JP6776014B2 - Color material dispersion for color filters, photosensitive coloring resin composition for color filters, color filters, and display devices - Google Patents

Description

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

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

Many of the conventional display devices comply with sRGB (IEC61966-2-1), which is an international standard for color spaces. However, there is an increasing demand for a display device compatible with Adobe RGB, which has a wider color reproduction range than sRGB, in order to obtain an expression closer to the real thing and further improve the color reproducibility. The Adobe RGB standard is a definition of a color space proposed by Adobe Systems. In Adobe RGB, the three primary colors are defined as follows for chromaticity coordinates x and y in the XYZ color system. The AdobeRGB standard is characterized by having a wider color reproduction range 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 demand for specifications that meet the DCI (Digital Cinema Initiatives) standard, which has a wider color reproduction range in the red and green directions than sRGB.

Color filters are used in these liquid crystal display devices and organic light emission display devices. For example, in the formation of a color image of a liquid crystal display device, the light that has passed through the color filter is colored as it is in the color of each pixel constituting the color filter, and the light of those colors is combined to form a color image. As the light source at that time, in addition to the conventional cold cathode fluorescent lamp, an organic light emitting element that emits white light or an inorganic light emitting element that emits white light may be used. Further, in the organic light emitting display device, a color filter is used for color adjustment and the like.
Therefore, in color filters, there is an increasing demand for higher brightness, higher contrast, and improved color reproducibility.

In the color filter, the region connecting the three points of red, green, and blue pixels is the limit of the color that can be reproduced. That is, a color filter having a larger triangle consisting of three points of red, green, and blue pixels has a wider range of colors that can be reproduced on the screen by the display device.
In order to achieve a color space having a wide color reproduction range such as Adobe RGB and DCI, in particular, the green pixels of the color filter are chromaticity of green with high color density {(x = 0.20 to 0.30, y = 0). .55 to 0.75), even more preferably (x = 0.20 to 0.30, y = 0.57 to 0.75), even more preferably (x = 0.20 to 0.30, y = It was required to have a region of 0.60 to 0.75)}.

Conventionally, green pigments widely used for green pixels include C.I. I. Pigment Green 7 (hereinafter sometimes abbreviated as PG7), C.I. I. Pigment Green 36 (hereinafter, may be abbreviated as PG36), C.I. I. Pigment Green 58 (hereinafter, may be abbreviated as PG58).
However, when green pixels are produced so as to achieve the high color density green chromaticity region using PG7, there is a problem that the brightness of the green pixels is lowered. Forming green pixels using PG7 as the main green color material results in a dark color filter.
Further, when the green pixel is formed by using the PG36 so as to achieve the green chromaticity region of the high color density, there is a problem that the brightness of the green pixel is lowered, though not as much as that of the PG7.
Further, when PG58 is used, although the brightness is increased, when producing green pixels included in the chromaticity region of green having a high color density, it is necessary to make the green pixels extremely thick, which is a problem in mass productivity. In addition, it was difficult to maintain the color filter performance because only the green pixels were thickened. Further, even if only PG58 is used, there is a region that cannot be achieved in the high color density green chromaticity region, and there is a limit in producing green pixels so as to form a larger triangle.

On the other hand, the green pixel has a problem that a display defect is likely to occur. More specifically, in the horizontal electric field type liquid crystal display device, since the colored layer of the color filter exists in the liquid crystal driving electric field, it is greatly affected by the electrical characteristics of the colored layer. When PG36 is used for the green pixel, various display defects such as a liquid crystal alignment disorder due to the electrical characteristics of the green pixel and a burn-in phenomenon due to a switching threshold deviation occur in the horizontal electric field type liquid crystal display device. When PG58 is used for the green pixel, such a display defect occurs more prominently and becomes a problem.

According to Patent Document 1, in a horizontal electric field type liquid crystal display device, 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 without providing a protective layer made of transparent resin. As a color filter capable of ensuring performance and corresponding to high color reproducibility, it is disclosed that the colored layer forming green pixels contains a specific amount or less of PG36 and has a specific dielectric tangent (tan δ) value. There is.
However, in the technique disclosed in Patent Document 1, although the display defect is reduced, the brightness is insufficient and the wide color reproducibility is also insufficient.

JP-A-2009-162979

The present invention has been made in view of the above circumstances, and is capable of forming a colored layer having high brightness and excellent color reproducibility while being excellent in color material dispersion stability and suppressing the occurrence of display defects. A photosensitive coloring resin composition for a color filter, which can form a colored layer having high brightness and excellent color reproducibility while suppressing the occurrence of display defects, using the liquid and the color material dispersion liquid, and the photosensitive coloring resin composition for the color filter. A color filter using a colored resin composition, which has high brightness and excellent color reproducibility while suppressing the occurrence of display defects, and by using the color filter, high brightness while suppressing the occurrence of display defects. It is an object of the present invention to provide a display device having excellent color reproducibility.

The color material dispersion liquid for a color filter according to the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent.
The coloring material is C.I. I. Contains Pigment Green 59, and yellow colorant
The dispersant is a polymer having a structural unit represented by the following general formula (I).

Further, the photosensitive coloring resin composition for a color filter according to the present invention is photosensitive for a color filter containing a coloring material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. It is a colored resin composition and
The coloring material is C.I. I. Contains Pigment Green 59, and yellow colorant
The dispersant is a polymer having a structural unit represented by the following general formula (I).

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

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

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

According to the present invention, a color material dispersion liquid capable of forming a colored layer having high brightness and excellent color reproducibility while suppressing the occurrence of display defects, which is excellent in color material dispersion stability, is used. However, a display using a photosensitive coloring resin composition for a color filter and a photosensitive coloring resin composition for a color filter capable of forming a colored layer having high brightness and excellent color reproducibility while suppressing the occurrence of display defects. A color filter with high brightness and excellent color reproducibility while suppressing the occurrence of defects, and a display device with high brightness 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 liquid for a color filter, the photosensitive coloring resin composition for a color filter, the color filter, and the display device according to the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acrylic represents each of acrylic and methacrylic, and (meth) acrylate represents each of acrylate and methacrylate.

[Color material dispersion]
The color material dispersion liquid for a color filter according to the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent.
The coloring material is C.I. I. Contains Pigment Green 59, and yellow colorant
The dispersant is a polymer having a structural unit represented by the following general formula (I).

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

In the color material dispersion liquid of the present invention, the color material is C.I. I. Since a polymer containing Pigment Green 59 and a yellow colorant and having a structural unit represented by the general formula (I) is used in combination as a dispersant, the colorant dispersion stability is excellent and display defects occur. It is possible to form a colored layer having high brightness and excellent color reproducibility while being suppressed.
C.I. used as a coloring material in the present invention. I. Pigment Green 59 (hereinafter, may be abbreviated as PG59) is a single color and exhibits a bluish green color, has a relatively strong coloring power, and has high brightness. Therefore, by combining it with a yellow coloring material, it can be used in the coloring material. Even if the content of PG59 is suppressed, or the P / V ratio ((mass of color material component in composition) / (mass of solid content other than color material component in composition) ratio) is suppressed, the above-mentioned high. It is possible to produce green pixels included in the green chromaticity region of the color density. It is presumed that display defects are likely to occur in green pixels due to the green color material having a phthalocyanine skeleton, but when the color material dispersion of the present invention is used, the pixels of the green color material having the phthalocyanine skeleton are used. Since the content can be reduced and the P / V ratio can be reduced, it is presumed that green pixels in which the occurrence of display defects is suppressed can be achieved.
Further, the PG 59 used as the coloring material in the present invention can achieve a chromaticity region that cannot be achieved by the PG 58 in the green chromaticity region having a high color density. Further, since PG59 and the yellow color material are used in combination with a polymer having a structural unit represented by the general formula (I), the color material dispersibility and the color material dispersion stability are excellent, so that the brightness can be increased. While achieving high contrast, 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.

Further, in recent color filters, it is necessary to solve various problems in mass production of color filters with the technology for improving the dispersibility of color materials in order to realize the demands for high brightness and high contrast. There is. That is, in order to increase the concentration of the coloring material in the resin composition, it is inevitably necessary to increase the amount of the dispersant, which causes problems such as generation of development residue and delay in development time. Further, in the manufacturing process of the color filter, it is required that the solid content of the colored resin composition once dried is excellent in the property of being dissolved in the solvent again and the resolubility in the solvent. For example, if the photosensitive colored resin composition adheres to the tip of the die lip during coating with a die coater, a solidified product is generated by drying, but the solidified product dissolves in the photosensitive colored resin composition when the coating is resumed. If it is not easy, a part of the solidified substance on the die lip is peeled off and easily adheres to the colored layer of the color filter, which causes foreign matter defects. In particular, when the concentration of the coloring material in the colored resin composition is increased, the solvent resolubility tends to be insufficient, and there has been a problem that the yield is lowered due to the generation of the above-mentioned foreign matter in the manufacturing process of the color filter.
On the other hand, in the color material dispersion liquid of the present invention, PG59 and the yellow color material are combined with a polymer having a structural unit represented by the general formula (I) as a dispersant, so that the generation of development residue is suppressed. , A photosensitive colored resin composition having excellent solvent resolubility can be produced. Since the PG59 and the yellow color material are combined with the polymer having the structural unit represented by the general formula (I) as the dispersant, the PG59 and the yellow color material are included in the structural unit represented by the general formula (I). It adheres firmly to the nitrogen part and has excellent color material dispersibility, and PG59 and the yellow color material that firmly adsorb to the nitrogen part and are surrounded by the dispersant are easily washed away while being adsorbed by the dispersant during development, and are easily washed away on the substrate. It is presumed that the coloring material is not left behind and the generation of residue is likely to be suppressed. Similarly, it is presumed that the PG59 and the yellow color material, which are firmly adsorbed on the nitrogen moiety and surrounded by the dispersant, are easily washed away while being adsorbed on the dispersant in the resoluble solvent.

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

<Color material>
In the present invention, the coloring material is C.I. I. It contains Pigment Green 59 (PG59).
The PG59 is a color capable of displaying x = 0.10 to 0.30 and y = 0.30 to 0.64 as chromaticity coordinates in the XYZ color system of JIS Z8701 measured by itself using a C light source. It is a color material characterized in that x = 0.13 to 0.20 and y = 0.32 to 0.60 can be displayed.

The PG59 is characterized in that it can display the xy chromaticity coordinate region surrounded by the following equations 1, 2 and 3 in the XYZ color system of JIS Z8701 measured by itself using a C light source.
(Equation 1)
y = 6.715 × x-0.286
However, in Equation 1, 0.121 <x <0.133
(Equation 2)
y = 7147.200 x x ⁵ -8466.000 x x ⁴ +3891.400 x x ³ -854.200 x x ² +86.380 x x-2.579
However, in equation 2, 0.133 <x <0.310
(Equation 3)
y = 1189.500 x x ⁶ + 1817.000 x x ⁵ -3011.300 x x ⁴ + 1447.800 x x ³ -307.420 x x ² + 27.628 x x -0.285
However, in equation 3, 0.121 <x <0.310

Among the xy chromaticity coordinate regions surrounded by the equations 1, 2 and 3, the regions of x = 0.13 to 0.20 and y = 0.32 to 0.60 are the most characteristic and effective.

The PG59 used in the present invention has a wavelength (Tmax) of 505 to 535 nm at which the maximum transmittance of the spectral transmittance spectrum at 400 to 700 nm is assumed to be 5% at 450 nm. Further, the transmittance at the wavelength (Tmax) is 70% or more. Further, the PG59 used in the present invention has a transmittance of the spectral transmittance spectrum at 435 nm of 15% or less, and further, a transmittance of the spectral transmittance spectrum at 575 nm is 5% or less.

In order to form a coating film of PG59 by itself and measure the color, a coating liquid is prepared by blending PG59 with an appropriate dispersant, binder component and solvent, coated on a transparent substrate, dried, and required. It may be cured accordingly. As the binder component, a non-curable thermoplastic resin composition may be used as long as a transparent coating film capable of color measurement can be formed, or a photocurable (photosensitive) or thermosetting resin composition. May be used. Further, in the photosensitive coloring resin composition of the present invention described later, by using a composition containing only PG59 as a coloring material, a coating film containing only PG59 as a coloring material can be formed and color measurement can be performed.
As a transparent coating film containing a dispersant and a binder component that can perform color measurement, for example, the transmittance of the spectral transmittance spectrum at 380 to 780 nm is 95% or more as a guideline at a film thickness of 2.0 μm. can do.
The spectral transmittance spectrum can be measured using a spectroscopic measuring device (for example, Olympus microscopic device OSP-SP200). The measurement condition is a C light source.

Further, in the color material dispersion liquid of the present invention, PG59 is used in combination with a yellow color material as the color material.
Examples of the yellow color material include C.I. I. Pigment Yellow 1,3,12,13,14,15,16,17,20,24,31,55,60,61,65,71,73,74,81,83,93,95,97,98, 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, 168, 175, 185, and C.I. I. Pigment Yellow 150 derivative pigments.

C. I. As the derivative pigment of Pigment Yellow 150, specifically, mono, di, tri and tetra of an azo compound according to the following chemical formula (i) or one of the tautomeric structures thereof, which acts as a host of at least one guest compound. Anions and metals Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, particularly preferably metals corresponding to Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn and La. A complex can be mentioned. Such C.I. I. It is preferable to use the derivative pigment of Pigment Yellow 150 from the viewpoint of improving the brightness.

(In the above chemical formula, R is independently OH, NH ₂ , NH-CN, acylamino, alkylamino, or arylamino, and R'is independently -OH or -NH ₂ , respectively.)

Among them, the yellow color material is at least one anion selected from the group consisting of mono, di, tri and tetra anions of the azo compound represented by the general formula (i) and the azo compound having a tautomeric structure thereof. And the inclusion of at least two metal ions selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn improves brightness and contrast. It is preferable from the viewpoint of improvement.
By containing two or more kinds of metal ions, the crystal growth of the coloring material is suppressed and atomization becomes possible, and further, it is used in combination with a dispersant which is a polymer having a structural unit represented by the general formula (I). From this, it is inferred that a colored layer that is atomized in the colorant dispersion and has improved contrast can be formed.

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

In the azo compound represented by the general formula (i) and the azo compound having a tautomeric structure thereof, R is independently -OH, -NH ₂ , -NH-CN, or alkylamino. However, it is preferable from the viewpoint of hue, and the two Rs may be the same or different from each other.
In the general formula (i), the two Rs are either -OH, both -NH-CN, or one -OH and one -NH-CN, especially in terms of hue. Is more preferable, and it is even more preferable that both are −OH.

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

Among the at least two metals in the case of containing ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn. It preferably contains at least one metal that becomes a divalent or trivalent cation, preferably contains at least one selected from the group consisting of Ni, Cu, and Zn, and further contains at least Ni. Is preferable.
Further, it is preferable to contain Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn, and further, Ni Further, it is preferable to include at least one metal selected from the group consisting of Zn, Cu, Al and Fe. Above all, the at least two kinds of metals are preferably Ni and Zn, or Ni and Cu.

When the ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn are contained, the content ratio of at least two metals is appropriate. It may be prepared.
Among them, the content ratio of Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu and Mn is Ni: other at least the above. The type 1 metal is preferably contained in a molar ratio of 97: 3 to 10:90, and more preferably in a molar ratio of 90:10 to 10:90.
Among them, Ni and Zn are preferably contained in a molar ratio of Ni: Zn of 90:10 to 10:90, and more preferably contained in a molar ratio of 80:20 to 20:80.
Alternatively, Ni and Cu are preferably contained in a molar ratio of Ni: Cu of 97: 3 to 10:90, and more preferably in a molar ratio of 96: 4 to 20:80.

When it contains ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, C.I. I. The derivative pigment of Pigment Yellow 150 may further contain metal ions different from the ions of the specific metal. For example, it may contain at least one metal ion selected from the group consisting of Li, Cs, Mg, Na, K, Ca, Sr, Ba, and La.

C. I. In the derivative pigment of Pigment Yellow 150, as an embodiment containing ions of at least two kinds of metals, there are cases where ions of at least two kinds of metals are contained in a common crystal lattice and one kind each in another crystal lattice. There is a case where crystals containing the metal ions of the above are aggregated. Above all, it is preferable that ions of at least two kinds of metals are contained in the common crystal lattice from the viewpoint of further improving the contrast. Whether the common crystal lattice contains at least two types of metal ions or the other crystal lattice contains crystals containing one type of metal ion is aggregated. For example, it can be appropriately determined by using the X-ray diffraction method with reference to Japanese Patent Application Laid-Open No. 2014-12838.

C. I. The derivative pigment of Pigment Yellow 150 may further contain a compound represented by the following general formula (ii). In this case, C.I. I. The derivative pigment of Pigment Yellow 150 is a metal complex composed of an azo compound represented by the general formula (i) and an anion of the azo compound having a tautomeric structure thereof and a specific metal ion, and the following general formula (ii). Includes complex molecules with the represented compounds. Bonds between these molecules can be formed, for example, by intermolecular interactions, by Lewis acid-base interactions, or by coordination bonds. Further, the structure may be such that the guest molecule is incorporated in the lattice constituting the host molecule, such as an inclusion compound. Alternatively, the two substances may form a co-crystal and form a mixed substitution crystal in which the atom of the second component is located at the position of the regular lattice of the first component.

(In the general formula (ii), R "is an independent hydrogen atom or alkyl group.)

The alkyl group in "R" 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 is substituted with an −OH group. Is also good.
Above all, R "is preferably a hydrogen atom.

