structure residue in the formula (S ′) is a residue having a structure having copper phthalocyanine as a base skeleton, and the phthalocyanine may have a known substituent such as an alkyl group or a halogen atom.
As the copper phthalocyanine, a copper phthalocyanine pigment can be used, and examples thereof include pigment blue 15: 3, pigment blue 15: 4, and pigment blue 15: 6.

  In the chemical formula (S ′), the number of substituents n ′ is preferably 1 to 2, and more preferably 1 from the viewpoint of high affinity with the nitrogen moiety of the dispersant.

As the sulfonated derivative of copper phthalocyanine, a structure represented by the following formula (S ″) is particularly preferably used.
Formula (S ″): CuPc—SO ₃ ⁻ · X ⁺
(In the formula (S ″), CuPc is a copper phthalocyanine structure residue, X is any one of a hydrogen atom, a 1-3 valent metal atom, an organic amine, or ammonia.)
Examples of 1 to 3 metal atoms include lithium, potassium, sodium, calcium, magnesium, strontium, and aluminum. Examples of organic amines include monoalkylamines such as ethylamine and butylamine, dialkylamines such as dimethylamine and diethylamine, and trimethylamine. And alkanolamines such as trialkylamine monoethanolamine such as triethylamine, diethanolamine and triethanolamine.
Among these, X in the formula (S ″) is more preferably hydrogen, alkylamine or the like because of excellent viscosity stability and contrast.

  The sulfonated derivative of copper phthalocyanine can be prepared by using the known sulfonation as described above for copper phthalocyanine. Moreover, you may use a commercial item, for example, Solsperse 5000, Solsperse 12000 (above, Nippon Lubrizol company make) etc. are mentioned.

  As the sulfonated derivative of copper phthalocyanine, one kind can be used alone, or two or more kinds can be used in combination. For example, two or more kinds of sulfonated derivatives having different types, substitution positions, or substitution numbers of sulfonic acid groups and / or sulfonamide groups may be used.

  In the present invention, the sulfonated derivative of copper phthalocyanine is preferably contained in an amount of 1 to 15% by mass, more preferably 2 to 10% by mass based on the total content of PG7 and PG58. More preferably, 8% by mass is contained. By using it in such a content, it becomes possible to produce a coating film that achieves the demand for high brightness and high contrast without greatly changing the hue.

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

  The color material dispersion of the present invention is used as a preliminary preparation for preparing a photosensitive colored resin composition for a color filter described later. That is, the colorant dispersion is P / V (colorant component mass in the composition) / (in the composition), which is preliminarily prepared in the previous stage of preparing the photosensitive color resin composition for color filter described later. This is a colorant dispersion having a high ratio (solid content mass other than colorant components). Specifically, the ratio of (mass of color material component in composition) / (mass of solid content other than color material component in composition) is usually 1.0 or more. By mixing the colorant dispersion and each component described later, a photosensitive colored resin composition for a color filter having excellent dispersibility can be prepared. In the present invention, the colorant component mass when calculating the P / V ratio includes the pigment derivative.

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

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

  In addition, the second production method of the colorant dispersion according to the present invention in the case of using a dispersant that is a salt type block copolymer includes a solvent, the block copolymer, and the general formulas (1) to ( 3) One or more compounds selected from the group consisting of 3) and a coloring material are mixed, and at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) is combined with the compound. And a step of dispersing a coloring material and, if necessary, a pigment derivative while forming a salt. Even when the color material is dispersed while forming such a salt, two or more kinds of color materials may be co-dispersed, or after one or more kinds of color materials are dispersed or co-dispersed, two or more kinds of colors are dispersed. The color material dispersion of the present invention may be obtained by mixing the material dispersion.

In the case of using the salt type block copolymer, according to the first production method, after preparing the salt type block copolymer, the color material is dispersed using the salt type block copolymer as a dispersant. Therefore, from the point which can confirm the reaction end point and reaction rate of the block copolymer before salt formation, and the 1 or more types of compound selected from the group which consists of said general formula (1)-(3) correctly. preferable.
Further, according to the second production method, the color material is dispersed without preparing the salt type block copolymer by self-aggregation because the color material is dispersed while preparing the dispersant for the salt type block copolymer. A liquid can be prepared efficiently and dispersibility can be improved.

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

  Specifically, preliminary dispersion is performed with 2.0 mm zirconia beads having a relatively large bead diameter, and main dispersion is further performed with 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a 0.5-2 micrometer filter after dispersion | distribution.

[Photosensitive colored resin composition for color filter]
The photosensitive colored resin composition for a color filter according to the present invention includes a coloring material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. A composition comprising:
The color material is C.I. I. Pigment green 7, C.I. I. Pigment green 58, and yellow color material,
The yellow color material includes at least one anion selected from the group consisting of mono-, di-, tri-, and tetraanions of an azo compound represented by the following general formula (A) and an azo compound having a tautomer structure thereof: An ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (B): Including
The dispersant is a polymer having a structural unit represented by the following general formula (I).
The photosensitive colored resin composition for a color filter of the present invention is excellent in color material dispersion stability like the color material dispersion of the present invention, and as described in the section of the color material dispersion of the present invention, While suppressing the occurrence of display defects, it is possible to form a colored layer with high brightness and high contrast and excellent color reproducibility.

  The photosensitive colored resin composition for a color filter of the present invention contains at least a colorant, a dispersant, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. Other components may be contained as long as the effects are not impaired. Hereinafter, each component contained in the photosensitive colored resin composition for a color filter of the present invention will be described. Among the color materials, PG7 and PG58 which are essential components, and the specific yellow color material, a dispersant, a solvent, and Further, since the pigment derivative that may be included is the same as that described in the color material dispersion of the present invention, description thereof is omitted here.

<Color material>
The color material in the photosensitive colored resin composition for a color filter of the present invention contains PG7, PG58 and the specific yellow color material as essential components, but is used in combination with other pigments in order to adjust the color tone. May be.
It is not particularly limited as long as it can form a desired color when forming the color layer of the color filter, and various organic pigments, inorganic pigments, dispersible dyes may be used alone or in combination of two or more. Can be used. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. Examples of the organic pigment include compounds classified as pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. .) Can be listed with numbers.
Among other color materials, other yellow color materials, other green color materials, and orange color materials are preferably used.

Examples of other color materials include, but are not limited to, the following.
As an orange color material, C.I. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;
As a 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, 155, 156, 166, 167, 168, 175, 180, and 185 etc .;
As a green color material, C.I. I. Pigment Green 36 and 59.

The dispersible dyes include dyes that are dispersible by imparting various substituents to the dyes or insolubilizing in a solvent by using a known lake (chlorination) technique, and low solubility. Examples thereof include dyes that can be dispersed by using in combination with a solvent. By using such a dispersible dye in combination with the dispersant, the dispersibility and dispersion stability of the dye can be improved.
The dispersible dye can be appropriately selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.
As a guide, if the amount of dye dissolved in 10 g of solvent (or mixed solvent) is 10 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

  In the photosensitive colored resin composition for a color filter of the present invention, the total content of PG7 and PG58 with respect to the entire color material may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, it is preferable that the total content of PG7 and PG58 is 10 to 90% by mass with respect to the total amount of the color material from the viewpoint of widening the color reproducibility and increasing the contrast while suppressing the occurrence of display defects. The amount is more preferably 20 to 85% by mass, and still more preferably 30 to 80% by mass.

  In the photosensitive colored resin composition for a color filter of the present invention, the content ratio of the yellow color material with respect to PG7 and PG58 may be appropriately adjusted according to desired chromaticity, and is not particularly limited. Among them, it is preferable that the total content of the yellow color material is 10 to 90% by mass with respect to the total amount of the color material from the viewpoint of widening the color reproducibility and increasing the luminance while suppressing the occurrence of display defects. More preferably, it is 15-80 mass%, and it is still more preferable that it is 20-70 mass%.

  In the photosensitive colored resin composition for a color filter of the present invention, the content ratio of PG58 with respect to PG7 may be appropriately adjusted according to desired chromaticity, and is not particularly limited. Among them, it is preferable that PG58 is 5 to 700 parts by mass with respect to 100 parts by mass of PG7 from the viewpoint of increasing the luminance by increasing color reproducibility while suppressing the occurrence of display defects. More preferably, it is part by mass.

  Moreover, in the photosensitive coloring resin composition for color filters of this invention, in the range which does not impair the effect of this invention, PG7, PG58, and other color materials other than the said specific yellow color material in a color material However, the total content of PG7, PG58 and the specific yellow color material is preferably 70 to 100% by mass, and more preferably 80 to 100% by mass, based on the total amount of the color material. It is more preferable that

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

Acrylic resins such as an acrylic copolymer having a structural unit having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group include, for example, a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, a copolymer. It is a (co) polymer obtained by (co) polymerizing other polymerizable monomers by a known method.
Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. It is done. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

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

  Specific examples of the hydrocarbon ring include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), and adamantane. Rings: aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, fluorene; chain polycycles such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, and cardo structures represented by the following chemical formula (III) Is mentioned.

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

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

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

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

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

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

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

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

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

The alkali-soluble resin used in the present invention preferably has an ethylenic double bond in the side chain. In the case of having an ethylenic double bond, the alkali-soluble resins, or the alkali-soluble resin and the polyfunctional monomer can form a cross-linked bond in the curing step of the resin composition at the time of producing the color filter. By combining with the compound represented by the general formula (1) used in the present invention, the film strength of the cured film is further improved and the development resistance is improved, and the thermal contraction of the cured film is suppressed, Excellent adhesion.
The method for introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method of introducing an ethylenic double bond into a side chain by adding a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, to the carboxyl group of the alkali-soluble resin Or by introducing a structural unit having a hydroxyl group into a copolymer, adding a compound having an isocyanate group and an ethylenic double bond in the molecule, and introducing an ethylenic double bond into the side chain. Etc.

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

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

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

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

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

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

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

As the alkali-soluble resin, it is preferable to select and use an acid-soluble resin having an acid value of 50 mgKOH / g or more from the viewpoint of developability (solubility) with respect to an alkaline aqueous solution used for the developer. The alkali-soluble resin preferably has an acid value of 70 mgKOH / g or more and 300 mgKOH / g or less from the viewpoint of developability (solubility) with respect to an aqueous alkali solution used for the developer and adhesion to the substrate. It is preferable that they are 70 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 ethylenically unsaturated bond equivalent in the case of having an ethylenically unsaturated group in the side chain of the alkali-soluble resin is combined with the compound represented by the general formula (1) used in the present invention, the film strength of the cured film is obtained. Is improved, the development resistance is improved, and it is preferable to be in the range of 100 to 2000, particularly in the range of 140 to 1500 from the viewpoint of obtaining the effect of excellent adhesion to the substrate. When the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Moreover, since the ratio of other structural units, such as the structural unit which has the said carboxy group, and the structural unit which has a hydrocarbon ring, can be relatively increased if it is 100 or more, it is excellent in developability and heat resistance. Yes. The compound represented by the general formula (1) used in the present invention is preferably used in combination with the content described above.
Here, the ethylenically unsaturated bond equivalent is a weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).

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

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

  The alkali-soluble resin used in the photosensitive colored resin composition for color filters may be used singly or in combination of two or more, and the content is not particularly limited. The alkali-soluble resin is preferably in the range of 5 to 60% by mass, more preferably 10 to 40% by mass, based on the total solid content of the photosensitive colored resin composition for a filter. If the content of the alkali-soluble resin is less than the above lower limit, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin is more than the above upper limit, the film may be rough during development. Pattern chipping may occur. In the present invention, the solid content is everything except the above-mentioned solvent, and includes a liquid polyfunctional monomer.

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

These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. When the photosensitive colored resin composition for color filter of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three polymerizable double bonds (trifunctional). Preferred are poly (meth) acrylates of polyhydric alcohols having a valence of 3 or more and their dicarboxylic acid-modified products. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tris Succinic acid modified product of (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) ) Succinic acid modified product of acrylate, dipen Hexa (meth) acrylate are preferable.
Although there is no restriction | limiting in particular in content of the said polyfunctional monomer used in the photosensitive coloring resin composition for color filters, Preferably a polyfunctional monomer is 5 with respect to solid content whole quantity of the photosensitive coloring resin composition for color filters. -60 mass%, More preferably, it exists in the range of 10-40 mass%. If the polyfunctional monomer content is less than the above lower limit, photocuring will not proceed sufficiently, and the exposed part may be eluted during development, and if the polyfunctional monomer content is greater than the upper limit, alkali developability May decrease.

<Photoinitiator>
There is no restriction | limiting in particular as a photoinitiator used in the photosensitive coloring resin composition for color filters, It can use 1 type (s) or 2 or more types in combination from the conventionally well-known various photoinitiators. Specific examples thereof include those described in JP2013-029832A.
As a photoinitiator, only 1 type may be used, but you may use 2 or more types of compounds together. As the photoinitiator, it is preferable to include an oxime ester photoinitiator from the viewpoints of the effect of suppressing the occurrence of pattern chipping and the effect of suppressing the occurrence of water stain. When a dispersant having an acid value is used, water stain tends to occur particularly. However, when an oxime ester photoinitiator is combined, it is preferably used since water stain can be suppressed. The water stain refers to this phenomenon in which a trace of water stain is generated after rinsing with pure water after alkali development. Such water stain disappears after post-baking, so there is no problem as a product, but it is detected as unevenness in the appearance inspection of the patterning surface after development, and there is a problem that it is impossible to distinguish between normal products and abnormal products. Arise. Therefore, if the inspection sensitivity of the inspection apparatus is lowered in the appearance inspection, the yield of the final color filter product is lowered as a result, which becomes a problem.

As the oxime ester photoinitiator, those having an aromatic ring are preferable from the viewpoint of reducing the contamination of the photosensitive colored resin composition for color filters and the contamination of the apparatus due to decomposition products, and a condensed ring containing an aromatic ring is preferable. It is more preferable to have a condensed ring including a benzene ring and a hetero ring.
As the oxime ester photoinitiator, 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime), JP 2000-80068 A, JP 2001-233842 A, Special Table 2010-527339, Special Table 2010-527338, It can be appropriately selected from oxime ester photoinitiators described in JP2013-041153A and the like. As commercially available products, Irgacure OXE-01, Adeka Arcles NCI-930, TR-PBG-345, TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) and the like may be used.

  As the oxime ester photoinitiator used in the present invention, it is particularly preferable to use an oxime ester photoinitiator that generates an alkyl radical, and further to use an oxime ester photoinitiator that generates a methyl radical. It has excellent curability even for photosensitive colored resin compositions with high colorant density to achieve a wide color gamut using, development resistance, pattern chipping suppression effect, and water stain generation suppression effect Is preferable from the viewpoint of superiority. It is presumed that the radical transfer of the alkyl radical is easier to activate than the aryl radical. As an oxime ester photoinitiator that generates an alkyl radical, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (Product name: Irgacure OXE-02, manufactured by BASF), Methanone, [8-[[(Acetyloxy) imino] [2- (2,2,3,3-tetrafluoropropoxy) phenyl] methyl] -11- ( 2-ethylhexyl) -11H-benzo [a] carbazol-5-yl]-, (2,4,6-trimethylphenyl) (trade name: Irgacure OXE-03, manufactured by BASF), 1-pentanone, 1- [4 -[4- (2-Benzofuranylcarbonyl) phenyl] thio] phenyl] -4-methyl-, 1- (o-acetyloxime) (trade name: Irgacure O E-04, manufactured by BASF), ethanone, 1- [9-ethyl-6- (1,3-dioxolane, 4- (2-methoxyphenoxy) -9H-carbazol-3-yl]-, 1- (o- Acetyl oxime) (trade name ADEKA OPT-N-1919, manufactured by ADEKA), methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methylethoxy-) 2-methylphenyl]-, o-acetyloxime (trade name Adeka Arcles NCI-831, manufactured by ADEKA), 1-propanone, 3-cyclopentyl-1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl]-, 1- (o-acetyloxime) (trade name TR-PBG-304, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1-propanone, 3- Clopentyl-1- [2- (2-pyrimidinylthio) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (trade name TR-PBG-314, manufactured by Changzhou Power Electronics New Materials), Ethanone, 2-cyclohexyl-1- [2- (2-pyrimidinyloxy) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (trade name TR-PBG-326, Changzhou Power Electronics New Material Etanone, 2-cyclohexyl-1- [2- (2-pyrimidinylthio) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (trade name TR-PBG-331, Changzhou) 1) -octanone, 1- [4- [3- [1-[(acetyloxy) imino] ethyl] -6- [4-[(4,6-dimethyl-2-pyrimidinyl)] H O] -2-methylbenzoyl] -9H-carbazol-9-yl] phenyl]-, 1- (o-acetyloxime) (trade name: EXTA-9, manufactured by Union Chemical Co., Ltd.).