The content of the compound represented by the general formula (ii) is generally based on 1 mol of the azo compound represented by the general formula (i) and the azo compound having a remutable structure thereof. It is 5 mol or more and 300 mol or less, preferably 10 mol or more and 250 mol or less, and further preferably 100 mol or more and 200 mol or less.

In addition, C.I. I. Derivative pigments of Pigment Yellow 150 further include urea and substituted ureas such as phenylurea, dodecylurea and the like, and polycondensates thereof with aldehydes, especially formaldehyde; heterocycles such as barbituric acid, benzimidazolone, benzimidazole. Ron-5-sulfonic acid, 2,3-dihydroxyquinoline, 2,3-dihydroxyquinoxalin-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, cyanulic acid and the like may be contained.
In addition, C.I. I. Pigment Yellow 150 derivative pigments also include water-soluble polymers such as ethylene-propylene oxide-block polymers, polyvinyl alcohol, poly (meth) acrylic acids such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl- and ethyl hydroxy. It may contain modified cellulose such as ethyl cellulose.

C. I. Pigment Yellow 150 and its derivative pigments are, for example, JP-A-2001-354869, JP-A-2005-325350, JP-A-2007-25687, JP-A-2007-23287, JP-A-2007-23288. , 2008-24927, and Japanese Patent Application Laid-Open No. 2014-12838.
Further, as the yellow color material, a commercially available product can be appropriately used.

In the color material dispersion liquid of the present invention, the yellow color material is appropriately selected and used alone or in combination of two or more. As a suitable yellow color material, the same yellow color material is preferably used for the same reason as described in the photosensitive coloring resin composition for a color filter described later.
Above all, C.I. I. Pigment Yellow 138 (hereinafter, may be abbreviated as PY138), C.I. I. Pigment Yellow 139 (hereinafter, may be abbreviated as PY139), C.I. I. Pigment Yellow 185 (hereinafter, may be abbreviated as PY185), C.I. I. By using one or more selected from the group consisting of Pigment Yellow 150 (hereinafter, may be abbreviated as PY150) and its derivative pigments, color reproducibility with high brightness and high contrast is suppressed while the occurrence of display defects is suppressed. It is preferable because it is easy to achieve an excellent colored layer.
In the color material dispersion liquid of the present invention, the yellow color material can be used in combination with at least one of PY150 and its derivative pigment and PY138 to suppress the occurrence of display defects and to achieve a high-luminance coloring layer. Is preferable because it is easy to achieve.

Further, in the color material dispersion liquid of the present invention, PG59 and the yellow color material may be used in combination with other color materials as exemplified in the photosensitive resin composition described later, as long as the effects of the present invention are not impaired. Good. As the other color material, for example, another green color material, a blue color material, an orange color material, or the like is preferably used.
It is preferable that the color material dispersion liquid of the present invention further contains at least one of PG58 and PG7 for the same reason as described in the photosensitive coloring resin composition for a color filter described later.

In the color material dispersion liquid of the present invention, the content ratio of PG59 to the entire color material may be appropriately adjusted according to a desired chromaticity, and is not particularly limited. Above all, it is preferable to contain 5 to 95% by mass of PG59 with respect to the entire color material containing PG59 from the viewpoint of widening the color reproducibility and increasing the brightness while suppressing the occurrence of display defects, and 10 to 90%. It is more preferably contained in an amount of 20% by mass, and even more preferably contained in an amount of 20 to 80% by mass.

In the color material dispersion liquid of the present invention, the content ratio of the yellow color material to PG59 may be appropriately adjusted according to a desired chromaticity, and is not particularly limited. Above all, it is preferable to contain 10 parts by mass to 900 parts by mass of the yellow color material with respect to 100 parts by mass of PG59 from the viewpoint of widening the color reproducibility and increasing the brightness while suppressing the occurrence of display defects. , 20 parts by mass to 400 parts by mass is more preferable.

When PG59, a yellow color material, and other color materials are used in the color material dispersion liquid of the present invention, the content ratio is preferably the same as that of the photosensitive resin composition described later. However, since the photosensitive resin composition can be produced by appropriately mixing two or more kinds of the color material dispersion liquid, it is preferably used even if the content ratio is not the same as that of the photosensitive resin composition described later. Be done.

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

The average primary particle size of the coloring material in the present invention represents "volume distribution median diameter (D50)". The average primary particle size of the coloring material is the scanning transmission electron by attaching a dedicated bright-field STEM sample table and optional detector to the electric field radiation scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation. It can be used as a microscope (hereinafter abbreviated as "STEM"), take a STEM photograph of 200,000 times, import it into the software below, select 100 coloring materials arbitrarily on the photograph, and each diameter (passing length). ) Is measured, and it is obtained as a 50% cumulative particle size by volume from the volume-based distribution.
The measurement sample to be used for STEM is prepared by mixing a coloring material and toluene and dropping the mixture onto a collodion film-attached mesh. Further, when obtaining the volume-based particle size distribution and the volume distribution median diameter (D50) from the STEM photograph, the image analysis type particle size distribution measurement software "Mac-View Ver.4" manufactured by Mountech Co., Ltd. is used.

The average dispersed particle size of the coloring material in the coloring material dispersion liquid varies depending on the type of the coloring material used, but is preferably in the range of 10 to 100 nm, and more preferably in the range of 15 to 60 nm. preferable.
The average dispersed particle size of the colored material in the colored material dispersion is at least the dispersed particle size of the colored material particles dispersed in the dispersion medium containing a solvent, which is measured by a laser light scattering particle size distribution meter. Is. To measure the particle size with a laser light scattering particle size distribution counter, the color material dispersion is appropriately diluted with a solvent used in the color material dispersion to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times). It can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, a nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distributed particle size here is the volume average particle size.

In the color material dispersion liquid of the present invention, the content of the color material is not particularly limited. The content of the coloring material is 5 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 coloring material dispersion liquid from the viewpoint of dispersibility and dispersion stability. It is preferable to mix.
In particular, when a coating film or a colored layer having a high color material concentration is formed, the ratio of 30 to 80 parts by mass, more preferably 40 to 75 parts by mass, is based on 100 parts by mass of the total solid content in the color material dispersion liquid. It is preferable to mix with.

<Dispersant>
In the present invention, as the dispersant, a polymer having a structural unit represented by the general formula (I) is used. The structural unit represented by the general formula (I) has basicity and functions as an adsorption site for a coloring material.
By using a polymer having a structural unit represented by the general formula (I) in the color material dispersion liquid of the present invention, the adsorption performance to the color material is improved, and the dispersibility and dispersion stability of the color material are improved. 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 independently alkylene groups) and combinations thereof.
Above all, from the viewpoint of dispersibility, A in the general formula (I) is preferably a -CONH- group or a divalent linking group containing a -COO- group.

Examples of the hydrocarbon group in the hydrocarbon group which may contain a hetero atom in R ² and R ³ include an alkyl group, an aralkyl group, an aryl group and the like.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group and the like, and the number of carbon atoms of the alkyl group is 1 to 18 are preferable, and among them, a methyl group or an ethyl group is more preferable.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The number of carbon atoms of the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xsilyl group and the like. The number of carbon atoms of the aryl group is preferably 6 to 24, more preferably 6 to 12. The preferable number of carbon atoms does not include the number of carbon atoms of the substituent.
The hydrocarbon group containing a hetero atom has a structure in which the carbon atom in the hydrocarbon group is replaced with the hetero atom. Examples of the hetero atom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.
Further, the hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom and a bromine atom.

The fact that R ² and R ³ are bonded to each other to form a ring structure means that R ² and R ³ form a ring structure via a nitrogen atom. Heteroatoms may be contained in the ring structure formed by R ² and R ³ . The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

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

The structural unit represented by the general formula (I) is an alkyl group-substituted amino such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. Examples thereof include group-containing (meth) acrylate and the like, alkyl group-substituted amino group-containing (meth) acrylamide such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide. Of these, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.
The structural unit represented by the general formula (I) may consist 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 (1) to ( When one or more compounds selected from the group consisting of the compounds represented by 3) form a salt, the adsorbability of the coloring material is further improved at the salt forming site, and the color material dispersion stability and development are further improved. It is preferable because it suppresses residues and has excellent solvent resolubility.

(In the general formula (1), ^Ra is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or −O−. It represents R ^e, R ^e is a straight chain of 1 to 20 carbon atoms, branched chain or cyclic alkyl group, a vinyl group, an optionally substituted phenyl group or a benzyl group, or 1 to 4 carbon atoms Represents a (meth) acryloyl group via an alkylene group. In general formula (2), R ^b , R ^b' , and R ^{b "} 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- Representing R ^f , R ^f has a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, and a substituent. It represents a (meth) acryloyl group via a phenyl group or a benzyl group, or an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom. In the general formula (3). , R ^c and R ^d are independently hydrogen atoms, hydroxyl groups, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, vinyl groups, phenyl groups or benzyl groups which may have substituents, respectively. or represents the -O-R ^e, R ^e is a straight chain of 1 to 20 carbon atoms, branched chain or cyclic alkyl group, a vinyl group, an optionally substituted phenyl group or a benzyl group, or the number of carbon atoms Represents a (meth) acryloyl group mediated by 1 to 4 alkylene groups, provided that at least one of R ^c and R ^d contains a carbon atom).

In the general formulas (1) to (3), a linear or branched chain having 1 to 20 carbon atoms in R ^a , R ^b , R ^b' , R ^{b "} , R ^c , R ^d , R ^e , and R ^f . Alternatively, the cyclic alkyl group may be either a straight chain or a branched chain, and may include a cyclic structure. Specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, etc. 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- Examples thereof include an undecyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a tetradecyl group, an octadecyl group and the like. A linear, branched or cyclic alkyl group having 1 to 15 carbon atoms is preferable, and a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms is more preferable. Examples thereof include 1 to 8 linear, branched or cyclic alkyl groups.
^Furthermore, R ^a, R c, in ^{R d,} and ^{R e,} The substituent of the phenyl group or benzyl group which may have a substituent, for example, an alkyl group having 1 to 5 carbon atoms, an acyl group , Acyloxy group and the like.

In R ^b , R ^b' , R ^{b "} , and R ^f , examples of the substituent of the phenyl group or the benzyl group which may have a substituent include an acidic group or an ester group thereof, and the number of carbon atoms is 1 to 1. Examples thereof include an alkyl group of 5 and an acyl group and an acyloxy group.
Further, 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. Examples include 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 means a group that releases a proton in water and exhibits acidity. Specific examples of the acidic group include a carboxy group (-COOH). sulfo group _(-SO 3 H), a phosphono group (-P (= O) (OH ) 2), phosphinico group (> P (= O) ( OH)), boronic acid group (-B _(OH) 2), borinic acid group (> BOH) and the like, carboxylato group (-COO ^-) may be an anion in which a hydrogen atom is dissociated as such, further alkali metal ions and salts such as sodium ions and potassium ions It may be an acidic salt formed.
The ester group of the acidic group includes a carboxylic acid ester (-COOR), a sulfonic acid ester (-SO ₃ R), a phosphoric acid ester (-P (= O) (OR) ₂ ), and (> P (= O). ) (OR)), boronic acid ester (-B (OR) ₂ ), boronic acid ester (> BOR) and the like. Among them, the ester group of the acidic group is preferably a carboxylic acid ester (-COOR) from the viewpoint of dispersibility and dispersion stability. Note that R here is a hydrocarbon group and is not particularly limited, but from the viewpoint of dispersibility and dispersion stability, it is preferably an alkyl group having 1 to 5 carbon atoms, and a methyl group or an ethyl group. More preferably.

The compound of the general formula (2) has a carboxy group, a boronic acid group, a boric acid group, anions thereof, and alkali metal salts thereof from the viewpoints of dispersibility, dispersion stability, alkali developability, and suppression of development residue. , And one or more functional groups selected from these esters, and more preferably having a functional group selected from a carboxy group, a carboxylato group, a carboxylic acid base, 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, etc.), both the acidic group equal side and the halogen atom side hydrocarbon of the compound are terminal nitrogen. Although salt can be formed with the site, it is presumed that the terminal nitrogen site and the hydrocarbon on the halogen atom side are stably salt-formed as compared with the case where the terminal nitrogen site and the acidic group are salt-formed. Then, it is presumed that the dispersibility and dispersion stability are improved by adsorbing the coloring material on the stable salt forming site.

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

^Ra 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 has an aromatic ring, the affinity with the skeleton of the coloring material described later is improved, the dispersibility and dispersion stability of the coloring material are excellent, and a coloring composition having excellent contrast is obtained. It is preferable because it can be used.

The molecular weight of one or more compounds selected from the group consisting of the general formulas (1) to (3) is preferably 1000 or less, and particularly 50 to 800, from the viewpoint of improving the dispersibility of the coloring material. It is preferably 50 to 400, more preferably 80 to 350, and most preferably 100 to 330.

Examples of the compound represented by the general formula (1) include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfate, monoethylsulfuric acid, monon-propylsulfuric 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, and the like. Tetradecyllolide, hexadecyllolide, phenethyl chloride, benzyl chloride, benzyl bromide, benzyl iodide, chlorobenzene, α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethyl Examples thereof include benzoic acid, 4-iodophenylbenzoic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, α-bromophenylacetate methyl, 3- (bromomethyl) phenylboronic acid, and the like. Examples of the compound represented by the general formula (3) include monobutyl phosphate, dibutyl phosphate, methyl phosphate, dibenzyl phosphate, diphenyl phosphate, phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate and the like. ..
A group consisting of phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, dibutyl phosphate, benzyl chloride, benzyl bromide, vinyl sulfonic acid, and p-toluenesulfonic acid monohydrate because of its particularly excellent dispersion stability. One or more selected from the above is preferable, and among them, one or more selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, benzyl chloride, benzyl bromide, and p-toluenesulfonic acid monohydrate may be used. preferable.
Further, it is represented by the general formula (2) having an acidic group and an ester group thereof from the viewpoint that the dispersion stability is excellent and the effect of suppressing the development residue is improved by combining with a block copolymer having an acid value described later. The compounds to be used are also preferably used and consist of 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 determined by the general formula (I). Since it is salt-formed with the terminal nitrogen moiety of the constituent unit represented by the above general formula (I), the above general formula ( The amount of one or more compounds selected from the group consisting of 1) to (3) is preferably 0.01 mol or more, more preferably 0.1 mol or more, and 0.2 mol or more. Is more preferable, and 0.3 mol or more is particularly preferable. When it is at least the above lower limit value, the effect of improving the dispersibility of the coloring material by 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 considered that the development adhesion and the solvent resolubility are excellent.
The one or more compounds selected from the group consisting of the general formulas (1) to (3) may be used alone or in combination of two or more. When two or more types are combined, the total content is preferably within the above range.

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

[Block copolymer]
Assuming that the block containing the structural unit represented by the general formula (I) is the A block, the structural unit represented by the general formula (I) has basicity in the A block, and the adsorption site for the coloring material. Functions as. 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. When the above is formed, the salt-forming portion functions as a stronger adsorption site for the coloring material. On the other hand, the B block that does not include the structural unit represented by the general formula (I) is made to function as a block having solvent affinity. Therefore, the block copolymer used in the present invention functions as a color material dispersant by sharing the functions between the A block that adsorbs the color material and the B block that has solvent affinity.

{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, the 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. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is preferable to contain 3 to 100 pieces, more preferably 3 to 50 pieces, and further preferably 3 to 30 pieces.
The structural unit represented by the general formula (I) may function as a color material adsorption site, may consist of one type, or may include two or more types of structural units.

The A block may have a structural unit other than the structural unit represented by the general formula (I) within the range of achieving the object of the present invention, and may be the same as the structural unit represented by the general formula (I). Any structural unit that can be polymerized can be contained. For example, as the structural unit other than the structural unit represented by the general formula (I) that the basic block portion may contain, specifically, for example, the structural unit represented by the general formula (II) described later and the like. Can be mentioned.
The content ratio of the structural unit represented by the general formula (I) in the A block in the block copolymer before salt formation shall be 50 to 100% by mass with respect to the total mass of all the structural units of the A block. Is preferable, 80 to 100% by mass is more preferable, and 100% by mass is most preferable. This is because the higher the proportion of the structural unit represented by the general formula (I), the better the adsorptive power to the coloring material, and the better the dispersibility and dispersion stability of the block copolymer. The content ratio of the structural unit is calculated from the charged mass when synthesizing the A block having the structural unit represented by the general formula (I).

Further, in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (I) has good dispersibility and dispersion stability, and thus all the structural units of the block copolymer. It is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total mass of. The content ratio of each structural unit in the block copolymer is calculated from the mass charged when the block copolymer before salt formation is synthesized.
The structural unit represented by the general formula (I) may be composed of one type as long as it has an affinity with the coloring material, or may include two or more types of structural units. Good.

{B block}
The B block is a block that does not include the structural unit represented by the general formula (I). As the B block, from among the monomers having an unsaturated double bond that can be copolymerized with the monomer that induces the structural unit represented by the general formula (I), it is appropriate depending on the solvent so as to have a solvent-friendly property. It is preferable to select and use it. As a guide, 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 for inducing the structural unit represented by the general formula (I), and among them, the following general formula The structural unit represented by (II) is preferable.