  In addition, it is preferable to use a photoinitiator having a tertiary amine structure in combination with the oxime ester photoinitiator from the viewpoint of improving sensitivity. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure that is an oxygen quencher in the molecule, radicals generated from the initiator are hardly deactivated by oxygen, and sensitivity can be improved. is there. As a commercial item of the photoinitiator having the tertiary amine structure, for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (for example, Irgacure 369, manufactured by BASF), 4,4′-bis (diethylamino) benzophenone (for example, High Cure ABP, Kawaguchi Pharmaceutical).

  The content of the photoinitiator used in the photosensitive colored resin composition for color filters is not particularly limited, but the photoinitiator is preferably 3 to the total solid content of the photosensitive colored resin composition for color filters. It is 40 mass%, More preferably, it exists in the range of 10-30 mass%. If this content is less than the above lower limit, the photocuring will not proceed sufficiently, and the exposed part may be eluted during development, while if it exceeds the above upper limit, the yellowing of the resulting colored layer will become strong and the luminance will be high. May decrease.

<Optional components>
The photosensitive colored resin composition for color filters may contain various additives as necessary.
Examples of the additive include an antioxidant, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter. Can be mentioned.

  The photosensitive colored resin composition for color filters of the present invention preferably further contains an antioxidant from the viewpoint of heat resistance. The antioxidant may be appropriately selected from conventionally known antioxidants. Specific examples of antioxidants include, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like. From the viewpoint, it is preferable to use a hindered phenol-based antioxidant.

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

<Combination ratio of each component in photosensitive colored resin composition for color filter>
The total content of the color materials is preferably blended in a proportion of 3 to 65 mass%, more preferably 4 to 60 mass%, based on the total solid content of the photosensitive colored resin composition for color filters. If it is more than the said lower limit, the colored layer at the time of apply | coating the photosensitive coloring resin composition for color filters to predetermined | prescribed film thickness (usually 1.0-5.0 micrometers) has sufficient color density. Moreover, if it is below the said upper limit, while being excellent in storage stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. When forming a colored layer having a particularly high color material concentration, the content of the color material is from 15 to 65% by mass, more preferably from 25 to 65% by mass, based on the total solid content of the photosensitive colored resin composition for color filters. It is preferable to mix | blend in the ratio of 60 mass%.
Further, the content of the dispersant is not particularly limited as long as it can uniformly disperse the coloring material. 1 to 40% by mass can be used. Furthermore, it is preferable to mix | blend in the ratio of 2-30 mass% with respect to the solid content whole quantity of the photosensitive coloring resin composition for color filters, and it is preferable to mix | blend especially in the ratio of 3-25 mass%. If it is more than the said lower limit, it is excellent in the storage stability of the dispersibility and dispersion stability of a color material, and the photosensitive coloring resin composition for color filters. Moreover, if it is below the said upper limit, developability will become favorable. When a colored layer having a particularly high colorant concentration is formed, the content of the dispersant is 2 to 25% by mass, more preferably 3 to the total solid content of the photosensitive colored resin composition for color filters. It is preferable to mix | blend in the ratio of 20 mass%. In addition, in the case of a salt type block copolymer, the mass of the dispersing agent is one or more compounds selected from the group consisting of the block copolymer before salt formation and the above general formulas (1) to (3). And the total mass.
Moreover, what is necessary is just to set content of a solvent suitably in the range which can form a colored layer accurately. The total amount of the photosensitive colored resin composition for color filters containing the solvent is usually preferably in the range of 55 to 95% by mass, and more preferably in the range of 65 to 88% by mass. preferable. When the content of the solvent is within the above range, the coating property can be excellent.
In addition, the total content in the case of using the pigment derivative is not particularly limited as long as it can uniformly disperse the coloring material. For example, the photosensitive coloring resin composition for color filters 0.5-8 mass% can be used with respect to solid content whole quantity. Furthermore, it is preferable to mix | blend in the ratio of 1-6 mass% with respect to the solid content whole quantity of the photosensitive coloring resin composition for color filters, and it is preferable to mix | blend especially in the ratio of 1.5-4 mass%.

  In the photosensitive colored resin composition for a color filter of the present invention, the P / V ratio ((color material component mass in the composition) / (solid content mass other than color material components in the composition) ratio) is removed. In view of gas and heat shrinkage, it is preferably 0.1 or more, and more preferably 0.2 or more. On the other hand, it is excellent in display defect and manufacturing convenience, that is, solvent resolubility, development residue, From the viewpoint of excellent 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 preferably set to 0.8. More preferably, it is 6 or less.

<Hardened film of photosensitive colored resin composition for color filter>
The photosensitive coloring resin composition for a color filter has chromaticity coordinates in an XYZ color system of JIS Z8701 measured using a C light source, where x = 0.218 to 0.278 and y = 0.550-0. It is preferable that a cured film in the range of .638 can be formed.
Among these, from the viewpoint of improving color reproducibility, the chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source are x = 0.220-0.270, y = 0.560-0. It is preferable that a cured film in the range of .630 can be formed, and it is further possible to form a cured film in the range of x = 0.225 to 0.265 and y = 0.570 to 0.625. Preferably, it is even more preferable that a cured film in the range of x = 0.230 to 0.260 and y = 0.580 to 0.620 can be formed.

In particular, the cured film of the photosensitive colored resin composition for color filters has a film thickness of 2.8 μm or less, and chromaticity coordinates in the XYZ color system of JIS Z8701 measured by a C light source with a single pixel. , X = 0.218-0.278, y = 0.550-0.638, and the stimulus value Y can preferably display a color space in the range of Y = 30-65, and x = 0.218-0. It is more preferable that a color space in which 278, y = 0.550 to 0.638 and the stimulus value Y is in the range of Y = 40 to 55 can be displayed. The film thickness of the cured film here is that after the photosensitive colored resin composition for 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. The film thickness.
In the chromaticity coordinates in the XYZ color system of JIS Z8701 in which the film thickness is 2.8 μm or less and the color is measured with a C light source with a single pixel, x = 0.218 to 0.278, y = 0.550. ˜0.638 and green color material containing PG7 is 5 to 80 mass with respect to the total amount of the color material as a good blending ratio or combination for displaying a color space in which the stimulus value Y is in the range of Y = 30 to 65 %, PG58 is preferably 2 to 70% by mass, and the yellow colorant is preferably 18 to 90% by mass. Furthermore, the green colorant containing PG7 is 10 to 77% by mass and PG58 is 2% with respect to the total amount of the colorant. It is preferable that -50 mass% and a yellow color material are 20-70 mass%.

<Method for Producing Photosensitive Colored Resin Composition for Color Filter>
The method for producing the photosensitive colored resin composition for color filters of the present invention is not particularly limited. For example, the colorant dispersion of the present invention includes an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and the necessity. Accordingly, other components can be added and mixed using a known mixing means. Alternatively, using the dispersant, a color material dispersion of PG7, a color material dispersion of PG58, a color material dispersion of a yellow color material, and, if necessary, a color material dispersion of another color material PG7 color material dispersion, PG58 color material dispersion, yellow color material color dispersion, and if necessary, other color material color dispersion, and alkali-soluble resin And a polyfunctional monomer, a photoinitiator, and, if necessary, other components can be obtained by mixing using a known mixing means.

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

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

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

The colored layer can be formed by the following method, for example.
First, the above-described photosensitive colored resin composition for color filters of the present invention is applied to a substrate described later using a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. Apply on top to form a wet coating. Of these, spin coating and die coating can be preferably used.
Next, after drying the wet coating film using a hot plate or an oven, it is exposed through a mask having a predetermined pattern and cured by photopolymerization of an alkali-soluble resin and a polyfunctional monomer. Let it be a coating film. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition for the color filter to be used, the thickness of the coating film, and the like.

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

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

  The thickness of the light shielding part is set to about 0.2 to 0.4 μm in the case of a metal thin film, and is set to about 0.5 to 2 μm in the case where a black pigment is dispersed or dissolved in a binder resin. Is done.

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

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

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

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

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

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

<Organic light-emitting display device>
An organic light emitting display device according to the present invention includes the above-described color filter according to the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram illustrating another example of the display device of the present invention, and is a schematic diagram illustrating an example of an organic light emitting display device. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

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

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

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

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

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

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

(Synthesis Example 1: Preparation of Dispersant a)
A 500 ml 4-neck separable flask was decompressed and dried, and then replaced with Ar (argon).
While flowing Ar, 100 g of dehydrated THF, 2.0 g of methyltrimethylsilyldimethylketene acetal, 0.15 ml of 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), and 0.2 g of mesitylene were added. Thereto, 36.7 g of methyl methacrylate (MMA) was dropped over 45 minutes using a dropping funnel. As the reaction progressed, heat was generated, so the temperature was kept below 40 ° C. by cooling with ice. After 1 hour, 13.3 g 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-1. The weight average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 7,600, and the amine value was 95 mgKOH / g.
In a 100 mL round bottom flask, 29.35 parts by mass of block copolymer A-1 was dissolved in 29.35 parts by mass of PGMEA, and phenylphosphonic acid (PPA, Tokyo Chemical Industry Co., Ltd.), which is a compound represented by the above general formula (3). 3.17 parts by mass (the compound represented by the general formula (3) is 0.20 mol based on 1 mol of the DMMA unit of the block copolymer 1) and stirred at a reaction temperature of 30 ° C. for 20 hours. Thus, a salt type block copolymer A-1 (dispersant a) solution was obtained. Specifically, the amine value after salt formation was calculated as follows.
An NMR sample tube was charged with 1 g of a solution in which 9 parts by mass of salt-type block copolymer A-1 (solid after reprecipitation) and 91 parts by mass of chloroform-D1 NMR were mixed, and the 13C-NMR spectrum was measured by nuclear magnetic resonance. Using an apparatus (manufactured by JEOL Ltd., FT NMR, JNM-AL400), the measurement was performed under conditions of room temperature and 10,000 times of integration. Of the obtained spectral data, the integrated value of the carbon atom peak adjacent to the non-salt-formed nitrogen atom and the carbon atom peak adjacent to the salt-formed nitrogen atom at the terminal nitrogen site (amino group) From the ratio, the ratio of the number of amino groups that are salt-formed to the total number of amino groups is calculated, and is not different from the theoretical salt-forming ratio (the two acidic groups of all phenylphosphonic acids are in DMMA of the block copolymer A-1). It was confirmed that a salt was formed with the terminal nitrogen site).
The amine value after salt formation was calculated to be 57 mgKOH / g by subtracting the amine value (38 mgKOH / g) of 0.40 mol of DMMA unit from the amine value of 95 mgKOH / g before salt formation. Table 1 also shows Tg of the block copolymer before and after salt formation.

(Synthesis Example 2: Production of Dispersant b)
Add 250 parts by weight of THF and 0.6 parts by weight of lithium chloride to a 500 mL round bottom 4-neck separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and perform sufficient nitrogen replacement. It was. After cooling the reaction flask to −60 ° C., 4.9 parts by mass of 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. B block monomer 1-ethoxyethyl methacrylate (EEMA) 2.2 parts by weight, 2-hydroxyethyl methacrylate (HEMA) 18.7 parts by weight, 2-ethylhexyl methacrylate (EHMA) 12.8 parts by weight, methacryl 13.7 parts by mass of n-butyl acid (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA) were added dropwise using an addition funnel over 60 minutes. . After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, diluted with PGMEA to obtain a solid content solution of 30% by mass. 32.5 parts by mass of water was added, the temperature was raised to 100 ° C., and the mixture was allowed to react for 7 hours. The structural unit derived from EEMA was deprotected to obtain a structural unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, purified by filtration and vacuum drying, and a structural unit derived from a block containing a structural unit represented by the general formula (I) and a carboxy group-containing monomer A block copolymer A-2 (acid value: 8 mgKOH / g, Tg: 38 ° C.) containing a B block having solvophilic properties. The block copolymer A-2 thus obtained was confirmed by GPC (gel permeation chromatography), whereby the weight average molecular weight Mw was 7730. The amine value was 95 mgKOH / g.
29.35 parts by mass of block copolymer A-2 was dissolved in 29.35 parts by mass of PGMEA in a 100 mL round bottom flask, and phenylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a compound represented by the general formula (3). By adding 3.17 parts by mass (the compound represented by the general formula (3) is 0.20 mol based on 1 mol of the DMMA unit of the block copolymer 1) and stirring at a reaction temperature of 30 ° C. for 20 hours, A salt type block copolymer A-2 (dispersant b) solution was obtained. The acid value of the block copolymer after salt formation is the same as that of the block copolymer A-2 before salt formation, but the amine value after salt formation was specifically calculated in the same manner as in Synthesis Example 1.

(Synthesis Example 3: Production of Dispersant c)
A 500 ml 4-neck separable flask was decompressed and dried, and then replaced with Ar (argon).
While flowing Ar, 100 g of dehydrated THF, 2.0 g of methyltrimethylsilyldimethylketene acetal, 0.15 ml of 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), and 0.2 g of mesitylene were added. Using a dropping funnel, 33 g of methyl methacrylate was dropped over 45 minutes. As the reaction progressed, heat was generated, so the temperature was kept below 40 ° C. by cooling with ice. After 1 hour, 17 g of dimethylaminoethyl methacrylate 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-3. The weight average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 6,000, and the amine value was 120 mgKOH / g.
In a 100 mL round bottom flask, 24.15 parts by mass of block copolymer A-3 was dissolved in 24.15 parts by mass of PGMEA, and phenylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a compound represented by the general formula (3). Add 3.5 parts by mass (the compound represented by the general formula (3) is 0.20 mol with respect to 1 mol of the DMMA unit of the block copolymer A-3) and stir at a reaction temperature of 30 ° C. for 20 hours. As a result, a salt type block copolymer A-3 (dispersant c) solution having a solid content of 20% by mass was obtained. The amine value after salt formation was calculated in the same manner as in Synthesis Example 1.

(Synthesis Example 4: Synthesis of Dispersant d)
In Synthesis Example 2, except that the content is changed to the content shown in Table 1, in the same manner as in Synthesis Example 2, the salt copolymer before formation of salt A-4 and the salt-type block copolymer (dispersant d) solution were added. Synthesized. In Synthesis Example 4, 4.6 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used. Table 1 shows the acid value, Tg, and amine value of the obtained salt copolymer before salt formation and the salt-type block copolymer.

(Synthesis Example 5: Synthesis of Dispersant e)
Block copolymer A-5 (dispersant e) was synthesized in the same manner as in block copolymer A-2 (acid value 8 mgKOH / g, Tg 38 ° C.) before salt formation in Synthesis Example 2.

(Synthesis Examples 6 to 7: Synthesis of dispersant f and dispersant g)
In Synthesis Example 5, except that the monomers and contents shown in Table 1 were changed, the same procedure as in Synthesis Example 5 was followed, except for block copolymer A-6 (dispersant f) and block copolymer A-7 (dispersion). Agent g) was synthesized. Table 1 shows the acid value, Tg, and amine value of the obtained block copolymer.