(In the general formula (II), A'is a direct bond or a divalent linking group, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group, and-[CH (R ⁶ ) -CH (R). ⁷ ) -O] _x- R ⁸ or-[(CH ₂ ) _y- O] _z- R ⁸ is a monovalent group. R ⁶ and R ⁷ are independently hydrogen atoms or methyl groups, respectively. Yes, R ⁸ is a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO, or a monovalent group represented by -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 general formula (II), A'is a direct bond or a divalent linking group. The direct bond, the A 'has no atoms, i.e., a C in the general formula (II) (carbon atoms), and R ⁵ means that it is bound not via the other atom. The divalent linking group can be the same as A in the general formula (I). Among them, 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 Is shown.
The hydrocarbon group in 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, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or 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, a propenyl group and the like. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the obtained polymer, it is preferable that the double bond is at the end of the alkenyl group.
Examples of the substituent of the aliphatic hydrocarbon such as the alkyl group and the alkenyl group include a nitro group and a halogen atom.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xsilyl group and the like, and may further have a substituent. The number of carbon atoms of the aryl group is preferably 6 to 24, more preferably 6 to 12.
In addition, examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent. The number of carbon atoms of the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.
Examples of the substituent of the aromatic ring such as the aryl group and the aralkyl group include a linear and branched alkyl groups having 1 to 4 carbon atoms, an alkenyl group, a nitro group, a halogen atom and the like.
The preferable number of carbon atoms does not include the number of carbon atoms of the substituent.

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

The hydrocarbon group in R ⁸ can be the same as that shown in 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.
Further, R ⁵ in the structural unit represented by the general formula (II) may be the same as or different from each other.

As the R ^5, among others, preferably be selected to be excellent in compatibility with a solvent to be described later, specifically, for example, the solvent is generally a solvent for a color filter colored resin composition When a solvent such as a glycol ether acetate-based solvent, an ether-based solvent, or an ester-based solvent is used, methyl group, ethyl group, isobutyl group, n-butyl group, 2-ethylhexyl group, benzyl group and the like are preferable.

Further, the R ⁵ may be substituted with a substituent such as an alkoxy group, a hydroxyl group, an epoxy group or an isocyanate group as long as the dispersion performance of the block copolymer is not impaired, and the block copolymer may be used together. After synthesizing the polymer, the substituent may be added by reacting with a compound having the above substituent.

The number of structural units constituting the B block is not particularly limited, but the number may be 10 to 300 from the viewpoint that the solvent-affinity site and the color material adsorption site act effectively to improve the dispersibility of the color material. The number is preferably 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 above general formula (II) is the total mass of all the structural units of the B block from the viewpoint of improving the solvent resistance and the dispersibility of the coloring material. On the other hand, it is preferably 50 to 100% by mass, and more preferably 70 to 100% by mass. The content ratio of the structural unit is calculated from the charged mass when synthesizing the B block.

Further, in the block copolymer before salt formation, the content ratio of the structural unit represented by the above general formula (II) improves the dispersibility of the coloring material and the dispersion stability, and thus the entire composition of the block copolymer. It is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, based on the total mass of the units. The content ratio of the structural unit is calculated from the charged mass when synthesizing the block copolymer before salt formation.

The structural unit of the B block may be appropriately selected so as to function as a solvent-based moiety, and the structural unit represented by the above general formula (II) may consist of one type or two or more types. May include the building blocks of. Two or more kinds of 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 a 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 at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer and the compounds represented by the following general formulas (1) to (3). A salt-type block copolymer in which a salt is formed by one or more selected compounds;
When 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, the colorant dispersion stability is excellent and the generation of development residue is suppressed. It is preferable because it has excellent solvent resolubility and also has high development adhesion when it is used as a colored resin composition.
When the concentration of the coloring material is increased and the content of the dispersant is increased, the amount of the binder is relatively decreased, so that the colored resin layer is easily peeled off from the underlying substrate during development. When the dispersant contains a B block containing a structural unit derived from a carboxy group-containing monomer and has the specific acid value and glass transition temperature, the development adhesion is improved. If the acid value is too high, the developability is excellent, but it is presumed that the polarity is too high and peeling is likely to occur during development.

(Constituent 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 copolymerizable with the monomer for inducing the structural unit represented by the general formula (I) can be used.
Examples of such a monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer and the like. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic acid anhydride, ω-carboxy-polycaprolactone. Mono (meth) acrylate and the like can also be used. Further, as a precursor of the carboxy group, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, or citraconic anhydride may be used. Among them, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature and the like.

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

Further, in the present invention, it is preferable that the B block of the block copolymer contains a structural unit derived from a hydroxyl group-containing monomer from the viewpoint of improving development adhesion. When a structural unit derived from a hydroxyl group-containing monomer is contained, it is considered that the development adhesion is improved because it easily interacts with glass, a metal, or the like which is usually used as a substrate. When the B block contains a structural unit derived from a hydroxyl group-containing monomer, the developing speed is further improved.
The hydroxyl group here refers to an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.

As the structural unit derived from the hydroxyl group-containing monomer, a monomer containing an unsaturated double bond and a hydroxyl group that can be copolymerized with the monomer that induces the structural unit represented by the general formula (I) can be used. Examples of such a monomer 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, 1 mol addition of ε-caprolactone of 2-hydroxyethyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate.
Having a primary hydroxyl group is preferable to having a secondary hydroxyl group from the viewpoint of improving developability. The primary hydroxyl group means 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 means 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 (Tgi) of the homopolymer of each monomer is particularly high from the viewpoint that the glass transition temperature of the dispersant used in the present invention is set to a specific value or higher and the development adhesion is improved. It is preferable to use a hydroxyl group-containing monomer having a temperature of 0 ° C. or higher, and further preferably to use a hydroxyl group-containing monomer having a temperature of 10 ° C. or higher.
From the viewpoint of improving development adhesion, one or more selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate is preferable.

Further, 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 with respect to the total mass of all the structural units of the block copolymer. It is more preferably mass% or more, more preferably 3 mass% or more, and particularly preferably 4 mass% or more. When it is at least the above lower limit value, the development adhesion can be made preferable. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less. When it is not more than the above upper limit value, it can be preferable from the viewpoint that the introduction ratio of other useful monomers can be increased. The content ratio of the structural unit is calculated from the charged mass when synthesizing the block copolymer before salt formation.

Further, in the present invention, it is preferable that the B block contains a structural unit derived from an aromatic group-containing monomer from the viewpoint of improving solvent resolubility. When a structural unit derived from an aromatic group-containing monomer is contained, the compatibility with the solvent and other components is likely to be improved, and thus 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 is copolymerizable with the monomer that induces 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 ether such as phenylvinyl ether. Kind is mentioned.
As will be described later, the glass transition temperature (Tgi) of the homopolymer of each monomer is particularly high from the viewpoint that the glass transition temperature of the dispersant used in the present invention is set to a specific value or higher and the development adhesion is improved. It is preferable to use an aromatic group-containing monomer having a temperature of 0 ° C. or higher, and further preferably to use an aromatic group-containing monomer having a temperature of 10 ° C. or higher.
One or more selected from the group consisting of benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and phenoxyethyl (meth) acrylate from the viewpoint that solvent resolubility is easily improved. It is preferable that there is at least one selected from the group consisting of benzyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate.

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

Among them, the solvent-friendly B block is (i) a structural unit derived from a hydroxyl group-containing monomer and an aromatic group-containing monomer, and (ii) a structural unit derived from a hydroxyl group and an aromatic group-containing monomer. It is preferable to contain at least one type from the viewpoint of improving development adhesion and solvent resolubility.

(I) When each of the structural unit derived from the hydroxyl group-containing monomer and the structural unit derived from the aromatic group-containing monomer is contained, the structural unit derived from the hydroxyl group-containing monomer is relative 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, and more preferably 0.5 parts by mass or more. This is because if it is at least the above lower limit value, the development adhesion can be excellent. Similarly, the structural unit derived from the hydroxyl group-containing monomer is preferably contained in an amount of 15 parts by mass or less, and more preferably 7 parts by mass or less, based on 1 part by mass of the structural unit of the aromatic group-containing monomer. This is because if it is not more than the above upper limit value, the solvent resolubility can be excellent. Above all, the value of the glass transition temperature (Tgi) of the homopolymer is 10 with respect to 1 part by mass of the structural unit derived from the aromatic group-containing monomer in which the value of the glass transition temperature (Tgi) of the homopolymer is 10 ° C. or higher. It is particularly preferable to contain a structural unit derived from a hydroxyl group-containing monomer having a temperature of ° C. or higher in the above range. This is because the development adhesion can be further improved by containing the content at the above lower limit value or more, and the solvent resolubility can be further improved by containing the content at the above upper limit value or less.

Further, (ii) examples of the 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 and 2-acryloyloxyethyl-. Examples thereof include 2-hydroxyethyl-phthalic acid. 2-Hydroxy-3-phenoxypropyl (meth) acrylate has a glass transition temperature value (Tgi) of a homopolymer of 10 ° C. or higher, and has an effect and aromaticity obtained from a structural unit derived from a hydroxyl group-containing monomer. It is preferably used because any of the effects obtained from the structural unit derived from the group-containing monomer can be obtained. That is, it is preferable in that the development adhesion, the development speed, and the solvent resolubility are improved.
(Ii) When a structural unit derived from a hydroxyl group- or aromatic group-containing monomer is contained, one structural unit can improve development adhesion, development speed, and solvent resolubility, and thus can be used with other functional monomers. There is also the advantage that the introduction ratio can be increased.

Further, as will be described later, the value (Tgi) of the glass transition temperature of the homopolymer of the monomer is 10 from the viewpoint of setting the glass transition temperature of the dispersant used in the present invention to a specific value or higher and improving the development adhesion. The total amount of monomers having a temperature of ° C. or higher is preferably 75% by mass or more in the B block, and more preferably 85% by mass or more.

In the block copolymer, the ratio m / n of the number of units m of the constituent units of the A block and the number of units n of the constituent units of the B block shall be within the range of 0.05 to 1.5. Is preferable, and it is more preferably in the range of 0.1 to 1.0 from the viewpoint of dispersibility and dispersion stability of the coloring material.

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. Is more preferable, and 60 mgKOH / g or more is even more preferable. Further, the upper limit is more preferably 130 mgKOH / g or less, and even more preferably 120 mgKOH / g or less. If it is equal to or more than the above lower limit value, the dispersion stability is more excellent. Further, when it is not more than the above upper limit value, the compatibility with other components is excellent and the solvent resolubility is good.
In the present invention, the amine value of the block copolymer before salt formation is potassium hydroxide which is equivalent to the amount of hydrochloric acid required to neutralize 1 g of the solid content of the block copolymer before salt formation. It represents the mass (mg) of, and 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 dispersibility and dispersion stability of the coloring material. More preferably, it is more preferably 3000 to 12000.
Here, the weight average molecular weight (Mw) is determined as a standard polystyrene conversion value by gel permeation chromatography (GPC).
In the present invention, the weight average molecular weight Mw of the block copolymer is determined as a standard polystyrene-equivalent value by GPC (gel permeation chromatography). For the measurement, HLC-8120GPC manufactured by Toso Co., Ltd. was used, the elution solvent was N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide was added, and the polystyrene standard for the calibration curve was Mw377400, 210500, 96000, 50400. , 20650, 10850, 5460, 2930, 1300, 580 (above, Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Toso Co., Ltd.), and the measurement columns are TSK-GEL ALPHA-M x 2 (Toso). It was carried out as (manufactured by Co., Ltd.). The macromonomer, salt-type block copolymer, and graft copolymer, which are the raw materials for the block copolymer, are also subjected to the above conditions.

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

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

Further, as a method for preparing a salt-type block copolymer, from the general formulas (1) to (3), the polymer having the structural unit represented by the general formula (I) is dissolved or dispersed in a solvent. Examples thereof include a method of adding one or more compounds selected from the above group, stirring, and heating if necessary.
From the terminal nitrogen moiety of the structural unit represented by the general formula (I) of the polymer having the structural unit represented by the general formula (I) and the general formulas (1) to (3). The fact that one or more compounds selected from the above group form a salt and the ratio thereof can be confirmed by a known method such as NMR.

The amine value of the obtained salt-type block copolymer is smaller than that of the block copolymer before salt formation by the amount of salt formed. However, since the salt formation site is the same as the terminal nitrogen site corresponding to the amino group, or rather a strengthened color material adsorption site, salt formation tends to improve the color material dispersibility and the color material dispersion stability. is there. In addition, as with the amino group, if the salt formation site is too large, 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 dispersion stability of the coloring material and the solvent resolubility. The amine value of the obtained salt-type block copolymer (P2) is preferably 0 mgKOH / g or more and 130 mgKOH / g or less, and more preferably 0 mgKOH / g or more and 120 mgKOH / g or less.
When it is not more than the above upper limit value, the compatibility with other components is excellent and the solvent resolubility is good.

Among the salt-type block copolymers, the amine value of the salt-type block copolymer salt-formed by the compound represented by the general formula (2) is measured by the method described in JIS K 7237. Can be a value. In the compound of the general formula (2), the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the hydrocarbon on the halogen atom side form a salt, so that the compound is also in a salt-formed state by the measurement method. This is because the amine value can be measured without causing any change.
On the other hand, among the salt-type block copolymers, the amine value of the salt-type block copolymer salt-formed by the compound represented by the general formula (1) or (3) is before the salt formation described above. It can be obtained by calculating from the amine value of the block copolymer as follows. The compound represented by the general formula (1) or (3) is such a salt-type block because the nitrogen moiety at the terminal 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 changes and an accurate value cannot be measured.
First, the amine value of the block copolymer before salt formation is determined by the above-mentioned method. Next, using 13C-NMR, the group consisting of the general formula (1) or (3) with respect to the terminal nitrogen moiety of the salt-type block copolymer having the structural unit represented by the general formula (I). The reaction rate (ratio of nitrogen sites at the ends of salt formation) of one or more compounds selected from the above 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. Assuming that (the amine value of the block copolymer (P1) before salt formation measured by the method described in JIS K 7237) × (the nitrogen site ratio of the salt-formed terminal calculated from the 13C-NMR spectrum). It is obtained by subtracting the amine value consumed by salt formation, which is calculated by (%) / 100), 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 block}} × {Salt-formed terminal nitrogen moiety ratio (%) / 100} calculated from 13C-NMR spectrum

The acid value of the dispersant used in the present invention is preferably 1 mgKOH / g or more as a lower limit from the viewpoint of exhibiting the effect of suppressing the development residue. Above all, the acid value of the dispersant is more preferably 2 mgKOH / g or more because the effect of suppressing the development residue is more excellent. Further, the acid value of the dispersant used in the present invention is preferably 18 mgKOH / g or less as an upper limit from the viewpoint of preventing deterioration of development adhesion and solvent resolubility. Above all, the acid value of the dispersant is more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less, from the viewpoint of improving development adhesion and solvent resolubility.
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 adhesion 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, and is JIS. It is a value measured by the method described in K 0070.
Further, the acid value of the salt-type block copolymer in which the salt-type block copolymer is salt-formed by the compound represented by the general formula (2) is also a value measured by the method described in JIS K 0070. Is. In the compound of the general formula (2), the terminal nitrogen moiety and the halogen atom-side hydrocarbon of the structural unit represented by the general formula (I) form a salt, so that the compound is also in a salt-formed state by the measurement method. This is because it can be measured without causing any change.
On the other hand, when the salt-type block copolymer is a salt-type block copolymer in which a salt is formed by the compound represented by the general formula (1) or (3), the acidic group used for salt formation is used. The acid value will be calculated excluding. 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 the present application, the acid value of the salt-type block copolymer salt-formed by the compound represented by the general formula (1) or (3) is calculated by the 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 the state of salt formation. This is because accurate values 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 Acid Value of Block Polymer 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, for example, the acid value consumed by salt formation is measured by measuring a 13C-NMR spectrum using a nuclear magnetic resonance apparatus, and in the obtained spectral 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 salt-formed terminal nitrogen sites to the total number of terminal nitrogen sites is calculated. .. {Amine value of block copolymer before salt formation measured by the method described in JIS K 7237} × {By the nitrogen site ratio (%) / 100} at the end of salt formation calculated from the 13C-NMR spectrum. , The amine value consumed is calculated, and this value becomes the same value as the acid value consumed by salt formation.
However, when the compound represented by the general formula (1) is salt-formed in an amount of 1 mol or less with respect to 1 mol of the terminal nitrogen moiety of the structural unit represented by the general formula (I), 1 acidic group is used. When the compound represented by the general formula (3) having two salts is formed in 1 mol or less, or the compound represented by the general formula (3) having two acidic groups is salted in 0.5 mol or less. When the acidic group is formed, if the total amount of the acidic group is salt-formed with the terminal nitrogen moiety of the structural unit represented by the general formula (I), the acidic group is formed in the salt-type block copolymer after salt formation. Does not affect the acid value, so that 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 molar number exceeding the above, there are acidic groups that are not salt-formed in the dispersant even after salt formation. Therefore, as in the above formula, the acid value of the unsalted acidic group is added to the acid value of the block copolymer before salt formation to calculate the acid value of the dispersant.

Further, in the present invention, the glass transition temperature of the dispersant is preferably 30 ° C. or higher from the viewpoint of improving the development adhesion. That is, regardless of whether the dispersant is a pre-salt block copolymer or a salt-type block copolymer, the glass transition temperature thereof is preferably 30 ° C. or higher. If the glass transition temperature of the dispersant is low, especially if it is equal to or lower than the developer temperature (usually about 23 ° C.), the development adhesion may decrease. It is presumed that this is because when the glass transition temperature is equal to or lower than the developer temperature, the movement of the dispersant increases during development, and as a result, the development adhesion deteriorates. When the glass transition temperature is higher than the developer temperature, the molecular motion of the dispersant during development is suppressed, so 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) in accordance with JIS K7121.

However, the glass transition temperature (Tg) of the block copolymer without salt formation can be calculated by the following formula and used as an index.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that the block copolymer is copolymerized with n monomer components from i = 1 to n. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum of i = 1 to n. As the glass transition temperature value (Tgi) of the homopolymer of each monomer, the value of Polymer Handbook (3rd Edition) (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.
Since the glass transition temperature based on the calculated value is substantially the same as the value measured by the DSC, it can be used as an index of the glass transition temperature of the block copolymer without salt formation.

In the color material dispersion liquid of the present invention, at least one kind of polymer having a structural unit represented by the general formula (I) is used as the dispersant, and the content thereof is the type of color material used and further described later. It is appropriately selected according to the solid content concentration and the like in the photosensitive coloring resin composition for a color filter.
The content of the dispersant is 3 to 45 parts by mass, more preferably 5 to 35 parts by mass with respect to 100 parts by mass of the total solid content in the color material dispersion liquid 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 colorant concentration, the content of the dispersant is 3 to 25 parts by mass, more preferably 3 to 25 parts by mass, based on 100 parts by mass of the total solid content in the colorant dispersion liquid. It is preferable to mix in a ratio of 5 to 20 parts by mass.
In the present invention, the solid content is all other than the above-mentioned solvent, and includes monomers and the like dissolved in the solvent.

[solvent]
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the colorant dispersion and can dissolve or disperse them. The solvent can be used alone or in combination of two or more.
Specific examples of the solvent include alcohol-based solvents such as methyl alcohol, ethyl alcohol, i-propyl alcohol and methoxy alcohol; carbitol-based solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate and methoxypropion. Ester solvents such as methyl acid, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, n-butyl butyrate, clohexanol acetate; acetone, Ketone solvents such as methyl ethyl ketone, cyclohexanone, 2-heptanone; glycol ether acetate such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate Solvents: Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA); Diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl Glycol ether solvents such as ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether; N, N-dimethyl Aprotonic amide solvents such as formamide, N, N-dimethylacetamide, N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated carbides such as benzene, toluene, xylene and naphthalene. Hydrogen-based solvents; saturated hydrocarbon-based solvents such as N-heptane, N-hexane, and N-octane; organic solvents such as aromatic hydrocarbons such as toluene and xylene can be mentioned. Among these solvents, glycol ether acetate-based solvent, carbitol acetate-based solvent, glycol ether-based solvent, and ester-based solvent are preferably used in terms of solubility of other components. Among them, the solvents used in the present invention include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, butyl carbitol acetate (BCA), and 3-methoxy. Solubility and application of other components must be at least one selected from the group consisting of -3-methyl-1-butyl acetate, ethyl lactate, methyl 2-hydroxypropionate, and 3-methoxybutyl acetate. It is preferable from the viewpoint of aptitude.

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

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

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

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

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

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

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

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

The color material dispersion liquid of the present invention preferably contains the above solvent in the range of 55 to 95% by mass, particularly 65 to 90% by mass, based on the total amount of the color material dispersion liquid containing the solvent. It is preferably in the range of%, and more preferably in the range of 70 to 88% by mass. If the amount of solvent is too small, the viscosity tends to increase and the dispersibility tends to decrease. On the other hand, if the amount of the solvent is too large, the concentration of the coloring material decreases, and it may be difficult to achieve the target chromaticity coordinates.

(Other ingredients)
The color material dispersion liquid of the present invention may further contain a dispersion auxiliary resin and other components, if necessary, as long as the effects of the present invention are not impaired.
Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified in the photosensitive coloring resin composition for a color filter described later. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant particles to come into contact with each other, which may have the effect of stabilizing the dispersion and reducing the amount of the dispersant due to the effect of stabilizing the dispersion.
In addition, as other components, for example, a surfactant for improving wettability, a silane coupling agent for improving adhesion, a defoaming agent, an anti-repellent agent, an antioxidant, an antioxidant, an ultraviolet absorber, and an ultraviolet absorber. And so on.

The color material dispersion liquid of the present invention is used as a preliminary preparation for preparing a photosensitive coloring resin composition for a color filter, which will be described later. That is, the color material dispersion liquid is (mass of color material component in composition) / (color material component in composition) that is preliminarily prepared in the stage before preparing the photosensitive coloring resin composition for a color filter described later. It is a color material dispersion having a high ratio of solid content other than). Specifically, the ratio (mass of color material component in composition) / (mass of solid content other than color material component in composition) is usually 1.0 or more. By mixing the color material dispersion liquid and each component described later, it is possible to prepare a photosensitive coloring resin composition for a color filter having excellent dispersibility.

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

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

Further, when a dispersant which is a salt-type block copolymer is used, the second method for producing the coloring material dispersion liquid according to the present invention is a solvent, the block copolymer, and the general formulas (1) to (1) to (1). At least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the compound by mixing one or more compounds selected from the group consisting of 3) and the coloring material. It has a step of dispersing the coloring material while forming a salt of. Even when the coloring materials are dispersed while forming such a salt, two or more kinds of coloring materials may be co-dispersed, or after one or more kinds of coloring materials are dispersed or co-dispersed, two or more kinds of colors The color material dispersion liquid of the present invention may be obtained by mixing the material dispersion liquid.

When a salt-type block copolymer is used, according to the first production method, after preparing the salt-type block copolymer, the salt-type block copolymer is used as a dispersant to disperse the coloring material. Therefore, it is possible to accurately confirm the reaction end point and the reaction rate of the block copolymer before salt formation and one or more compounds selected from the group consisting of the general formulas (1) to (3). preferable.
Further, according to the second production method, since the coloring material is dispersed while preparing the dispersant for the salt-type block copolymer, the salt-type block copolymer does not self-aggregate and the coloring material is dispersed. The liquid can be efficiently prepared and the dispersibility can be improved.

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

Specifically, pre-dispersion may be performed with 2.0 mm zirconia beads having a relatively large bead diameter, and then main dispersion may be performed with 0.1 mm zirconia beads having a relatively small bead diameter. Further, after dispersion, it is preferable to filter with a filter of 0.5 to 2 μm.

[Photosensitive colored resin composition for color filters]
The photosensitive coloring resin composition for a color filter according to the present invention is a photosensitive coloring resin for a color filter containing a coloring material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. It ’s a composition
The coloring material is C.I. I. Contains Pigment Green 59, and yellow colorant
The dispersant is a polymer having a structural unit represented by the following general formula (I).
The photosensitive coloring resin composition for a color filter of the present invention is excellent in color material dispersion stability like the color material dispersion liquid of the present invention, and as described in the section of the color material dispersion liquid of the present invention. It is possible to form a colored layer having high brightness and excellent color reproducibility while suppressing the occurrence of display defects.
Further, since the photosensitive coloring resin composition for a color filter of the present invention combines PG59 and a yellow color material with a polymer having a structural unit represented by the general formula (I) as a dispersant, the color of the present invention is described above. As described in the section of the material dispersion liquid, it is possible to form a colored layer having excellent solvent resolubility while suppressing the generation of development residue.

The photosensitive coloring resin composition for a color filter of the present invention contains at least a coloring material, a dispersant, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and is of the present invention. Other components may be further contained as long as the effect is not impaired. Hereinafter, each component contained in the photosensitive coloring resin composition for a color filter of the present invention will be described, but the PG59 and the yellow color material, the dispersant, and the solvent, which are essential components of the color materials, will be described in the above invention. Since it is the same as that described in the color material dispersion liquid, the description here will be omitted.

<Color material>
The coloring material in the photosensitive coloring resin composition for a color filter of the present invention contains PG59 and a yellow coloring material as essential components, but other pigments may be used in combination in order to adjust the color tone.
It is not particularly limited as long as it can develop a desired color when the colored layer of the color filter is formed, and various organic pigments, inorganic pigments, and dispersible dyes are mixed alone or in combination of two or more. Can be used. Among them, organic pigments are preferably used because they have high color development and high heat resistance. Examples of the organic pigment include compounds classified as Pigments in the color index (CI; published by The Society of Dyers and Colorists), specifically, the following color index (CI). .) Examples include those with numbers.
As the other color materials, among them, other green color materials, blue color materials, and orange color materials are preferably used.

Examples of other coloring 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 blue color material, C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
As a green color material, C.I. I. Pigment Green 7, 36, 58.

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

Above all, in the photosensitive coloring resin composition for a color filter of the present invention, C.I. I. Pigment Green 58 and C.I. I. It is preferable to contain at least one of Pigment Green 7. Above all, it is preferable to further include PG58 from the viewpoint that high-luminance green pixels can be formed while achieving the target chromaticity and suppressing display defects. When PG59 and PG58 are mixed and used, it is possible to widen the color reproducibility, reduce the P / V ratio, and improve the brightness as compared with using PG58 alone.
Further, among them, it is preferable to further contain PG7 from the viewpoint of further reducing the P / V ratio and improving plate-making property such as development resistance while achieving the target chromaticity and suppressing display defects.

In the photosensitive coloring resin composition for a color filter of the present invention, the content ratio of PG59 to the entire coloring material may be appropriately adjusted according to a desired chromaticity, and is not particularly limited. Above all, from the viewpoint of widening the color reproducibility and increasing the brightness while suppressing the occurrence of display defects, it is preferable to contain 5 to 95% by mass of PG59 with respect to the entire color material containing PG59, and 10 to 10 It is more preferably contained in an amount of 90% by mass, and even more preferably contained in an amount of 20 to 80% by mass.

In the photosensitive coloring resin composition for a color filter of the present invention, the content ratio of the yellow color material to PG59 may be appropriately adjusted according to a desired chromaticity, and is not particularly limited. Above all, from the viewpoint of widening the color reproducibility and increasing the brightness while suppressing the occurrence of display defects, it is preferable to contain 10 to 900 parts by mass of the yellow color material with respect to 100 parts by mass of PG59. It is more preferable to contain ~ 400 parts by mass.

In the photosensitive coloring resin composition for a color filter of the present invention, the yellow color material is appropriately selected and used alone or in combination of two or more. Among them, PY138, PY139, PY185, PY150 and derivative pigments thereof. It is preferable to use one or more selected from the group consisting of two or more because it is easy to achieve a colored layer having high brightness and high contrast and excellent color reproducibility while suppressing the occurrence of display defects.
In the present invention, PY150 and its derivative pigments are preferably used when displaying a chromaticity region of y = 0.550 to 0.610 and x = 0.205 to 0.324, and the chromaticity region is preferable. The P / V ratio is more easily reduced, which is preferable.
Further, PY138 is preferably used when high brightness is achieved in the chromaticity region of y = 0.550 to 0.610 and x = 0.205 to 0.324, and among them, x = 0.246 to 0. It is preferably used when high brightness is achieved in the chromaticity region of 324.
Further, PY185 is suitable for widening the color reproduction range, and even when y = 0.610 to 0.626, it is preferable to display the chromaticity region of x = 0.205 to 0.324, and further. It is preferable to use it when displaying a chromaticity region as high as y = 0.659.

In the photosensitive coloring resin composition for a color filter of the present invention, in particular, when PY150 and at least one of its derivative pigments are used in combination with PY138, the desired chromaticity, brightness, and film thickness are adjusted. Although it may be adjusted as appropriate, the ratio of the total amount of at least one of PY150 and its derivative pigment to PY138 is preferably 5:95 to 95: 5. Above all, from the viewpoint of brightness and the P / V ratio, the ratio of the total amount of at least one of PY150 and its derivative pigment to PY138 is more preferably 10:90 to 90:10, and the brightness and P / From the point of view of V, it is more preferably 20:80 to 80:20.

Further, when the photosensitive coloring resin composition for a color filter of the present invention further contains a green color material other than PG59, the content ratio of the green color material containing PG59 to the entire color material is adjusted to a desired chromaticity. It may be adjusted as appropriate, and is not particularly limited. Above all, it is preferable to contain 10 to 90% by mass of a green color material containing PG59 with respect to the entire color material from the viewpoint of widening the color reproducibility and increasing the brightness while suppressing the occurrence of display defects. It is more preferable to contain 20 to 80% by mass.
Further, the content ratio of the yellow color material to the green color material including PG59 may be appropriately adjusted according to a desired chromaticity, and is not particularly limited. Among them, from the viewpoint of widening the color reproducibility and increasing the brightness while suppressing the occurrence of display defects, 100 parts by mass of the green color material containing PG59 and 10 to 900 parts by mass of the yellow color material are contained. It is preferable, and it is more preferable to contain 20 to 400 parts by mass.

Further, when the photosensitive coloring resin composition for a color filter of the present invention further contains at least one of PG58 and PG7, at least one of PG58 and PG7 is added to 5 to 5 for the entire green color material containing PG59. It is preferably contained in an amount of 50% by mass, more preferably 5 to 40% by mass from the viewpoint of display failure, brightness and the P / V ratio, and further from the viewpoint of brightness and the P / V ratio. It is more preferably contained in an amount of 5 to 30% by mass.

Further, in the photosensitive coloring resin composition for a color filter of the present invention, other coloring materials other than the green color material and the yellow color material are further contained in the coloring material as long as the effect of the present invention is not impaired. However, the total content of the green color material containing PG59 and the yellow color material is preferably 70 to 100% by mass, particularly 80 to 100% by mass, based on the total content of the color material. Is more preferable.

<Alkali-soluble resin>
The alkali-soluble resin in the present invention has an acidic group, acts as a binder resin, and is appropriately selected from a developing solution used for pattern formation, particularly preferably an alkali-soluble developing solution. Can be used.
The preferred alkali-soluble resin in the present invention is a resin having a carboxy group as an acidic group, and specific examples thereof include an acrylic copolymer having a carboxy group and an epoxy (meth) acrylate resin having a carboxy group. Among these, those having a carboxy group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain are particularly preferable. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. Further, these acrylic copolymers and epoxy acrylate resins may be used by mixing two or more kinds.

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

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

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

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

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

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

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

Further, the alkaline soluble resin preferably has a maleimide structure represented by the following general formula (4).

[In general formula (4), ^RM is a optionally substituted hydrocarbon ring. ]

When the alkaline soluble resin has a maleimide structure represented by the general formula (4), it has a nitrogen atom in the hydrocarbon ring, and therefore is a basic polymer having a structural unit represented by the general formula (I). The compatibility with the dispersant is very good, and the effect of suppressing the development residue is improved.

Specific examples of the hydrocarbon ring which may be substituted in ^RM of the general formula (4) include the same as 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, Examples include an aromatic hydrocarbon ring such as a naphthyl group, and a group in which a part of these groups is substituted with a substituent.

In the alkali-soluble resin used in the present invention, it is easier to adjust the amount of each structural unit by using an acrylic copolymer having a structural unit having a hydrocarbon ring in addition to the structural unit having a carboxy group. It is preferable because it is easy to increase the amount of the structural unit having the hydrocarbon ring to improve the function of the structural unit.
The acrylic copolymer having a structural unit having a carboxy group and the above-mentioned hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer". be able to.

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

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

The epoxy (meth) acrylate resin having a carboxy group is not particularly limited, and for example, an epoxy (meth) obtained by reacting a reaction product of an epoxy compound with an unsaturated group-containing monocarboxylic acid with an acid anhydride. ) An acrylate compound is suitable.
The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known ones and used.

Among the epoxy (meth) acrylate resins having a carboxy group, those containing a structure (cardo structure) in which two benzene rings are bonded to a fluorene skeleton represented by the following chemical formula (A) in the molecule have an effect of suppressing display defects. Is preferable, the curability of the colored layer is improved, and the residual film ratio of the colored layer is increased.

The exact mechanism of the epoxy (meth) acrylate resin having a carboxy group containing the cardo structure (hereinafter referred to as cardo resin) is unknown, but since the fluorene skeleton contains a π-conjugated system, it is highly sensitive to radicals. It is considered that there is, and by combining the oxime ester-based photopolymerization initiator described later with the cardo resin, the required performances such as sensitivity, developability, and development adhesion can be improved. Further, since the cardo resin has high solvent resolubility, it is preferable from the viewpoint that a colored resin composition without agglomerates can be designed even at a high color concentration.

Examples of the cardo resin include a polymerizable compound represented by the following general formula (B) described in JP-A-2007-119720 and an epoxy having a fluorene skeleton described in JP-A-2006-308698. A reaction product (polycondensate product) of a meta) acrylate and a polybasic acid is preferably used.

(Here, in the above general formula (B), X represents a group represented by the following general formula (D), and Y independently represents a residue of a polyvalent carboxylic acid or an acid anhydride thereof. R ⁱ represents a group represented by the following general formula (C), j is an integer of 0 to 4, k is an integer of from 0 to 3, n represents an integer of 1 or more.)

(Here, in the above general formula (C), R ⁱⁱ indicates a hydrogen atom or a methyl group, and R ⁱⁱⁱ independently indicates a hydrogen atom or a methyl group.)

(Here, in the above general formula (D), R ^iv is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a halogen atom, and R ^v is -O- or -OCH ₂ CH. ₂ Indicates O-.)

The cardo resin used in the present invention is, for example, an epoxy compound of a fluorene bisphenol compound to obtain an epoxy compound of a fluorene bisphenol compound, which is reacted with (meth) acrylic acid to form an epoxy (meth) acrylate, and this epoxy (meth) acrylate Can be obtained by reacting with a polyvalent carboxylic acid or an acid anhydride thereof.
The fluorene bisphenol compound, in the general formula (D), a ^{R v} is -O-, what this -O- becomes -OH may preferably be mentioned.
Fluolenbisphenol compounds include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis (4-hydroxy-3-methoxyphenyl). ) Fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3) -Chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-) Examples thereof include bisphenol compounds such as 3,5-dibromophenyl) fluorene, and mixtures thereof.