(Synthesis Example 8: Synthesis of Dispersant h)
In Synthesis Example 2, a block copolymer A-8 before salt formation was synthesized in the same manner as in Synthesis Example 2 except that the monomers and contents shown in Table 1 were changed. The salt-type block copolymer A-8 (dispersant) was prepared in the same manner as in Synthesis Example 2, except that the block copolymer A-8 before salt formation was used and the amount was changed to the amount shown in Table 1 as the salt-forming compound. h) A solution was obtained. Table 1 shows the acid value, Tg, and amine value of the obtained salt copolymer before salt formation and the salt-type block copolymer.

Abbreviations in the table are as follows.
PME-200: methoxypolyethylene glycol monomethacrylate (trade name; PME-200, manufactured by NOF Corporation, Bremer PME-200, ethyleneoxy group repeat number = 4)
DMAPMA: dimethylaminopropyl methacrylamide

(Synthesis Example 9: Synthesis of alkali-soluble resin A solution)
A mixed solution of 40 parts by mass of BzMA, 15 parts by mass of MMA, 25 parts by mass of MAA, and 3 parts by mass of AIBN was dropped into a polymerization tank containing 150 parts by mass of PGMEA at 100 ° C. for 3 hours in a nitrogen stream. did. After completion of dropping, the mixture was further heated at 100 ° C. for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution was 7000.
Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol are added to the obtained polymer solution and heated at 110 ° C. for 10 hours to react. Air was bubbled through the solution. The obtained alkali-soluble resin A is a resin in which a side chain having an ethylenic double bond is introduced into the main chain formed by copolymerization of BzMA, MMA, and MAA using GMA, and has a solid content of 42.6 mass. %, Acid value 74 mgKOH / g, and weight average molecular weight 12000. The weight average molecular weight was measured with Shodex GPC System-21H (Polystyrene) using polystyrene as a standard substance and THF as an eluent. The acid value was measured based on JIS K 0070.

(Synthesis Example 10: Synthesis of alkali-soluble resin B solution)
In Synthesis Example 9, an alkali-soluble resin B solution was obtained in the same manner as in Synthesis Example 9 except that 40 parts by mass of cyclohexyl methacrylate was used instead of 40 parts by mass of BzMA as a comonomer species at the time of polymerization. The solid content was 42.6% by mass, the acid value was 74 mgKOH / g, and the weight average molecular weight was 12,000.

(Synthesis Example 11: Synthesis of alkali-soluble resin C solution)
In Synthesis Example 9, an alkali-soluble resin C solution was obtained in the same manner as in Synthesis Example 9 except that 40 parts by mass of styrene was used instead of 40 parts by mass of BzMA as a comonomer species during polymerization. The solid content was 42.6% by mass, the acid value was 74 mgKOH / g, and the weight average molecular weight was 12,000.

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

(Synthesis Example 13 Dye Derivative A (PY138 Sulfonated Derivative A: Synthesis of Z = SO ₃ H, n ′ = 1 in Formula (S) above))
While cooling 374.76 parts by mass of 11% by mass fuming sulfuric acid to 10 ° C., 74.96 parts by mass of PY138 was added. Subsequently, it stirred at 90 degreeC for 6 hours. The reaction solution was added to 1600 parts by mass of ice water and stirred for 15 minutes, and then the precipitate was filtered. The obtained wet cake was washed three times with 800 parts by mass of water. The wet cake was vacuum-dried at 80 ° C. to obtain PY138 sulfonated derivative A. The molecular weight of the target product was confirmed by TOF-MS.

Example 1
(1) Production of colorant dispersion G1
6.22 parts by mass of the dispersant a solution of Synthesis Example 1 as a dispersant and C.I. I. Pigment Green 7 (PG7, trade name: Chromofine Green 6428EC, manufactured by Dainichi Seika Kogyo Co., Ltd.) 4.48 parts by mass, C.I. I. 4.21 parts by mass of Pigment Green 58 (PG58, trade name: FASTOGEN GREEN A110, manufactured by DIC Corporation), 3.65 parts by mass of Azo derivative 1 obtained in Production Example 1 as a yellow color material, and Synthesis Example 13 0.65 part by weight of the obtained PY138 sulfonated derivative A, 14.59 parts by weight of the alkali-soluble resin A solution obtained in Synthesis Example 9, 66.20 parts by weight of PGMEA, and a particle size of 2.0 mm zirconia beads 100 The mass part is put into a mayonnaise bin, shaken for 1 hour as a preliminary crushing with a paint shaker (manufactured by Asada Tekko Co., Ltd.), then the zirconia beads 200 having a particle size of 0.1 mm are taken out. Mass parts were added, and similarly, this dispersion was dispersed for 4 hours with a paint shaker to obtain a colorant dispersion G1.

(2) Production of Photosensitive Colored Resin Composition G1 for Color Filter 1.41 parts by mass of the color material dispersion G1 obtained in (1) above, and 1. the alkali-soluble resin A solution obtained in Synthesis Example 9 90 parts by mass, 0.60 parts by mass of polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -ON (photoinitiator: trade name Irgacure 907, manufactured by BASF Corporation) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiation Agent: 0.04 parts by mass of trade name Irgacure 369, manufactured by BASF), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O- Acetyloxy 0.02 parts by mass (photoinitiator: trade name Adeka Arcles NCI-831, manufactured by ADEKA) and 0.07 mass by weight of a fluorosurfactant (trade names: MegaFuck F559, manufactured by DIC Corporation) Part, 4.84 parts by mass of PGMEA, and 4.88 parts by mass of 3-methoxy-3-methyl-1-butylacetate were added to obtain a photosensitive colored resin composition G1 for color filters.
(3) Formation of colored layer On photosensitive glassy resin composition G1 obtained in (2) above on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and 100 mm × 100 mm. Then, after applying using a spin coater, it is dried at 80 ° C. for 3 minutes using a hot plate, irradiated with 60 mJ / cm ² of ultraviolet light using an ultrahigh pressure mercury lamp, and further post-treated for 30 minutes in a 230 ° C. clean oven. By baking, the colored layer G1 was formed by adjusting the film thickness so that the film thickness after curing was 2.80 μm.

(Examples 2-10, 20-24, Comparative Examples 1-7)
Production of Color Material Dispersions G2 to G10, G20 to G24, and CG1 to CG7 In Examples 2 to 10 and Comparative Examples 6 to 7, in (1) of Example 1, as shown in Table 2 and Table 4, respectively. Instead of the dispersant a solution, the type and amount used of the dispersant were changed so that the solid content was the same part by mass, and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass. In the same manner as (1), colorant dispersions G2 to G10 and CG6 to CG7 were obtained. In Examples 20 to 23, the color material was changed to the formulation shown in Table 3 in (1) of Example 2 and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass. ), Colorant dispersions G20 to G23 were obtained. In Example 24, the colorant was changed to the formulation shown in Table 3 in (1) of Example 2, and the dye derivative A (PY138 sulfonated derivative A obtained in Synthesis Example 13) was used as the dye derivative. Except for changing 0.33 parts by mass and pigment derivative B (copper phthalocyanine sulfonated derivative, Solsperse 12000 (manufactured by Nihon Lubrizol)) to 0.32 parts by mass, the same as (1) of Example 2, A colorant dispersion G24 was obtained.
In Comparative Examples 1, 4, and 5, CG1, CG4, and CG5 were obtained in the same manner as in (1) of Example 1, except that the color material was changed in (1) of Example 1. In Comparative Examples 2 and 3, CG2 was obtained in the same manner as in Example 1 (1) except that the colorant was changed to the formulation shown in Table 4 in Example 2 (1).
(2) Production of photosensitive colored resin compositions G2 to G10, G20 to G24, and CG1 to CG7 for color filters In place of the color material dispersion G1 in (2) of Example 1, the above color material dispersions G2 to G10, respectively. , G20 to G24, and CG1 to CG7, except that the amount of the alkali-soluble resin was adjusted so that the P / V ratio was the values shown in Tables 2 to 4 in order to obtain a film thickness of 2.8 μm. Were the same as (2) of Example 1 to obtain photosensitive colored resin compositions G2 to G10, G20 to G24, and CG1 to CG7 for color filters.
(3) Formation of colored layer In (3) of Example 1, the above photosensitive colored resin compositions G2 to G10, G20 to G24, and CG1 to CG7 were used in place of the photosensitive colored resin composition G1. Were the same as (3) of Example 1 to obtain colored layers G2 to G10, G20 to G24, and CG1 to CG7.

(Examples 11 to 19)
(1) Production of Photosensitive Colored Resin Compositions G11 to G19 for Color Filter In Examples 11, 12, 14, and 15, the above-described color material dispersion G2 instead of the color material dispersion G1 in (2) of Example 1 Further, as shown in Table 3 for the photoinitiator, NCI831: oxime ester photoinitiator (Adeka Arcles NCI-831, manufactured by ADEAKA) instead of 0.02 parts by mass, respectively TR-PBG: oxime ester -Based photoinitiator (TR-PBG-304, Changzhou Power Electronics New Materials Co., Ltd.) 0.02 parts by mass, OXE03: Oxime ester photoinitiator (Irgacure OXE-03, manufactured by BASF) 0.02 parts by mass, NCI930: Oxime ester photoinitiator (Adeka Arcles NCI-930, manufactured by ADEAKA) 0.02 parts by mass, or OXE04: Oximes Photosensitive colored resin composition G11, 12, 14 for color filter, in the same manner as in (2) of Example 1, except that the tellurium-based photoinitiator (Irgacure OXE-04, manufactured by BASF) was changed to 0.02 mass. And 15 were obtained.
In Example 13, the ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime in (2) of Example 1 was used. ) 0.02 parts by mass, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Corporation) 10 parts by mass and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name Irgacure 369, manufactured by BASF) except 0.05 parts by mass In the same manner as in Example 1, (2), a photosensitive colored resin composition G13 for color filters was obtained.
Moreover, in Examples 16-18, the said color material dispersion liquid G2 was used instead of the color material dispersion liquid G1 in (2) of Example 1, and also alkali-soluble resin A obtained by the synthesis example 9 as alkali-soluble resin. Instead of the solution, the alkali-soluble resin B solution obtained in Synthesis Example 10 was changed to the alkali-soluble resin C solution obtained in Synthesis Example 11 or the alkali-soluble resin D solution obtained in Synthesis Example 12, respectively. Photosensitive colored resin compositions G16 to G18 for color filters were obtained in the same manner as (2) of Example 1 except that the amount used was adjusted so that the solid content would be the same parts by mass.
In Example 19, a photosensitive colored resin composition G19 for a color filter was obtained in the same manner as in Example 18 except that the solvent in Example 18 was changed to that shown in Table 3.
(2) Formation of colored layer In (3) of Example 1, (3) of Example 1 except that the photosensitive colored resin compositions G11 to G19 were used instead of the photosensitive colored resin composition G1, respectively. ) To obtain colored layers G11 to G19.

Here, each abbreviation in the table is as follows.
PG36: C.I. I. Pigment Green 36 (trade name: FASTOGEN GREEN 2YK-50, manufactured by DIC Corporation)
PY138: C.I. I. Pigment Yellow 138 (trade name: Chromo Fine Yellow 6206EC, manufactured by Dainichi Seika Kogyo Co., Ltd.)
PY150: C.I. I. Pigment Yellow 150 derivative (trade name: LEVASCREEN YELLOW G04, manufactured by LANXESS)
PR177: C.I. I. Pigment Red 177 (trade name: Chromophthaled Red A3B, manufactured by BASF)
PB15: 6: C.I. I. Pigment Blue 15: 6 (trade name: FASTOGEN EP-210, manufactured by DIC Corporation)
byk-2000: Disperbyk-2000 (produced by BYK Chemie, a polymer having a structural unit represented by the general formula (I), wherein the compound represented by the general formula (2) forms a salt. Coalescence, solid content 40% by mass)
N21116: Disperbyk-LPN21116 (a polymer having a structural unit represented by general formula (I), manufactured by BYK Chemie, a salt type block copolymer in which a compound represented by general formula (2) forms a salt, (Solid content 40% by mass)
byk-161: trade name Disperbyk-161 (by Big Chemie, urethane dispersant, solid content 30% by mass)
PB822: Trade name Ajisper PB822 (manufactured by Ajinomoto Fine-Techno Co., Ltd., polyester dispersant, solid content 30% by mass)
IRG369: Photoinitiator having tertiary amine structure (Irgacure 369, manufactured by BASF)
IRG907: Photoinitiator having tertiary amine structure (Irgacure 907, manufactured by BASF)
NCI831: oxime ester photoinitiator (Adeka Arcles NCI-831, manufactured by ADAEKA)
TR-PBG: Trade name TR-PBG-304 (Changzhou Power Electronics New Materials Co., Ltd., oxime ester photoinitiator)
OXE03: trade name Irgacure OXE-03 (manufactured by BASF, oxime ester photoinitiator)
NCI930: Brand name Adeka Arcles NCI-930 (manufactured by ADEAKA, oxime ester photoinitiator)
OXE04: trade name Irgacure OXE-04 (manufactured by BASF, oxime ester photoinitiator)
Solvent A: Propylene glycol monomethyl ether acetate (PGMEA)
Solvent B: 3-methoxy-3-methyl-1-butyl acetate

(Examples 25-33, Comparative Example 8)
(1) Production of Color Material Dispersions G25 to G33 and CG8 In Examples 25 to 33 and Comparative Example 8, as shown in Table 5 in Example 1 (1), the types and blending of color materials, respectively. Example 1 (1) except that the amount was changed, and further, the type and amount of the dispersant were changed so that the solid content was the same mass part, and the amount of PGMEA was adjusted so that the total was 100 parts by mass. ), Color material dispersions G25 to G33 and color material dispersion CG8 were obtained.
(2) Production of photosensitive colored resin compositions G25 to G33 and CG8 for color filters The above-mentioned color material dispersions G25 to G33 and CG8 are used in place of the color material dispersion G1 in (2) of Example 1, respectively. In the same manner as in (2) of Example 1, except that the amount of the alkali-soluble resin was adjusted so that the P / V ratio would be the value shown in Table 5 in order to make the thickness 2.8 μm, the color Photosensitive colored resin compositions G25 to G33 for filters and CG8 were obtained.
(3) Formation of colored layer In (1) of Example 1, Example 1 except that the photosensitive colored resin compositions G25 to G33 and CG8 were used instead of the photosensitive colored resin composition G1, respectively. In the same manner as (3), colored layers G25 to G33 and CG8 were obtained.

(Example 34)
(1) Production of colorant dispersion
6.22 parts by mass of the dispersant b solution of Synthesis Example 2 as a dispersant, I. Pigment Green 7 (PG7, trade name: Chromofine Green 6428EC, manufactured by Dainichi Seika Kogyo) is 12.35 parts by mass, PY138 sulfonated derivative A obtained in Synthesis Example 13 is 0.65 parts by mass, and Synthesis Example 9 14.59 parts by mass of the obtained alkali-soluble resin A solution, 66.20 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle size of 2.0 mm were put into a mayonnaise bin, and a paint shaker (Asada Tekko 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 similarly disperse in a paint shaker for 4 hours. To obtain a green color material dispersion g1.
In the green color material dispersion liquid g1, C.I. I. Instead of using 12.35 parts by mass of CI Pigment Green 7, C.I. I. A green color material dispersion g2 was obtained in the same manner as in the green color material dispersion g1 except that 12.35 parts by mass of Pigment Green 58 (PG58, trade name: FASTOGEN GREEN A110, manufactured by DIC Corporation) was used.
In the green color material dispersion liquid g1, C.I. I. Instead of using 12.35 parts by mass of CI Pigment Green 7, 12.35 parts by mass of Azo derivative 1 was used as a color material in the same manner as the green color material dispersion g1 to obtain a yellow color material dispersion y. .