Examples of the polyvalent carboxylic acid and its acid anhydride used in the reaction of the epoxy (meth) acrylate resin having a fluorene skeleton include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid. , Methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, dicarboxylic acids such as glutaric acid or their acid anhydrides; biphenyltetracarboxylic acid, benzophenone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, Biphenylsulfonetetracarboxylic acid, 4- (1,2-dicarboxyethyl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, butanetetracarboxylic acid, tetracarboxylic acid such as pyromellitic acid or Examples thereof include tricarboxylic acids such as trimellitic acid or acid anhydrides thereof, or acid anhydrides thereof. These can be used alone or in combination of two or more.
The cardo resin used in the present invention is preferably an epoxy (meth) acrylate having a fluorene skeleton, which is an adduct of a fluorene epoxy (meth) acrylic acid derivative and a dicarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. Acid adducts can be mentioned.
Commercial names of commercially available cardo resins that can be used in the present invention include INR-16M (manufactured by Nagase Chemtech Co., Ltd.) and the like.
The epoxy (meth) acrylate resin having a carboxy group may be used alone or in combination of two or more.

The alkali-soluble resin used in the photosensitive coloring resin composition for a color filter may be used alone or in combination of two or more, and the content thereof is not particularly limited, but the color may be used. 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 the 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 become rough during development. Pattern chipping may occur. In the present invention, the solid content is all other than the above-mentioned solvent, and includes a liquid polyfunctional monomer and the like.

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

One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination. When the photosensitive colored resin composition for a color filter of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional monomer has three polymerizable double bonds (trifunctional). Those having the above are preferable, and poly (meth) acrylates of trivalent or higher polyhydric alcohols and dicarboxylic acid-modified products thereof are preferable, and specifically, trimethylpropantri (meth) acrylate and pentaerythritol tri. (Meta) acrylate, pentaerythritol tri (meth) acrylate succinic acid modified product, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate ) A succinic acid-modified product of acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable.
The content of the polyfunctional monomer used in the photosensitive coloring resin composition for a color filter is not particularly limited, but the polyfunctional monomer is preferably 5 with respect to the total solid content of the photosensitive coloring resin composition for a color filter. It is in the range of ~ 60% by mass, more preferably 10 to 40% by mass. If the content of the polyfunctional monomer is less than the above lower limit, photocuring does not proceed sufficiently, and the exposed portion may elute during development, and if the content of the polyfunctional monomer is more than the above upper limit, alkali developability May decrease.

<Light initiator>
The photoinitiator used in the photosensitive coloring resin composition for a color filter is not particularly limited, and one or a combination of two or more of various conventionally known photoinitiators can be used. Specific examples include those described in Japanese Patent Application Laid-Open No. 2013-029832.
As the photoinitiator, only one kind may be used, but two or more kinds of compounds may be used in combination. The photoinitiator preferably contains an oxime ester-based photoinitiator because it has a high effect of suppressing the occurrence of pattern chipping and an effect of suppressing the occurrence of water stains. When a dispersant having an acid value is used, water stains tend to occur particularly easily, but when combined with an oxime ester-based photoinitiator, water stains can be suppressed, and thus water stains are preferably used. In addition, water stain refers to this phenomenon in which traces of water stain are generated after alkaline development and rinsing with pure water. Since such water stains disappear after post-baking, there is no problem as a product, but there is a problem that it is detected as unevenness abnormality in the appearance inspection of the patterning surface after development, and it is not possible to distinguish between a normal product and an abnormal product. Occurs. Therefore, if the inspection sensitivity of the inspection device is lowered in the visual inspection, as a result, the yield of the final color filter product is lowered, which becomes a problem.

The oxime ester-based photoinitiator preferably has an aromatic ring, and is preferably a condensed ring containing an aromatic ring, from the viewpoint of reducing contamination of the photosensitive coloring resin composition for a color filter by decomposition products and contamination of the apparatus. It is more preferable to have a fused ring containing a benzene ring and a hetero ring.
Examples of the oxime ester-based photoinitiator include 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime), JP-A-2000-80068, JP-A-2001-233842, JP-A-2010-527339, JP-A-2010-527338, It can be appropriately selected from the oxime ester-based photoinitiators described in JP-A-2013-041153 and the like. Commercially available products include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, manufactured by BASF), ADEKA OPT-N-1919, ADEKA Arkuru's NCI-930, Adeca Arkuru's NCI-831 (above, ADEKA). , TR-PBG-304, TR-PBG-326, TR-PBG-345, TR-PBG-3057 (all manufactured by Joshu Powerful Electronics New Materials Co., Ltd.) and the like may be used.

As the oxime ester-based photoinitiator used in the present invention, it is possible to use an oxime ester-based photoinitiator that generates an alkyl radical, and further to use an oxime ester-based photoinitiator that generates a methyl radical. It has excellent curability even for a photosensitive resin composition in which the colorant concentration is increased in order to achieve a wide color reproduction range by using, and has development resistance, an effect of suppressing the occurrence of pattern chipping, and an effect of suppressing the occurrence of water stains. It is preferable because of its superiority. It is presumed that alkyl radicals are more likely to activate radical transfer than aryl radicals. Examples of the oxime ester-based photoinitiator that generates an alkyl radical include etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime). (Product name: Irgacure OXE-02, manufactured by BASF), Metanon, [8-[[(Acetyloxy) imino] [2- (2,2,3,3-tetrafluoropropoxy) phenyl] methyl] -11-( 2-Ethylhexyl) -11H-benzo [a] carbazole-5-yl]-, (2,4,6-trimethylphenyl) (trade name: Irgacure OXE-03, manufactured by BASF), etanone, 1- [9-ethyl -6- (1,3-dioxolane, 4- (2-methoxyphenoxy) -9H-carbazole-3-yl]-, 1- (o-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA) ), Metanon, (9-ethyl-6-nitro-9H-carbazole-3-yl) [4- (2-methoxy-1-methylethoxy-2-methylphenyl]-, o-acetyloxime (trade name: Adecaarc) Luz NCI-831, manufactured by ADEKA), 1-propanone, 3-cyclopentyl-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyl) Oxime) (trade name TR-PBG-304, manufactured by Joshu Powerful Electronics New Materials Co., Ltd.), 1-propanone, 3-cyclopentyl-1- [2- (2-pyrimidinylthio) -9H-carbazole-3-yl]-, 1- (o-Acetyloxyme) (trade name TR-PBG-314, manufactured by Joshu Strong Electronics New Materials Co., Ltd.), Etanone, 2-cyclohexyl-1- [2- (2-pyrimidinyloxy) -9H-carbazole-3-3 Il]-, 1- (o-acetyloxime) (trade name TR-PBG-326, manufactured by Joshu Strong Electronics New Materials Co., Ltd.), Etanone, 2-cyclohexyl-1- [2- (2-pyrimidinylthio) -9H- Carbazole-3-yl]-, 1- (o-acetyloxime) (trade name TR-PBG-331, manufactured by Joshu Strong Electronics New Materials Co., Ltd.), 1-octanone, 1- [4- [3- [1-[ (Acetyloxy) imino] ethyl] -6- [4-[(4,6-dimethyl-2-pyrimidinyl) thio] -2-methylbenzoyl] -9H-carbazole-9-yl] phenyl]-, 1-( o-Acetyloxime) (trade name: EXTA-9, manufactured by Union Chemical) and the like.

Further, it is preferable to use an oxime ester-based photoinitiator in combination with a photoinitiator having a tertiary amine structure from the viewpoint of improving sensitivity. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure which is an oxygen quencher in the molecule, the radicals generated from the initiator are not easily deactivated by oxygen, and the sensitivity can be improved. is there. Examples of commercially available photoinitiators having a tertiary amine structure include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (eg, Irgacure 907, manufactured by BASF). 2-Benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (eg, Irgacure 369, manufactured by BASF), 4,4'-bis (diethylamino) benzophenone (eg, Hycure ABP, etc.) (Made by Kawaguchi Yakuhin), etc.

The content of the photoinitiator used in the photosensitive coloring resin composition for a color filter is not particularly limited, but the photoinitiator is preferably 3 to 3 to the total solid content of the photosensitive coloring resin composition for a color filter. It is in the range of 40% by mass, more preferably 10 to 30% by mass. If this content is less than the above lower limit, photocuring may not proceed sufficiently and the exposed portion may elute during development, while if it is more than the above upper limit, the yellowing of the obtained colored layer becomes strong and the brightness becomes high. May decrease.

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

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

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

<Arbitrary additive component>
The photosensitive coloring resin composition for a color filter may contain various additives, if necessary.
Additives include, for example, antioxidants, polymerization inhibitors, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, UV absorbers, adhesion promoters and the like. Can be mentioned.

It is preferable that the photosensitive coloring resin composition for a color filter of the present invention further contains an antioxidant from the viewpoint of heat resistance. The antioxidant may be appropriately selected from conventionally known ones. Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like, and have heat resistance. From this point of view, it is preferable to use a hindered phenolic antioxidant.

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

<Mixing ratio of each component in the photosensitive colored resin composition for color filters>
The total content of the coloring material is preferably 3 to 65% by mass, more preferably 4 to 60% by mass, based on the total solid content of the photosensitive coloring resin composition for the color filter. When it is at least the above lower limit value, the colored layer when the photosensitive coloring resin composition for a color filter is applied to a predetermined film thickness (usually 1.0 to 5.0 μm) has a sufficient color density. Further, if it is not more than the above upper limit value, a colored layer having excellent storage stability, sufficient hardness, and adhesion to a substrate can be obtained. In particular, when a colored layer having a high color material concentration is formed, the content of the color material is 15 to 65% by mass, more preferably 25 to 65% by mass, based on the total solid content of the photosensitive coloring resin composition for a color filter. It is preferable to blend in a proportion of 60% by mass.
The content of the dispersant is not particularly limited as long as it can uniformly disperse the coloring material. For example, the content of the dispersant is relative to the total solid content of the photosensitive coloring resin composition for a color filter. It can be used in an amount of 1 to 40% by mass. Further, the photosensitive coloring resin composition for a color filter is preferably blended in a proportion of 2 to 30% by mass, particularly preferably 3 to 25% by mass, based on the total solid content. When it is at least the above lower limit value, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive coloring resin composition for a color filter is excellent. Further, when it is not more than the above upper limit value, the developability is good. In particular, when a colored layer having a high colorant concentration is formed, the content of the dispersant is 2 to 25% by mass, more preferably 3 to 25% by mass, based on the total solid content of the photosensitive coloring resin composition for a color filter. It is preferable to blend in a proportion of 20% by mass. In the case of a salt-type block copolymer, the mass of the dispersant is one or more compounds selected from the block copolymer before salt formation and the group consisting of the general formulas (1) to (3). Is the total mass of and.
Further, the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. It is usually preferably in the range of 55 to 95% by mass, and more particularly preferably in the range of 65 to 88% by mass with respect to the total amount of the photosensitive coloring resin composition for a color filter containing the solvent. preferable. When the content of the solvent is within the above range, the coatability can be made excellent.

In the photosensitive coloring resin composition for a color filter of the present invention, the P / V ratio ((mass of color material component in composition) / (mass of solid content other than color material component in composition) ratio) is removed. From the viewpoint of gas and heat shrinkage, it is preferably 0.1 or more, more preferably 0.2 or more, and on the other hand, it is excellent in display failure and manufacturing convenience, that is, solvent resolubility, development residue, and the like. From the viewpoint of excellent development adhesion, development resistance, water stain generation suppressing effect, etc., it is preferably 0.6 or less, and more preferably 0.5 or less.

<Cured film of photosensitive colored resin composition for color filter>
The photosensitive coloring resin composition for a color filter has chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source, x = 0.180 to 0.330, y = 0.500 to 0. It is preferable that a cured film in the range of .750 can be formed.
Above all, from the viewpoint of improving color reproducibility, the chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source are x = 0.188 to 0.324 and y = 0.550 to 0. It is preferable that a cured film in the range of .750 can be formed, and further, it is possible to form a cured film in the range of x = 0.200 to 0.324 and y = 0.570 to 0.750. It is more preferable that a cured film in the range of x = 0.205 to 0.324 and y = 0.580 to 0.750 can be formed.

Above all, 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 by a C light source with a single pixel, x = 0.200 to 0.300, y = 0. It is preferable to be able to display a color space in the range of .570 to 0.750 and a stimulus value Y of 37 ≦ Y, and further, x = 0.200 to 0.300, y = 0.570 to 0.750 and a stimulus value Y. More preferably, it can display a color space in the range of 40 ≦ Y.
As a good blending ratio or combination for displaying the color space in the range of 37 ≦ Y, the total content of the coloring materials is 20 to 45 mass with respect to the total solid content of the photosensitive coloring resin composition for the color filter. The content ratio (G: Y) of the green color material (G) containing PG59 and the yellow color material (Y) is preferably 80:20 to 20:80 as a combination in the color material. In the above, the content ratio of PG59 to the green color material (G) containing PG59 is preferably 30% by mass or more.

<Manufacturing method of photosensitive colored resin composition for color filter>
The method for producing the photosensitive coloring resin composition for a color filter of the present invention is not particularly limited. It can be obtained by adding other components accordingly and mixing using a known mixing means. Alternatively, using the dispersant, a color material dispersion of PG59, a color material dispersion of yellow color material, and, if necessary, a color material dispersion of another color material are prepared, respectively, and contain PG59. Color material dispersion liquid, a color material dispersion liquid containing a yellow color material, and if necessary, a color material dispersion liquid of another color material, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and the like. 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 including at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers is photosensitive for the color filter according to the present invention. It has a colored layer that is a cured product of the colored resin composition.

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

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

The colored layer can be formed, for example, by the following method.
First, the above-mentioned photosensitive coloring resin composition for a color filter of the present invention is transparent, which will be described later, by using a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, and a die coating method. It is applied onto a substrate to form a wet coating. Of these, the spin coating method and the die coating method can be preferably used.
Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to the wet coating film through a mask having a predetermined pattern, and an alkali-soluble resin, a polyfunctional monomer, or the like is photopolymerized and cured. Use as 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.
In addition, heat treatment may be performed in order to accelerate the polymerization reaction after exposure. The heating conditions are appropriately selected depending on the mixing ratio of each component in the photosensitive coloring resin composition for a color filter to be used, the thickness of the coating film, and the like.

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

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

The film thickness of the light-shielding portion 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 of a black pigment dispersed or dissolved in a binder resin. Will be done.

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

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

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

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

As a method for forming the liquid crystal layer, a method generally used as a method for producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and an opposing substrate, the liquid crystal is heated to form an isotropic liquid, and the liquid crystal is made into the liquid crystal cell by using the capillary effect. The liquid crystal layer can be formed by injecting in the state of the above and sealing with an adhesive. Then, the enclosed liquid crystal can be oriented by slowly cooling the liquid crystal cell to room temperature.
In the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like. Then, the liquid crystal layer can be formed by superimposing the color filter and the opposing substrate under reduced pressure and adhering them with the sealant. Then, the enclosed liquid crystal can be oriented by slowly cooling the liquid crystal cell to room temperature.

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

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

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
The acid value of the block copolymer before salt formation was determined by a method according to the method described in JIS K 0070.
The amine value of the block copolymer before salt formation was determined by a method according to the method described in JIS K 7237.
The weight average molecular weight (Mw) of the block copolymer before salt formation was determined as a standard polystyrene-equivalent value by GPC (gel permeation chromatography) according to the above-mentioned measurement method of the present invention.
The glass transition temperature (Tg) of the block copolymer before and after salt formation is measured by differential scanning calorimetry (DSC) (EXSTAR DSC 7020, manufactured by SII Nanotechnology) by a method according to the method described in JIS K7121. Was measured using.

(Synthesis Example 1: Preparation of Dispersant a)
A 500 ml 4-port separable flask was depressurized, dried, and then replaced with Ar (argon).
While Ar-flowing, 100 g of dehydrated THF, 2.0 g of methyltrimethylsilyldimethylketen acetal, 0.15 ml of a 1 M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), and 0.2 g of mesitylene were added. Using a dropping funnel, 36.7 g of methyl methacrylate (MMA) was added dropwise thereto over 45 minutes. Since heat was generated as the reaction proceeded, the temperature was kept below 40 ° C. by cooling with ice. After 1 hour, 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 LiBr10 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 is dissolved in 29.35 parts by mass of PGMEA, and phenylphosphonic acid (PPA, Tokyo Kasei), which is a compound represented by the general formula (3), is dissolved. (Manufactured) 3.17 parts by mass (0.20 mol of the compound represented by the general formula (3) is 0.20 mol with respect to 1 mol of DMMA unit of block copolymer 1), and the mixture is stirred at a reaction temperature of 30 ° C. for 20 hours. To obtain a salt-type block copolymer A-1 (dispersant a) solution. Specifically, the amine value after salt formation was calculated as follows.
1 g of a solution prepared by mixing 9 parts by mass of salt-type block copolymer A-1 (solid matter after reprecipitation) and 91 parts by mass of chloroform-D1 NMR in an NMR sample tube is placed, and the 13C-NMR spectrum is subjected to nuclear magnetic resonance. The measurement was performed using an apparatus (manufactured by JEOL Ltd., FT NMR, JNM-AL400) under the conditions of room temperature and 10000 integration times. Of the obtained spectral data, the integrated value of the carbon atom peak adjacent to the unsalted nitrogen atom and the carbon atom peak adjacent to the salt-formed nitrogen atom at the terminal nitrogen moiety (amino group). From the ratio, the ratio of the number of amino groups formed by salt to the total number of amino groups is calculated, and it is not different from the theoretical salt formation ratio (two acidic groups of total phenylphosphonic acid are the DMMA of block copolymer A-1). It was confirmed that it formed a salt with the nitrogen site at the end).
The amine value after salt formation was calculated as 57 mgKOH / g by subtracting the amine value (38 mgKOH / g) for 0.40 mol of the DMMA unit from the amine value of 95 mgKOH / g before salt formation. The Tg of the block copolymer before and after salt formation is also shown in Table 1.

(Synthesis Example 2: Production of Dispersant b)
Add 250 parts by mass of THF and 0.6 parts by mass of lithium chloride to a 500 mL round bottom 4-port separable flask equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and perform sufficient nitrogen substitution. It was. After cooling the reaction flask to −60 ° C., 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 18.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), methacrylic acid for B block monomer 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 over 60 minutes using an addition funnel. .. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to obtain a solid content of 30% by mass. 32.5 parts by mass of water was added, the temperature was raised to 100 ° C., and the mixture was reacted for 7 hours to deprotect the structural unit derived from EEMA 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 is a structural unit derived from an A block containing a structural unit represented by the general formula (I) and a carboxy group-containing monomer. A block copolymer A-2 (acid value 8 mgKOH / g, Tg 38 ° C.) containing B block having a solvent-like property was obtained. When the block copolymer A-2 thus obtained was confirmed by GPC (gel permeation chromatography), the weight average molecular weight Mw was 7730. The amine value was 95 mgKOH / g.
In a 100 mL round bottom flask, 29.35 parts by mass of block copolymer A-2 is dissolved in 29.35 parts by mass of PGMEA, and phenylphosphonic acid (manufactured by Tokyo Kasei), which is a compound represented by the general formula (3), is dissolved. 3.17 parts by mass (0.20 mol of the compound represented by the general formula (3) is 0.20 mol with respect to 1 mol of the DMMA unit of block copolymer 1) is added, and the mixture is stirred 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-port separable flask was depressurized, dried, and then replaced with Ar (argon).
While Ar-flowing, 100 g of dehydrated THF, 2.0 g of methyltrimethylsilyldimethylketen acetal, 0.15 ml of a 1 M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), and 0.2 g of mesitylene were added. Using a dropping funnel, 33 g of methyl methacrylate was added dropwise thereto over 45 minutes. Since heat was generated as the reaction proceeded, the temperature was kept below 40 ° C. by cooling with ice. After 1 hour, 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 LiBr10 mM) was 6,000, and the amine value was 120 mgKOH / g.
Block copolymer A-3 is dissolved in 24.15 parts by mass of PGMEA in a 100 mL round bottom flask, and phenylphosphonic acid (manufactured by Tokyo Kasei), which is a compound represented by the general formula (3), is dissolved. Add 3.5 parts by mass (0.20 mol of the compound represented by the general formula (3) is 0.20 mol with respect to 1 mol of the DMMA unit of block copolymer A-3), and stir at a reaction temperature of 30 ° C. for 20 hours. To obtain a salt-type block copolymer A-3 (dispersant c) solution having a solid content of 20% by mass. 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, the pre-salt block copolymer A-4 and the salt-type block copolymer (dispersant d) solution were prepared in the same manner as in Synthesis Example 2, except that the content was changed to the content shown in Table 1. 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 pre-salt block copolymer and salt-type block copolymer.

(Synthesis Example 5: Synthesis of Dispersant e)
The block copolymer A-5 (dispersant e) was synthesized in the same manner as the 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, block copolymer A-6 (dispersant f) and block copolymer A-7 (dispersion) were obtained in the same manner as in Synthesis Example 5, except that the monomers and contents shown in Table 1 were changed. 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, 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 used in the same manner as in Synthesis Example 2 except that the amount of the block copolymer A-8 before salt formation 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 pre-salt block copolymer and salt-type block copolymer.

The abbreviations in the table are as follows.
PME-200: Methoxypolyethylene glycol monomethacrylate (trade name: PME-200, manufactured by NOF CORPORATION, Blemmer PME-200, number of repeating ethyleneoxy groups = 4)
DMAPMA: Dimethylaminopropylmethacrylamide

(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 added dropwise to a polymerization tank containing 150 parts by mass of PGMEA at 100 ° C. over 3 hours. did. After completion of the dropping, the mixture was further heated at 100 ° C. for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution was 7,000.
Next, 20 parts by mass of GMA, 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and the mixture was heated at 110 ° C. for 10 hours to obtain main chain methacrylic acid. The reaction between the carboxylic acid group of the acid and the epoxy group of glycidyl methacrylate was carried out. During the reaction, air was bubbled into the reaction solution to prevent polymerization of glycidyl methacrylate. The reaction was followed by measuring the acid value of the solution. The obtained alkali-soluble resin A is a resin in which a side chain having an ethylenic double bond is introduced into a main chain formed by copolymerization of BzMA, MMA, and MAA using GMA, and has an acid value of 74 mgKOH / g. The weight average molecular weight was 12000. The alkali-soluble resin A solution had a solid content of 40% by mass.

(Synthesis Examples 10 to 15: Synthesis of alkali-soluble resin B to G solutions)
In Synthesis Example 9, instead of using 40 parts by mass of BzMA as the comonomer species at the time of polymerization, 40 parts by mass of the ethylenically unsaturated monomer shown in Tables 7 and 8 was used, but in the same manner as in Synthesis Example 9, the alkali was used. Soluble resin B to G solutions were obtained. The obtained alkali-soluble resins B to G had an acid value of 74 mgKOH / g and a weight average molecular weight of 12000. The alkali-soluble resin B to G solutions had a solid content of 40% by mass.

(Synthesis Example 16: Synthesis of Alkali-Soluble Resin H Solution)
Synthesis Example 9 The above Synthesis Example 9 except that 20 parts by mass of styrene and 20 parts by mass of N-phenylmaleimide (Tokyo Chemical Industry Co., Ltd.) were used instead of 40 parts by mass of BzMA as the comonomer species at the time of polymerization in Synthesis Example 9. In the same manner as above, an alkali-soluble resin H solution was obtained. The obtained alkali-soluble resin H had an acid value of 74 mgKOH / g and a weight average molecular weight of 12000. The alkali-soluble resin H solution had a solid content of 40% by mass.

(Synthesis Example 17 Preparation of Azo Derivative 1)
In 550 g of distilled water, 23.1 g of diazobarbituric acid and 19.2 g of barbituric acid were introduced. Then, it was adjusted to azobarbituric acid (0.3 mol) using an aqueous potassium hydroxide solution, and mixed with 750 g of distilled water. 5 g of 30% hydrochloric acid was added dropwise. Then, 38.7 g of melamine was introduced. Then, 0.39 mol of nickel chloride solution and 0.21 mol of zinc chloride solution were mixed and added, and the mixture was stirred at a temperature of 80 ° C. for 8 hours. The pigment was isolated by filtration, washed, dried at 120 ° C., and ground in a mortar to obtain Azo derivative 1 (Ni-azo-1, Ni: Zn = 65: 35 (molar ratio) azo pigment). ..

(Synthesis Example 18 Preparation of Azo Derivative 2)
Synthesis Example 17 except that 0.57 mol of nickel chloride solution and 0.03 mol of copper chloride solution were used instead of 0.39 mol of nickel chloride solution and 0.21 mol of zinc chloride solution. In the same manner as in Example 17, Azo derivative 2 (Ni-azo-2, Ni: Cu = 95: 5 (molar ratio) azo pigment) was obtained.

(Synthesis Example 19 Preparation of Azo Derivative 3)
Synthesis Example 17 except that 0.42 mol of nickel chloride solution and 0.18 mol of copper chloride solution were used instead of 0.39 mol of nickel chloride solution and 0.21 mol of zinc chloride solution. In the same manner as in Example 17, Azo derivative 3 (Ni-azo-3, Ni: Cu = 70: 30 (molar ratio) azo pigment) was obtained.

(Synthesis Example 20 Preparation of Azo Derivative 4)
Synthesis Example 17 except that 0.21 mol of nickel chloride solution and 0.39 mol of zinc chloride solution were used instead of 0.39 mol of nickel chloride solution and 0.21 mol of zinc chloride solution. In the same manner as in Example 17, Azo derivative 4 (Ni-azo-4, Ni: Zn = 35: 65 (molar ratio) azo pigment) was obtained.

( Reference example 1)
(1) Production of Color Material Dispersion Liquid G1
As a dispersant, 6.22 parts by mass of the dispersant a solution of Synthesis Example 1 was used, and C.I. I. Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC Corporation) with 5.33 parts by mass and C.I. I. Pigment Yellow 138 (PY138, trade name: Chromofine Yellow 6206EC, manufactured by Dainichi Seika Kogyo Co., Ltd.) by 7.67 parts by mass, the alkali-soluble resin A solution obtained in Synthesis Example 9 by 14.59 parts by mass, and PGMEA. 66.20 parts by mass, particle size 2.0 mm 100 parts by mass of zirconia beads are placed in a mayonnaise bottle and shaken with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as preliminary crushing, and then the particle size is 2.0 mm. The zirconia beads were taken out, 200 parts by mass of zirconia beads having a particle size of 0.1 mm were added, and the zirconia beads were similarly dispersed for 4 hours with a paint shaker as the main crushing to obtain a color material dispersion liquid G1.

(2) Production of Photosensitive Colored Resin Composition G1 for Color Filter 11.40 parts by mass of the coloring material dispersion liquid G1 obtained in (1) above, and the alkali-soluble resin A solution obtained in Synthesis Example 9 was obtained. 64 parts by mass, 0.60 parts by mass of polyfunctional monomer (trade name: Aronix M-403, manufactured by Toa Synthetic Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -On (photoinitiator: trade name Irgacure 907, manufactured by BASF Co., Ltd.) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator) Agent: Trade name Irgacure 369, manufactured by BASF) 0.04 parts by mass, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-) Acetyloxym) (photoinitiator: trade name: Adeca Arcurus NCI-831, manufactured by ADEKA) 0.02 parts by mass, fluorine-based surfactant (brand name Megafuck F559, manufactured by DIC Co., Ltd.) 0.07 7.14 parts by mass and 7.14 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition G1 for a color filter.
(3) Formation of Colored Layer The photosensitive colored resin composition G1 obtained in (2) above is placed on a glass substrate ("NA35" manufactured by NH Technoglass Co., Ltd.) having a thickness of 0.7 mm and a thickness of 100 mm x 100 mm. After applying with a spin coater, dry at 80 ° C. for 3 minutes using a hot plate, irradiate with ultraviolet rays of 60 mJ / cm ² using an ultra-high pressure mercury lamp, and post for 30 minutes in a clean oven at 230 ° C. By baking, the colored layer G1 was formed by adjusting the film thickness with a C light source so that the chromaticity was y = 0.570 and x = 0.260.

( Reference Examples 2 to 10, Comparative Examples 1 to 5)
(1) Production of Color Material Dispersion Liquids G2 to G10 and CG1 to CG5
In Reference Example 1 (1), as shown in Table 2, the type and amount of the dispersant used were changed so that the solid content was the same mass part instead of the dispersant a solution, and Comparative Examples 1 to 1 In No. 3, the coloring material dispersion liquids G2 to G10 and CG1 to CG5 were obtained in the same manner as in (1) of Reference Example 1 except that the coloring material was changed and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass. It was.
(2) Production of Photosensitive Colored Resin Compositions G2 to G10 and CG1 to CG5 for Color Filters
In Reference Examples 2 to 10 and Comparative Examples 1 to 5, the above-mentioned color material dispersions G2 to G10 and CG1 to CG5 are used instead of the color material dispersion G1 in (2) of Reference Example 1 to increase the film thickness. Photosensitivity for color filters in the same manner as in Reference Example 1 (2), except that the amount of the alkali-soluble resin was adjusted so that the P / V ratios were the values shown in Table 2 so as to be 35 μm. Colored resin compositions G2 to G10 and CG1 to CG5 were obtained.
(3) Formation of colored layer
In Reference Example 1 (3), in place of the photosensitive colored resin composition G1, each of the above photosensitive colored resin composition G2～G10, except for using CG1～CG5, similar to Reference Example 1 (3) The colored layers G2 to G10 and CG1 to CG5 were obtained.

( Reference Examples 11-14)
(1) Production of Photosensitive Colored Resin Compositions G11 to G14 for Color Filters
In Reference Examples 11 to 12, the colorant dispersion G2 is used instead of the colorant dispersion G1 in Reference Example 1 (2), and the photoinitiator is NCI831: oxime ester-based light as shown in Table 2. Instead of 0.02 parts by mass of the initiator (Adeca Arcurus NCI-831, manufactured by ADEAKA), TR-PBG: Oxym ester-based photoinitiator (TR-PBG-304, manufactured by Joshu Strong Electronics New Materials Co., Ltd.) 0.02 Photosensitive coloring for color filters in the same manner as in Reference Example 1 (2), except that 0.02 parts by mass or OXE03: oxime ester-based photoinitiator (Irgacure OXE-03, manufactured by BASF) was used. Resin compositions G11-12 were obtained.
Further, in Reference Example 13, using the color material dispersion G2 in place of the colorant dispersion liquid G1 in Reference Example 1 (2), further ethanone in Reference Example 1 (2), 1- [9-ethyl -6- (2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) 0.02 parts by mass, 2-methyl-1- (4-methylthiophenyl)- 2-Morphorinopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Co., Ltd.) 0.10 parts by mass, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) − Butanon-1 (photoinitiator: trade name: Irgacure 369, manufactured by BASF) Photosensitive coloring resin composition G13 for color filter in the same manner as in (2) of Reference Example 1 except that it was changed to 0.05 parts by mass. Got
Further, in Reference Example 14, the color material dispersion G2 was used instead of the color material dispersion G1 in (2) of Reference Example 1, and the alkali-soluble resin A solution obtained in Synthesis Example 9 was used as the alkali-soluble resin. Instead, change to an alkali-soluble resin I solution (epoxy (meth) acrylate resin having a carboxy group containing a cardo structure, product number INR-16M manufactured by Nagase Chemtech Co., Ltd.) so that the solid content is the same by mass. A photosensitive colored resin composition G14 for a color filter was obtained in the same manner as in (2) of Reference Example 1 except that the amount used was adjusted.
(3) Formation of colored layer
In Reference Example 1 (3), in place of the photosensitive colored resin composition G1, except that each using the above photosensitive colored resin composition G11 to G14, in the same manner as in Reference Example 1 (3), colored Layers G11 to G14 were obtained.

Here, each abbreviation in the table is as follows.
G36: C.I. I. Pigment Green 36 (Product name: FASTOGEN GREEN 2YK-50, manufactured by DIC Corporation)
G58: C.I. I. Pigment Green 58 (Product name: FASTOGEN GREEN A110, manufactured by DIC Corporation)
G7: C.I. I. Pigment Green 7 (Product name: Chromo Fine Green 6428EC, manufactured by Dainichiseika Kogyo)
Y138: C.I. I. Pigment Yellow 138 (Product name: Chromo Fine Yellow 6206EC, manufactured by Dainichiseika Kogyo Co., Ltd.)
byk-2000: Disperbyk-2000 (manufactured by Big Chemie, a polymer having a structural unit represented by the general formula (I), and a salt-type block co-weight in which the compound represented by the general formula (2) forms a salt. Combined, solid content 40% by mass)
N21116: Disperbyk-LPN21116 (manufactured by Big Chemie, a polymer having a structural unit represented by the general formula (I), and a salt-type block copolymer in which a compound represented by the general formula (2) forms a salt, Solid content 40% by mass)
byk-161: Product name Disperbyk-161 (manufactured by Big Chemie, urethane-based dispersant, solid content 30% by mass)
PB822: Product name Ajispar PB822 (manufactured by Ajinomoto Fine-Techno Co., Ltd., polyester dispersant, solid content 30% by mass)
IRG369: Photoinitiator with tertiary amine structure (Irgacure 369, manufactured by BASF)
IRG907: Photoinitiator with tertiary amine structure (Irgacure 907, manufactured by BASF)
NCI831: Oxime ester-based photoinitiator (Adeca Arcurus NCI-831, manufactured by ADEAKA)
TR-PBG: Oxime ester-based photoinitiator (TR-PBG-304, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.)
OXE03: Oxime ester-based photoinitiator (Irgacure OXE-03, manufactured by BASF)

( Reference Examples 15 to 19, Example 20, Comparative Examples 6 to 8)
(1) Production of Color Material Dispersion Liquids G15 to G20 and CG6 to CG8
In (1) of Reference Example 1, as shown in Table 3, the type and amount of colorant used were changed, and the type and amount of dispersant were changed so that the solid content was the same mass part. The color material dispersion liquids G15 to G20 and CG6 to CG8 were obtained in the same manner as in Reference Example 1 (1) except that the amount of PGMEA was adjusted so that the total amount was 100 parts by mass.
(2) Production of Photosensitive Colored Resin Compositions G15 to G20 and CG6 to CG8 for Color Filters
The P / V ratios are shown in the table in order to make the film thickness 2.8 μm by using the color material dispersions G15 to G20 and CG6 to CG8 instead of the color material dispersion G1 in (2) of Reference Example 1. Photosensitive colored resin compositions for color filters G15 to G20 and CG6 to CG8 were obtained in the same manner as in (2) of Reference Example 1 except that the amount of the alkali-soluble resin was adjusted so as to have the value shown in 3. It was.
(3) Formation of colored layer
In Reference Example 1 (3), in place of the photosensitive colored resin composition G1, each of the above photosensitive colored resin composition G15～G20, except for using CG6～CG8, similar to Reference Example 1 (3) The colored layers G15 to G20 and CG6 to CG8 were obtained. In Comparative Example 8 in which PG58 was used as the coloring material, the chromaticity of y = 0.610 and x = 0.210 could not be realized with the C light source.