(2) Production of photosensitive colored resin composition G34 for color filter 4.14 parts by mass of green color material dispersion g1 obtained in (1) above, 3.89 parts by mass of green color material dispersion g2 and yellow 3.38 parts by mass of the colorant dispersion y, 1.90 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 9, and a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.) 0.60 part by mass, 0.09 mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Corporation) Parts, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name Irgacure 369, manufactured by BASF) 0.04 parts by mass, ethanone, 1- [9 -Ethyl-6- (2-methyl) Rubenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (photoinitiator: trade name Adeka Arcles NCI-831, manufactured by ADEKA) 0.02 parts by mass, fluorine-based interface 0.07 parts by mass of an activator (trade name Megafax F559, manufactured by DIC Corporation), 4.84 parts by mass of PGMEA, and 4.88 parts by mass of 3-methoxy-3-methyl-1-butyl acetate are added, A photosensitive colored resin composition G34 for color filters was obtained.
(3) Formation of colored layer In (3) of Example 1, the same procedure as (3) of Example 1 except that the photosensitive colored resin composition G34 was used instead of the photosensitive colored resin composition G1. Thus, a colored layer G34 was obtained.
The obtained photosensitive colored resin composition G34 for color filters has the same composition as the photosensitive colored resin composition G2 for color filters of Example 2, and the photosensitive colored resin composition G34 for color filters and the colored layer. The evaluation result of G34 became the same as the evaluation result of the photosensitive colored resin composition G2 for color filters and the colored layer G2.

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

<Optical performance evaluation, contrast evaluation>
The contrast, chromaticity (x, y), and luminance (Y) of the colored layers obtained in Examples and Comparative Examples were measured using Otsuka Electronics' spectroscopic characteristic measurement device LCF-1500M and Aisaka Electric's contrast measurement device CT-1B. Measured.
(Contrast evaluation criteria)
-Value when C = 0 and y = 0.550, (x = 0.218, 0.278) A: over 9000 B: 7000-9000
C: Less than 7000 · Value when C = 0 and y = 0.583, x = 0.244 A: Exceeding 8000 B: 6000 to 8000
C: Less than 6000. Value when C = 0 and y = 0.607, x = 0.276 A: Exceeding 8000 B: 6000 to 8000
C: Less than 6000. Value when y = 0.638 (x = 0.218, 0.278) with C light source A: Exceeding 7000 B: 5000 to 7000
C: Less than 5000

<Display failure evaluation>
Display defect evaluation of the colored layers obtained in Examples and Comparative Examples was performed using a dielectric impedance measurement system 126096W (manufactured by Toyo Technica).
(Display defect evaluation criteria)
A: Dielectric loss tangent (tan δ) at 100 Hz is less than 0.023 B: Dielectric tangent (tan δ) at 100 Hz is 0.023 to 0.048
C: Dielectric loss tangent (tan δ) at 100 Hz exceeds 0.048 If the above evaluation criterion is A or B, it can be used practically, but if the evaluation result is A, the display defect suppressing effect is high.

<Solvent resolubility evaluation>
The tip of a glass substrate having a width of 0.5 cm and a length of 10 cm was immersed in the photosensitive colored resin composition for a color filter obtained in Examples and Comparative Examples and applied to a 1 cm portion of the glass substrate. The pulled glass substrate was placed in a thermo-hygrostat so that the glass surface was horizontal, and dried at a temperature of 23 ° C. and a humidity of 80% RH for 10 minutes. Next, the glass substrate to which the dried coating film was adhered was immersed in PGMEA for 15 seconds. At this time, the redissolved state of the dried coating film was visually discriminated and evaluated. The results are shown in Tables 2 to 5.
(Solvent re-solubility evaluation criteria)
AA: The dried coating film was completely dissolved in 8 seconds or less. A: The dried coating film was completely dissolved. B: A flake of the dried coating film was formed in the solvent, and the solution was colored. C: The dried coating film was dissolved in the solvent. The flakes did not occur and the solution did not color. If the above evaluation criteria were AA, A or B, it was evaluated that the solvent resolubility was good and could be used practically without any problem, but the evaluation result was A and further AA. Is more effective.

<Development residue evaluation>
The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each spinned on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After applying using a coater, the coating was dried at 60 ° C. for 3 minutes using a hot plate to form a colored layer having a thickness of 2.5 μm. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. After observing the unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer by visual observation, the glass substrate is thoroughly wiped with a lens cleaner (trade name Toraysee MK Clean Cloth, manufactured by Toray Industries, Inc.), The coloring degree of the lens cleaner was visually observed. The results are shown in Tables 2-5.
(Development residue evaluation criteria)
AA: Even in the same evaluation with a colored layer having a thickness of 3.5 μm, no development residue was visually confirmed and the lens cleaner was not colored at all. A: No development residue was visually confirmed, and the lens cleaner was completely colored. B: Development residue was not visually confirmed, and the color of the lens cleaner was slightly confirmed. C: Development residue was visually confirmed, and the color of the lens cleaner was confirmed. D: Development residue was visually confirmed. When the above evaluation criteria are AA, A, B, or C, it can be used practically, but if the evaluation result is B, further A, and further AA, the effect is more excellent. ing.

<Development adhesion evaluation>
The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each spinned on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After applying using a coater, the coating was dried at 60 ° C. for 3 minutes using a hot plate to form a colored layer having a thickness of 2.5 μm. This colored layer was irradiated with ultraviolet rays of 60 mJ / cm ² using a super high pressure mercury lamp through a photomask having a mask opening width of ² to 80 μm. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. The substrate after development was observed with an optical microscope, and the presence or absence of a colored layer with respect to the mask opening line width was observed. The results are shown in Tables 2 to 5.
(Development adhesion evaluation criteria)
A: A colored layer was observed in a portion having a mask opening line width of less than 10 μm B: A colored layer was observed in a portion having a mask opening line width of 10 μm or more and less than 20 μm C: A portion having a mask opening line width of 20 μm or more and less than 50 μm A colored layer was observed in D: A colored layer was observed in a portion having a mask opening line width of 50 μm or more and less than 80 μm. E: A colored layer was not observed in a portion having a mask opening line width of 80 μm or less.
If the above evaluation criteria are A, B or C, it can be used practically, but if the evaluation result is B, further A, and further AA, the photosensitive colored resin composition for color filters is suitable for higher definition. Yes.

<Development resistance evaluation>
The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each coated on a glass substrate having a thickness of 0.7 mm (NH Techno Glass Co., Ltd., “NA35”) using a spin coater. did. After heating and drying on an 80 ° C. hot plate for 3 minutes, ultraviolet rays of 40 mJ / cm ² were irradiated using an ultrahigh pressure mercury lamp. The film thickness at this point is measured and set to T1 (μm). Thereafter, shower development was performed using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. The film thickness after development is measured and set to T2 (μm). T2 / T1 × 100 (%) was calculated. The results are shown in Tables 2-5.
(Development resistance evaluation criteria)
A: 95% or more B: 90% or more and less than 95% C: less than 90% If the evaluation result is B, it can be used practically, but if the evaluation criterion is A, the effect is more excellent.

<Water stain evaluation>
The photosensitive colored resin composition for a color filter obtained in each example and each comparative example was thick after post-baking using a spin coater on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.). After coating with a film thickness to form a colored layer of 1.6 μm, it is dried for 3 minutes at 60 ° C. using a hot plate and exposed to 60 mJ / cm ² of ultraviolet light using an ultrahigh pressure mercury lamp without a photomask. By irradiating, a colored layer was formed on the glass substrate. Next, spin development is performed using 0.05 wt% potassium (KOH) as a developer, the developer is subjected to an indirect solution for 60 seconds and then washed with pure water, and the washed substrate is rotated for 10 seconds to remove water. Immediately after centrifugation, the contact angle of pure water was measured as described below to evaluate water stain.
The contact angle of pure water was measured by dropping 1.0 μL of pure water on the surface of the colored layer immediately after removing the water by centrifugation, and determining the static contact angle 10 seconds after the landing according to the θ / 2 method. Measured. The measuring device was measured using a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd.
(Evaluation criteria)
A: Contact angle of 80 ° or more B: Contact angle of 65 ° or more and less than 80 ° C: Contact angle of 50 ° or more and less than 65 ° D: Contact angle of less than 50 ° If the water stain evaluation standard is A or B, it can be used practically. However, if the evaluation result is A, the effect is more excellent.