Here, each abbreviation in the table is as follows.
Y150: C.I. I. Pigment Yellow 150 (Product name: LEVASCREEN YELLOW G04, manufactured by LANXESS Co., Ltd.)
Ni-azo-1: Azo derivative 1 of Synthesis Example 17

( Reference Examples 21 to 25, Comparative Example 9)
(1) Production of Color Material Dispersion Liquids G21 to G25 and CG9
In (1) of Reference Example 1, as shown in Table 4, the type and amount of colorant used were changed, and the type and amount of dispersant were changed so that the solid content was the same mass part. The color material dispersion liquids G21 to G25 and CG9 were obtained in the same manner as in (1) of Reference Example 1 except that the amount of PGMEA was adjusted so that the total amount was 100 parts by mass.
(2) Production of Photosensitive Colored Resin Compositions G21 to G25 and CG9 for Color Filters
In order to make the film thickness 2.8 μm by using the color material dispersions G21 to G25 and CG9 instead of the color material dispersion G1 in (2) of Reference Example 1, the P / V ratios are shown in Table 4, respectively. Photosensitive colored resin compositions for color filters G21 to G25 and CG9 were obtained in the same manner as in (2) of Reference Example 1 except that the amount of the alkali-soluble resin was adjusted so as to have the indicated value.
(3) Formation of colored layer
In the same manner as in Reference Example 1 (3), except that the above-mentioned photosensitive colored resin compositions G21 to G25 and CG9 were used instead of the photosensitive colored resin composition G1 in (3) of Reference Example 1. , Colored layers G21 to G25 and CG9 were obtained. In Comparative Example 9 in which PG58 was used as the coloring material, the chromaticity of y = 0.626 and x = 0.205 could not be realized with the C light source.

Here, each abbreviation in the table is as follows.
Y185: C.I. I. Pigment Yellow 185 (Product name: Pariodol (registered trademark) Yellow D1155, manufactured by BASF Limited)

( Reference Examples 26 to 28, Comparative Example 10)
(1) Production of Color Material Dispersion Liquids G26 to G28 and CG10
In (1) of Reference Example 1, as shown in Table 5, the type and amount of colorant used were changed, and the type and amount of dispersant were changed so that the solid content was the same mass part. The color material dispersion liquids G26 to G28 and CG10 were obtained in the same manner as in Reference Example 1 (1) except that the amount of PGMEA was adjusted so that the total amount was 100 parts by mass.
(2) Production of Photosensitive Colored Resin Compositions G26 to G28 and CG10 for Color Filters
In order to make the film thickness 3.3 μm by using the color material dispersions G26 to G28 and CG10 instead of the color material dispersion G1 in (2) of Reference Example 1, the P / V ratios are shown in Table 5, respectively. Photosensitive colored resin compositions G26 to G28 and CG10 for color filters were obtained in the same manner as in (2) of Reference Example 1 except that the amount of the alkali-soluble resin was adjusted so as to have the indicated value.
(3) Formation of colored layer
In the same manner as in Reference Example 1 (3), except that the above-mentioned photosensitive colored resin compositions G26 to G28 and CG10 were used instead of the photosensitive colored resin composition G1 in (3) of Reference Example 1. , Colored layers G26 to G28 and CG10 were obtained.

( Reference Examples 29 to 31, Comparative Example 11)
(1) Production of Color Material Dispersion Liquids G29 to G31 and CG11
In (1) of Reference Example 1, as shown in Table 6, the type and amount of coloring material used were changed, and the type and amount of dispersant were changed so that the solid content was the same mass part. The color material dispersion liquids G29 to G31 and CG11 were obtained in the same manner as in Reference Example 1 (1) except that the amount of PGMEA was adjusted so that the total amount was 100 parts by mass.
(2) Production of Photosensitive Colored Resin Compositions G29 to G31 and CG11 for Color Filters
In order to make the film thickness 3.3 μm by using the color material dispersions G29 to G31 and CG11 instead of the color material dispersion G1 in (2) of Reference Example 1, the P / V ratios are shown in Table 6, respectively. Photosensitive colored resin compositions G29 to G31 and CG11 for color filters were obtained in the same manner as in (2) of Reference Example 1 except that the amount of the alkali-soluble resin was adjusted so as to have the indicated value.
(3) Formation of colored layer
In the same manner as in Reference Example 1 (3), except that the above-mentioned photosensitive colored resin compositions G29 to G31 and CG11 were used instead of the photosensitive colored resin composition G1 in (3) of Reference Example 1. , Colored layers G29 to G31 and CG11 were obtained.

( Reference Example 32)
(1) Production of color material dispersion
As a dispersant, 6.22 parts by mass of the dispersant b solution of Synthesis Example 2 was used, and C.I. I. Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC Co., Ltd.) is 13 parts by mass, the alkali-soluble resin A solution obtained in Synthesis Example 9 is 14.59 parts by mass, PGMEA is 66.20 parts by mass, and grains. Put 100 parts by mass of zirconia beads with a diameter of 2.0 mm into a mayonnaise bottle, shake with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as preliminary crushing, and then take out the zirconia beads with a particle size of 2.0 mm and take out the particle size. 200 parts by mass of 0.1 mm zirconia beads were added and dispersed in a paint shaker for 4 hours as the main crushing to obtain a green color material dispersion liquid g.
As a dispersant, 6.22 parts by mass of the dispersant b solution of Synthesis Example 2 was used, and C.I. I. Pigment Yellow 138 (PY138, trade name: Chromofine Yellow 6206EC, manufactured by Dainichi Seika Kogyo Co., Ltd.) was 13 parts by mass, the alkali-soluble resin A solution obtained in Synthesis Example 9 was 14.59 parts by mass, and PGMEA was 66. 20 parts by mass and 2.0 mm particle size zirconia beads 100 parts by mass are placed in a mayonnaise bottle and shaken with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as preliminary crushing, and then 2.0 mm particle size zirconia beads. Was taken out, 200 parts by mass of zirconia beads having a particle size of 0.1 mm were added, and the mixture was similarly dispersed for 4 hours with a paint shaker as the main crushing to obtain a yellow color material dispersion liquid y.

(2) Production of Photosensitive Colored Resin Composition G32 for Color Filter The green color material dispersion g obtained in (1) above is 4.67 parts by mass, and the yellow color material dispersion y is 6.73 parts by mass. 0.64 parts by mass of the alkali-soluble resin A solution obtained in Example 9, 0.60 parts by mass of a polyfunctional monomer (trade name: Aronix M-403, manufactured by Toa Synthetic Co., Ltd.), 2-methyl-1- 0.09 parts by mass of (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Co., Ltd.), 2-benzyl-2-dimethylamino-1- 0.04 parts by mass of (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name Irgacure 369, manufactured by BASF), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazole-3-yl]-, 1- (O-acetyloxime) (photoinitiator: trade name Adeca Arclus NCI-831, manufactured by ADEKA) 0.02 parts by mass, fluorine-based surfactant (trade name) 0.07 parts by mass of Megafuck F559 and DIC Co., Ltd. and 7.14 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition G32 for a color filter.
(3) Formation of colored layer
In the same manner as in Reference Example 1 (3), the colored layer G32 was formed in the same manner as in Reference Example 1 (3), except that the photosensitive colored resin composition G32 was used instead of the photosensitive colored resin composition G1. Obtained.
The obtained photosensitive coloring resin composition G32 for a color filter has the same composition as the photosensitive coloring resin composition G2 for a color filter of Reference Example 2, and the photosensitive coloring resin composition G32 for a color filter and the coloring layer The evaluation results of G32 were the same as the evaluation results of the photosensitive coloring resin composition G2 for color filters and the coloring layer G2.

(Examples 33 , 35 to 37 , Reference Example 34 )
(1) Production of Color Material Dispersion Liquids G33 to G37
In (1) of Reference Example 1, as shown in Table 7, the type and amount of coloring material used were changed, and the type and amount of dispersant were changed so that the solid content was the same mass part. The color material dispersion liquids G33 to G37 were obtained in the same manner as in Reference Example 1 (1) except that the amount of PGMEA was adjusted so that the total amount was 100 parts by mass.
(2) Production of Photosensitive Colored Resin Compositions G33 to G37 for Color Filters
The above color material dispersions G33 to G37 are used instead of the color material dispersion G1 in (2) of Reference Example 1, and further, mercapto compound A (pentaerythritol tetrakis (3-mercaptopropionate)) is 0.03. In Reference Example 34 and Examples 35 to 37, an alkali-soluble resin B solution was used instead of the alkali-soluble resin A solution, and the solvent was further changed to that shown in Table 7 to increase the film thickness. For color filters in the same manner as in Reference Example 1 (2), except that the amount of the alkali-soluble resin was adjusted so that the P / V ratios were the values shown in Table 7 so as to be 2.35 μm. Photosensitive colored resin compositions G33 to G37 were obtained.
(3) Formation of colored layer
In Reference Example 1 (3), in place of the photosensitive colored resin composition G1, except that each using the above photosensitive colored resin composition G33～G37, in the same manner as in Reference Example 1 (3), colored Layers G33-G37 were obtained.

Here, each abbreviation in the table is as follows.
Ni-azo-1: Azo derivative 1 of Synthesis Example 17
Ni-azo-2: Azo derivative 2 of Synthesis Example 18
Ni-azo-3: Azo derivative 3 of Synthesis Example 19
Ni-azo-4: Azo derivative 4 of Synthesis Example 20
CHMA: Cyclohexyl methacrylate Solvent A: Propylene glycol monomethyl ether acetate (PGMEA)
Solvent B: 3-Methoxy-3-methyl-1-butylacetate mercapto compound A: pentaerythritol tetrakis (3-mercaptopropionate)

(Examples 38 to 54, Reference Example 55)
(1) Production of Photosensitive Colored Resin Compositions G38 to G55 for Color Filters In Examples 38 to 49 and Reference Example 55, in Example 33, instead of the alkali-soluble resin A solution, the alkali resin B shown in Table 8 was used. In Examples 38 to 49, the P / V ratios are shown in Table 8 in order to further change the solvent to those shown in Table 8 to obtain a film thickness of 2.35 μm. Photosensitive colored resin compositions for color filters G38 to G49 and G55 were obtained in the same manner as in (2) of Example 33 except that the amount of the alkali-soluble resin was adjusted so as to be a value.
Further, in Example 50, in Example 33, 0.09 parts by mass of a photoinitiator having an IRG907: tertiary amine structure (Irgacure 907, manufactured by BASF) as a photoinitiator and light having an IRG369: tertiary amine structure were used. Instead of using 0.04 parts by mass of the initiator (Irgacure 369, manufactured by BASF) and 0.02 parts by mass of the NCI831: oxime ester-based photoinitiator (Adeca Arcurus NCI-831, manufactured by ADEAKA), TR-PBG: Oxym The P / V ratios are shown in Table 8 in order to achieve a film thickness of 2.35 μm using 0.8 parts by mass of an ester-based photoinitiator (TR-PBG-304, manufactured by Joshu Strong Electronics New Materials Co., Ltd.). A photosensitive coloring resin composition G50 for a color filter was obtained in the same manner as in (2) of Example 33 except that the amount of the alkali-soluble resin was adjusted so as to be a value.
In Examples 51 to 52, the photoinitiator in Example 43 was used in place of 0.02 parts by weight of the NCI831: oxime ester-based photoinitiator (Adeca Arcurus NCI-831, manufactured by ADEAKA), as shown in Table 8. , NCI930: Oxyme ester-based photoinitiator (Adeca Arcurus NCI-930, manufactured by ADEAKA) 0.02 parts by mass, or OXE04: Oxyme ester-based photoinitiator (Irgacure OXE-04, manufactured by BASF) 0.02 parts by mass. The same as in (2) of Example 43, except that the amount of the alkali-soluble resin was adjusted so that the P / V ratios were the values shown in Table 8 in order to make the film thickness 2.35 μm. The photosensitive colored resin compositions G51 and G52 for color filters were obtained.
Further, in Example 53, the photoinitiator in Example 43 was 0.18 parts by mass of an IRG907: tertiary amine structure photoinitiator (Irgacure 907, manufactured by BASF) without using NCI831, and 2-benzyl-. 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name Irgacure 369, manufactured by BASF) To change to 0.09 parts by mass to make the film thickness 2.35 μm Photosensitive colored resin composition for color filter G53 in the same manner as in (2) of Example 43, except that the amount of the alkali-soluble resin was adjusted so that the P / V ratios were the values shown in Table 8. Got
Further, in Example 54, in order to make the film thickness 2.35 μm by using the same amount of mercapto compound B (pentaerythritol tetrakis (3-mercaptobutyrate)) instead of mercapto compound A in Example 43, the above P. A photosensitive coloring resin composition G54 for a color filter was obtained in the same manner as in (2) of Example 43, except that the amount of the alkali-soluble resin was adjusted so that the / V ratios were the values shown in Table 8. It was.
(2) Formation of Colored Layer In Example 1 (3), (3) of Example 1 except that the above-mentioned photosensitive colored resin compositions G38 to G55 were used instead of the photosensitive colored resin composition G1 respectively. ), The colored layers G38 to G55 were obtained.

Here, each abbreviation in the table is as follows.
CHMA: Cyclohexyl methacrylate, St: Styrene, DCPMA: Dicyclopentanyl methacrylate, ADMA: 1-adamantyl methacrylate, Maleimide: N-phenylmaleimide (Tokyo Kasei Kogyo Co., Ltd.), HEMA: 2-Hydroxyethyl methacrylate Solvent A: Propylene glycol Monomethyl Ether Acetate (PGMEA)
Solvent B: 3-Methoxy-3-methyl-1-butyl acetate Solvent C: Propylene glycol monomethyl ether (PGME)
Solvent D: Diethylene glycol ethyl methyl ether (EMDG)
Solvent E: 3-Methoxybutylacetate mercapto compound A: Pentaerythritol tetrakis (3-mercaptopropionate)
Mercapto Compound B: Pentaerythritol Tetrakis (3-mercaptobutyrate)

[Evaluation methods]
<Evaluation of dispersibility of color material dispersion>
The viscosities of the color material dispersions obtained in Examples and Comparative Examples were measured immediately after preparation and after storage at 25 ° C. for 30 days, and the viscosity change rate was calculated from the viscosities before and after storage to evaluate the viscosity stability. did. A vibration viscometer was used to measure the viscosity, and the viscosity at 25.0 ± 0.5 ° C. was measured. The results are shown in Tables 2-8.
(Dispersion stability evaluation standard)
A: Viscosity change rate before and after storage is less than 10% B: Viscosity change rate before and after storage is 10% or more and less than 15% C: Viscosity change rate before and after storage is 15% or more and less than 25% D: Before and after storage The rate of change in viscosity is 25% or more. However, it is a value when the coloring material is 13% by mass with respect to the total mass of the coloring material dispersion liquid including the solvent.
Even if the evaluation result is C, the color material dispersion can be used practically, but if the evaluation result is B, the color material dispersion is better, and if the evaluation result is A, the color material dispersion has dispersion stability. Are better.

<Optical performance evaluation, contrast evaluation>
The contrast, chromaticity (x, y), and brightness (Y) of the colored layers obtained in Examples and Comparative Examples were measured using the Tsubosaka Electric contrast measuring device CT-1B and the Olympus microspectroscopy measuring device OSP-SP200. It was measured.
In Comparative Example 8 in which PG58 was used as the coloring material, the chromaticity of y = 0.610 and x = 0.210 could not be realized with the C light source. In Comparative Example 9 in which PG58 was used as the coloring material, the chromaticity of y = 0.626 and x = 0.205 could not be realized with the C light source.
(Contrast evaluation standard)
-Values when y = 0.570 and x = 0.260 with C light source A: 12000 exceeded B: 10000-12000
C: Less than 10,000 (contrast evaluation standard)
-Values when y = 0.610 and x = 0.280 with C light source AA: Exceeds 13000 A: Excees 12000 Exceeds less than 13000 B: Exceeds 10000 to less than 12000 C: Less than 10000

<Display defect evaluation>
The display defect evaluation of the colored layer obtained in Examples and Comparative Examples was performed using a dielectric impedance measurement system 126096W (manufactured by Toyo Technica). The measurement was carried out while irradiating an LED light (Spot Ace SPA-10CW: manufactured by Hayashi Clock Co., Ltd.).
(Display defect evaluation criteria)
A: Dissipation factor (tan δ) at 100 Hz is less than 0.023 B: Dissipation factor (tan δ) at 100 Hz is 0.023 to 0.048
C: Dissipation factor (tan δ) at 100 Hz exceeds 0.048 If the above evaluation standard is A or B, it can be practically used, but if the evaluation result is A, the effect of suppressing display defects 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 coloring resin composition for a color filter obtained in Examples and Comparative Examples, and applied to a 1 cm long portion of the glass substrate. The pulled glass substrate was placed in a constant temperature and humidity chamber so that the glass surface was horizontal, and dried at a temperature of 23 ° C. and a humidity of 80% RH for 10 minutes. Next, the glass substrate to which the dried coating film was attached was immersed in PGMEA for 15 seconds. At this time, the redissolved state of the dry coating film was visually discriminated and evaluated. The results are also shown in Tables 2-8.
(Solvent resolubility evaluation standard)
AA: The dry coating film was completely dissolved in 8 seconds or less A: The dry coating film was completely dissolved B: Fragments of the dry coating film were formed in the solvent and the solution was colored C: The dry coating film was completely dissolved in the solvent If the above evaluation criteria are AA, A or B, and the evaluation criteria are AA, A or B, then practical use is possible, but if the evaluation result is A, the effect is more excellent.

<Evaluation of development residue>
The photosensitive coloring resin compositions for color filters obtained in Examples and Comparative Examples are spun on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a thickness of 100 mm × 100 mm, respectively. After coating with a coater, a colored layer having a thickness of 2.5 μm was formed by drying at 60 ° C. for 3 minutes using a hot plate. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer. After visually observing the unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer, wipe it off sufficiently with a lens cleaner (manufactured by Toray Industries, Inc., trade name: Toraysee MK Clean Cloth) soaked in ethanol. The degree of coloring of the lens cleaner was visually observed. The results are shown in Tables 2-8.
(Development residue evaluation criteria)
AA: 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. No B: No development residue was visually confirmed and the lens cleaner was slightly colored. C: The development residue was slightly confirmed visually and the lens cleaner was slightly colored. D: The development residue was visually confirmed. Confirmed and confirmed coloring of lens cleaner E: Development residue was confirmed visually and coloring of lens cleaner was confirmed If the above evaluation criteria are AA, A, B or C, it can be used practically. If the evaluation result is B, further A, and further AA, the effect is more excellent.

<Development adhesion evaluation>
The photosensitive coloring resin compositions for color filters obtained in Examples and Comparative Examples are spun on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a thickness of 100 mm × 100 mm, respectively. After coating with a coater, a colored layer having a thickness of 2.5 μm was formed by drying at 60 ° C. for 3 minutes using a hot plate. The colored layer was irradiated with ultraviolet rays of 60 mJ / cm ² using an ultra-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 mass% potassium hydroxide aqueous solution as an alkaline developer. The developed substrate was observed with an optical microscope, and the presence or absence of a colored layer with respect to the mask aperture line width was observed. The results are also shown in Tables 2-8.
(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 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 practically used, but if the evaluation result is B and further A, the photosensitive coloring resin composition for a color filter is suitable for higher definition.

<Development resistance evaluation>
The photosensitive coloring resin compositions for color filters obtained in Examples and Comparative Examples were applied onto a glass substrate (manufactured by NH Techno Glass Co., Ltd., “NA35”) having a thickness of 0.7 mm using a spin coater. did. After heat-drying on a hot plate at 80 ° C. for 3 minutes, ultraviolet rays of 40 mJ / cm ² were irradiated using an ultra-high pressure mercury lamp. The film thickness at this point is measured and set to T1 (μm). Then, shower development was carried out using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer. The film thickness after development is measured and set to T2 (μm). T2 / T1 × 100 (%) was calculated. The results are shown in Tables 2-8.
(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 practically used, but if the above evaluation standard is A, the effect is more excellent.

<Water stain evaluation>
The photosensitive coloring resin composition for a color filter obtained in each Example and each Comparative Example is thickened after post-baking on a glass substrate (manufactured by NH Technoglass Co., Ltd., "NA35") using a spin coater. After coating with a film thickness that forms a colored layer of 1.6 μm, it is dried at 60 ° C. for 3 minutes using a hot plate, and 60 mJ / cm ² ultraviolet rays are applied to the entire surface using an ultra-high pressure mercury lamp without using a photomask. By irradiating, a colored layer was formed on the glass substrate. Next, spin-development using 0.05 wt% potassium (KOH) as a developing solution, indirect solution in the developing solution for 60 seconds, and then washing with pure water for development treatment, and rotating the washed substrate for 10 seconds to add water. Immediately after centrifugation, the contact angle of pure water was measured as shown below to evaluate water stains.
To measure the contact angle of pure water, 1.0 μL of pure water is dropped on the surface of the colored layer immediately after the water is centrifugally removed, and the static contact angle 10 seconds after the drip is measured according to the θ / 2 method. I measured it. The measuring device was a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd..
(Evaluation criteria)
AA: Contact angle 85 degrees or more A: Contact angle 80 degrees or more and less than 85 degrees B: Contact angle 65 degrees or more and less than 80 degrees C: Contact angle 50 degrees or more and less than 65 degrees D: Contact angle less than 50 degrees Water stain evaluation standard is AA , A or B can be used practically, but if the evaluation result is A and further AA, the effect is more excellent.

<Evaluation of uneven drying>
After applying the photosensitive coloring resin composition for a color filter obtained in each Example and each Comparative Example on a glass substrate (manufactured by 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 substrate was observed using an interference fringe inspection lamp (Na lamp), and the presence or absence of drying unevenness generated in the coating film was visually evaluated.
(Evaluation criteria)
A: No uneven drying is observed.
B: Slight dry unevenness is observed.
C: Many uneven drying is observed.

[Summary of results]
From the results in Tables 2 to 8, the color material dispersion liquid of the example in which the dispersant which is a polymer having the structural unit represented by the general formula (I) is combined with PG59 and the yellow color material has viscosity stability. It was revealed to be good. On the other hand, it was clarified that the color material dispersions of Comparative Examples 4 to 5 in which a urethane-based dispersant and a polyester-based dispersant were combined with PG59 had poor viscosity stability. Further, the color material dispersions of Comparative Examples 1, 2 and 3 in which PG58, PG7 and PG36 are combined with a dispersant which is a polymer having a structural unit represented by the general formula (I) are combined with the same dispersant. It was clarified that the viscosity stability was inferior to that of Example 1. Further, the colorant dispersions of Comparative Examples 2 and 3 in which PG7 and PG36 were combined with a dispersant which is a polymer having a structural unit represented by the general formula (I) had poor dispersibility.

From Table 2, the photosensitive coloring resin compositions for color filters of Reference Examples 1 to 14 in which PG59 is combined with a yellow colorant PY138 and a dispersant which is a polymer having a structural unit represented by the general formula (I). It was clarified that when y = 0.570, the region of x = 0.260 can be displayed, the occurrence of display defects is suppressed, and a high-luminance colored layer can be formed. Further, the photosensitive coloring resin compositions for color filters of Reference Examples 1 to 14 in which PG59 is combined with a yellow color material PY138 and a dispersant which is a polymer having a structural unit represented by the general formula (I) are It was clarified that the color material dispersion stability was good, the contrast was excellent, the solvent resolubility was excellent, and the generation of development residue was suppressed.
Among them, as a dispersant, a block copolymer containing an A block containing a structural unit represented by the general formula (I) and a B block containing a structural unit derived from a carboxy group-containing monomer and having prosolve properties, or a block copolymer 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 acid value of the dispersant is 1 mgKOH / g or more and 18 mgKOH / g or less. In Reference Examples 2, 4, 8, 11 to 14 using the dispersant having a glass transition temperature of the dispersant of 30 ° C. or higher, the generation of development residue is particularly suppressed and the development adhesion is excellent. there were. Further, Reference Example 14 in which an epoxy (meth) acrylate resin having a carboxy group containing a cardo structure was used as the alkali-soluble resin in the photosensitive resin composition was compared with Reference Example 2 in terms of development adhesion, development resistance and water stain. It was excellent in suppressing the occurrence.
Among the examples, from the comparison of Reference Examples 2,11,12, and 13, as photoinitiators, the reference example using the oxime ester photoinitiators are developing resistance and water stains generation suppression effect is higher It was revealed.

Further, from Tables 3 and 4, when PG59 is combined with a yellow color material and a dispersant which is a polymer having a structural unit represented by the general formula (I), the color reproduction range is widened, and y = 0. Even in the case of 570 to 0.626, the chromaticity region of x = 0.205 to 0.324 can be displayed, and the chromaticity region of y = 0.659 can be displayed, but display defects occur. It was clarified that it was suppressed and a high-brightness colored layer could be formed.
Further, in Reference Example 27 of Table 5, when PG59 and the yellow color material are further combined with PG58, Reference Example 26 using PG59 alone as the green color material and Comparative Example 10 in which PG58 and Y138 are combined are used. It was also clarified that the brightness is further improved while reducing the P / V ratio. In Reference Example 28, it was also clarified that the P / V ratio can be further reduced by combining PG59 and PG58 as green color materials and PY138 and PY150 as yellow color materials.
Further, in Reference Example 30 of Table 6, when PG7 is further combined with PG59 and the yellow color material, the P / V ratio can be reduced and the brightness can be reduced as compared with Comparative Example 11 in which PG58 and Y138 are combined. It was revealed that can also be improved. In Reference Example 31, it was also clarified that the P / V ratio can be further reduced by combining PG59 and PG7 as green color materials and PY138 and PY150 as yellow color materials.
On the other hand, when PG58 is used as shown in Comparative Example 1, when y = 0.570, the region of x = 0.260 can be displayed, but display failure occurs, and the brightness is higher than that when PG59 is used. Was inferior. The development residue was also bad. Further, when PG7 or PG36 is used as shown in Comparative Examples 2 and 3, when y = 0.570, the region of x = 0.260 can be displayed, but the brightness is low. Further, even if a dispersant which is a polymer having a structural unit represented by the general formula (I) is combined, the dispersibility is poor, so that the contrast is low, the solvent resolubility, and the development residue are also inferior.
On the other hand, the photosensitive coloring resin compositions for color filters of Comparative Examples 4 to 5 in which a urethane-based dispersant or a polyester-based dispersant is combined with PG59 are inferior in dispersibility, and therefore are compared with Examples and Reference Examples . The brightness was low, the contrast was low, the solvent resolubility was poor, and the development residue was also inferior.

Further, from the results of Tables 7 and 8, among, as a yellow colorant, a mono azo compound of the azo compound and its tautomeric structures represented by the general formula (i), di-, tri- and tetra-anions It was clarified that when a yellow color material containing at least one anion and at least two metal ions selected from the group consisting of two was used, the brightness was improved and the contrast was further improved.

Further, among the examples, in the example in which a solvent having a boiling point of less than 150 ° C. (propylene glycol monomethyl ether acetate) was used as the first solvent in combination with a solvent having a boiling point of 150 ° C. or higher as the second solvent, uneven drying occurred. It was clarified that it became difficult and that the solvent resolubility was easily improved when 10% by mass or more of a solvent having a boiling point of 150 ° C. or higher was contained in the total solvent.

Further, among the examples, it was clarified that in the examples containing the maleimide structure having a hydrocarbon ring as the alkali-soluble resin, a colored layer in which the development residue is less likely to remain is formed.
Further, among the examples, it was clarified that in the examples containing both the maleimide structure having a hydrocarbon ring and the styrene structure as the alkali-soluble resin, a colored layer having improved brightness was formed.
Further, among the examples, it was clarified that in the example in which the oxime ester-based photoinitiator containing no carbazole skeleton was used as the oxime ester-based photoinitiator, a colored layer having improved brightness was formed.

Further, among the examples, it was clarified that in the example using the colored resin composition further containing the mercapto compound, a colored layer having a further improved effect of suppressing the occurrence of water stain was formed.

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

Claims (19)

A color material dispersion liquid containing a color material, a dispersant, and a solvent.
The coloring material is C.I. I. Contains Pigment Green 59, and yellow colorant
The yellow color material is composed of at least one anion selected from the group consisting of the azo compound represented by the following general formula (i) and the azo compound having a tautomeric structure thereof, mono, di, tri and tetra anion. Ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and compounds represented by the following general formula (ii). At least one kind of yellow color material including yellow color material containing
In the yellow color material, Ni and Zn or Ni and Cu are contained as ions of the at least two kinds of metals.
The dispersant is a polymer having a structural unit represented by the following general formula (I).
Color material dispersion for color filters.
(In the above general formula (i), R is independently -OH, -NH ₂ , -NH-CN, acylamino, alkylamino or arylamino, and R'is independently -OH or-, respectively. It is NH ₂ .
In the general formula (ii), R "is independently a hydrogen atom or an alkyl group.)
(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, and R ² and R ³ are hydrocarbons which may independently contain a hydrogen atom or a hetero atom. Representing a group, R ² and R ³ may be bonded to each other to form a ring structure.) The C.I. I. The color material dispersion for a color filter according to claim 1, wherein the pigment green 59 is contained in the color material in an amount of 5 to 95% by mass. In the yellow color material, Ni and Zn are contained as ions of the at least two kinds of metals in a molar ratio of Ni: Zn = 90:10 to 10:90, or Ni and Cu are contained in Ni: Cu =. The color material dispersion for a color filter according to claim 1 or 2, which comprises a molar ratio of 97: 3 to 10:90. The coloring material further comprises C.I. I. Pigment Green 58 and C.I. I. The color material dispersion liquid for a color filter according to any one of claims 1 to 3, which contains at least one of Pigment Green 7. 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 a 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 at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer and the compounds represented by the following general formulas (1) to (3). A salt-type block copolymer in which a salt is formed by one or more selected compounds;
The color material dispersion for a color filter according to any one of claims 1 to 4, wherein the acid value of the dispersant is 2 mgKOH / g or more and 18 mgKOH / g or less, and the glass transition temperature of the dispersant is 30 ° C. or more. liquid.
(In the general formula (1), R ^a Is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -OR. ^e Represents R ^e Is mediated by a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, 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. In the general formula (2), R ^b , R ^b' , And R ^{b "} Each independently has a hydrogen atom, an acidic group or an ester group thereof, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, and a vinyl group which may have a substituent. , Phenyl or benzyl group which may have substituents, or -OR ^f Represents R ^f Is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, a phenyl group or a benzyl which may have a substituent. It represents a (meth) acryloyl group via a group or an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom. In the general formula (3), R ^c And R ^d Each independently has a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -OR. ^e Represents R ^e Is mediated by a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, 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. However, R ^c And R ^d At least one of them contains a carbon atom. ) The color material dispersion liquid for a color filter according to any one of claims 1 to 5, which contains Ni and Cu as ions of at least two kinds of metals in the yellow color material. A photosensitive coloring 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 coloring material is C.I. I. Contains Pigment Green 59, and yellow colorant
The yellow color material contains at least one anion selected from the group consisting of the azo compound represented by the following general formula (i) and the azo compound having a tautomeric structure thereof, mono, di, tri and tetra anion. Ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and compounds represented by the following general formula (ii). At least one kind of yellow color material including yellow color material containing
In the yellow color material, Ni and Zn or Ni and Cu are contained as ions of the at least two kinds of metals.
The dispersant, Ri polymer der having a structural unit represented by the following formula (I),
The alkali-soluble resin has a hydrocarbon ring.
Photosensitive colored resin composition for color filters.
(In the above general formula (i), R is independently -OH, -NH ₂ , -NH-CN, acylamino, alkylamino or arylamino, and R'is independently -OH or-, respectively. It is NH ₂ .
In the general formula (ii), R "is independently a hydrogen atom or an alkyl group.)
(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, and R ² and R ³ are hydrocarbons which may independently contain a hydrogen atom or a hetero atom. Representing a group, R ² and R ³ may be bonded to each other to form a ring structure.) The C.I. I. The photosensitive coloring resin composition for a color filter according to claim 7 , wherein the pigment green 59 is contained in the coloring material in an amount of 5 to 95% by mass. In the yellow color material, Ni and Zn are contained as ions of the at least two kinds of metals in a molar ratio of Ni: Zn = 90:10 to 10:90, or Ni and Cu are contained in Ni: Cu =. The photosensitive colored resin composition for a color filter according to claim 7 or 8 , which comprises a molar ratio of 97: 3 to 10:90. The coloring material further comprises C.I. I. Pigment Green 58 and C.I. I. The photosensitive coloring resin composition for a color filter according to any one of claims 7 to 9 , which comprises at least one of Pigment Green 7. 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 a 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 at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer and the compounds represented by the following general formulas (1) to (3). A salt-type block copolymer in which a salt is formed by one or more selected compounds;
The photosensitive coloring for a color filter according to any one of claims 7 to 10, wherein the acid value of the dispersant is 2 mgKOH / g or more and 18 mgKOH / g or less, and the glass transition temperature of the dispersant is 30 ° C. or more. Resin composition.
(In the general formula (1), R ^a Is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -OR. ^e Represents R ^e Is mediated by a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, 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. In the general formula (2), R ^b , R ^b' , And R ^{b "} Each independently has a hydrogen atom, an acidic group or an ester group thereof, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, and a vinyl group which may have a substituent. , Phenyl or benzyl group which may have substituents, or -OR ^f Represents R ^f Is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, a phenyl group or a benzyl which may have a substituent. It represents a (meth) acryloyl group via a group or an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom. In the general formula (3), R ^c And R ^d Each independently has a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -OR. ^e Represents R ^e Is mediated by a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, 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. However, R ^c And R ^d At least one of them contains a carbon atom. ) The photosensitive colored resin composition for a color filter according to any one of claims 7 to 11, which contains Ni and Cu as ions of at least two kinds of metals in the yellow color material. The photosensitive coloring resin composition for a color filter according to any one of claims 7 to 12, wherein the alkali-soluble resin has a maleimide structure represented by the following general formula (4).
[In general formula (4), R ^M Is a hydrocarbon ring which may be substituted. ] The photosensitive coloring resin composition for a color filter according to any one of claims 7 to 13 , further comprising a mercapto compound. The photosensitive colored resin composition for a color filter according to any one of claims 7 to 14 , which contains an oxime ester-based photoinitiator as the photoinitiator and further contains a mercapto compound. The solvent is a solvent having a boiling point of less than 150 ° C. as a first solvent.
As the second solvent, a solvent having an alcoholic hydroxyl group is contained in the total solvent in an amount of 0.1% by mass or more and 10% by mass or less, or
The photosensitive colored resin composition for a color filter according to any one of claims 7 to 15 , which contains 3% by mass or more and 40% by mass or less of a solvent having a boiling point of 150 ° C. or higher as the second solvent. It is possible to form a cured film in which the chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source are in the range of x = 0.180 to 0.330 and y = 0.5000 to 0.750. The photosensitive colored resin composition for a color filter according to any one of claims 7 to 16 . A color filter including at least a transparent substrate and a colored layer provided on the transparent 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 7 to 17. A color filter characterized by having a colored layer which is a cured product of a product. A display device comprising the color filter according to claim 18 .