<Drying unevenness evaluation>
After applying the photosensitive colored resin composition for a color filter obtained in each example and each comparative example on a glass substrate (NH Techno Glass Co., Ltd., “NA35”) using a die coater, Vacuum baking was performed until the degree of vacuum reached 0.1 torr to form a colored layer having a thickness of 2.0 μm. Then, the obtained board | substrate was observed using the interference fringe inspection lamp (Na lamp), and the presence or absence of the drying nonuniformity which generate | occur | produces in a coating film was evaluated visually.
(Evaluation criteria)
A: Drying unevenness is not recognized at all.
B: Drying unevenness is slightly observed.
C: Many drying unevenness is recognized.

[Summary of results]
From the results in the table, Examples 1 to 1 in which PG7 is combined with PG58 and the specific yellow color material, and further, a dispersant that is a polymer having a structural unit represented by the general formula (I) are combined. The colorant dispersions 10 and 20 to 33 were found to have good viscosity stability. On the other hand, the color material dispersions of Comparative Examples 6 to 7 in which PG7 is combined with PG58 and the specific yellow colorant in combination with a urethane dispersant or a polyester dispersant have poor viscosity stability. Was revealed. In addition, in the color material dispersions of Comparative Examples 1 to 5 and 8 in which color materials different from the examples are combined, it is clarified that the viscosity dispersibility is inferior as compared with Example 1 using the same dispersant. It was.

Moreover, the color filter of Examples 1-33 which combined PG58 and the said specific yellow color material, and also combined the dispersing agent which is a polymer which has a structural unit represented by general formula (I). It is clear that the photosensitive colored resin composition for use has good colorant dispersion stability, and the colored layer using the colored resin composition has excellent contrast while suppressing the occurrence of display defects. It was done. Moreover, it was also clarified that the colored layer using the colored resin compositions of Examples 1 to 33 is excellent in solvent resolubility.
On the other hand, Comparative Examples 1 to 5 and 8 in which color materials different from the examples were combined were inferior in contrast. Furthermore, in Comparative Examples 1, 4, and 5, the P / V ratio in the colored resin composition was considerably increased, resulting in poor display, developing residue was deteriorated, and development adhesion was inferior. In Comparative Examples 2, 3, and 8, the P / V ratio in the colored resin composition was larger than in the Examples, and the resolubility, development residue, and development adhesion were higher than in Examples using the same dispersant under the same conditions. The sex was inferior.
Moreover, since the photosensitive coloring resin composition for color filters of Comparative Examples 6-7 which combined PG7, PG58 and the said specific yellow color material with the urethane type dispersing agent and the polyester type dispersing agent is inferior in dispersibility. The contrast was low, and the luminance was lower than in the examples.

  Further, among the examples, as a dispersant, a block containing an A block containing the structural unit represented by the general formula (I) and a B block containing a structural unit derived from a carboxy group-containing monomer and having solvophilicity Or a salt-type block copolymer in which a salt is formed with at least a part of the nitrogen moiety of the structural unit represented by the general formula (I), and the dispersant has an acid value of 1 mgKOH / g In Examples 2, 4, 5, 8, and 11 to 33 using the dispersant having a glass transition temperature of not less than 18 mgKOH / g and the dispersant having a glass transition temperature of 30 ° C. or higher, development of a development residue is particularly suppressed, and It had excellent development adhesion.

  In addition, among the examples, it was clarified that, in the examples using the oxime ester photoinitiator as the photoinitiator, the development resistance and the effect of suppressing the occurrence of water stain were increased.

Further, among the examples, in the examples in which a solvent having a boiling point of less than 150 ° C. (propylene glycol monomethyl ether acetate) as a first solvent and a solvent having a boiling point of 150 ° C. or more as a second solvent are combined, drying unevenness occurs. It became clear that the solvent resolubility was likely to be improved.
Further, among the examples, it was clarified that, in the examples including a maleimide structure having a hydrocarbon ring as the alkali-soluble resin, a colored layer in which a development residue hardly remains is formed. Furthermore, among the examples, it was revealed that a colored layer with improved luminance was formed in examples including both a maleimide structure having a hydrocarbon ring and a styrene structure as the alkali-soluble resin.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Counter substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer
73 hole transport layer 74 light emitting layer 75 electron injection layer 76 cathode 80 organic light emitter 100 organic light emitting display device

Claims (13)

A color material dispersion for a color filter containing a color material, a dispersant, and a solvent,
The color material is C.I. I. Pigment green 7, C.I. I. Pigment green 58, and yellow color material,
The yellow color material includes at least one anion selected from the group consisting of mono-, di-, tri-, and tetraanions of an azo compound represented by the following general formula (A) and an azo compound having a tautomer structure thereof: An ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (B): Including
A color material dispersion for a color filter, wherein the dispersant is a polymer having a structural unit represented by the following general formula (I).
(In General Formula (A), each R ^a is independently —OH, —NH ₂ , —NH—CN, acylamino, alkylamino, or arylamino, and each R ^b is independently —OH or — NH _2. )
(In the general formula (B), each R ^c is independently a hydrogen atom or an alkyl group.)
(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, R ² and R ³ are each independently a hydrogen atom or a hydrocarbon that may contain a hetero atom. Represents a group, and R ² and R ³ may combine with each other to form a ring structure.)   Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn as at least two kinds of metals in the yellow color material The color material dispersion for color filters according to claim 1, which is contained.   The color material dispersion for a color filter according to claim 1 or 2, wherein at least two kinds of metals in the yellow color material are Ni and Zn, or Ni and Cu.   In at least two kinds of metals in the yellow color material, Ni and Zn are included at a molar ratio of Ni: Zn of 90:10 to 10:90, or Ni and Cu are included at 97: 3 to Ni: Cu. The color material dispersion for a color filter according to any one of claims 1 to 3, comprising a molar ratio of 10:90.   Furthermore, the color material dispersion liquid for color filters of any one of Claims 1-4 containing a pigment derivative. A photosensitive colored resin composition for a color filter containing a coloring material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent,
The color material is C.I. I. Pigment green 7, C.I. I. Pigment green 58, and yellow color material,
The yellow color material includes at least one anion selected from the group consisting of mono-, di-, tri-, and tetraanions of an azo compound represented by the following general formula (A) and an azo compound having a tautomer structure thereof: An ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a compound represented by the following general formula (B): Including
The photosensitive coloring resin composition for color filters whose said dispersing agent is a polymer which has a structural unit represented by the following general formula (I).
(In General Formula (A), each R ^a is independently —OH, —NH ₂ , —NH—CN, acylamino, alkylamino, or arylamino, and each R ^b is independently —OH or — NH _2. )
(In the general formula (B), each R ^c is independently a hydrogen atom or an alkyl group.)
(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, R ² and R ³ are each independently a hydrogen atom or a hydrocarbon that may contain a hetero atom. Represents a group, and R ² and R ³ may combine with each other to form a ring structure.)   Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn as at least two kinds of metals in the yellow color material The photosensitive coloring resin composition for color filters of Claim 6 containing.   The photosensitive colored resin composition for a color filter according to claim 6 or 7, wherein at least two kinds of metals in the yellow color material are Ni and Zn, or Ni and Cu.   In at least two kinds of metals in the yellow color material, Ni and Zn are included at a molar ratio of Ni: Zn of 90:10 to 10:90, or Ni and Cu are included at 97: 3 to Ni: Cu. The photosensitive colored resin composition for a color filter according to any one of claims 6 to 8, which is contained at a molar ratio of 10:90.   Furthermore, the photosensitive coloring resin composition for color filters of any one of Claims 6-9 containing a pigment derivative.   A cured film having chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source in the range of x = 0.128 to 0.278 and y = 0.550 to 0.638 can be formed. The photosensitive colored resin composition for color filters according to any one of claims 6 to 10.   A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a photosensitive colored resin composition for a color filter according to any one of claims 6 to 11. A color filter having a colored layer which is a cured product.   A display device comprising the color filter according to claim 12.