WO2016104493A1

WO2016104493A1 - Coloring material dispersant for color filter, photosensitive colored resin composition for color filter, color filter, liquid crystal display device, and organic light-emitting display device

Info

Publication number: WO2016104493A1
Application number: PCT/JP2015/085810
Authority: WO
Inventors: 健朗長井; 中村　和彦; 力飛塚本; 一貴五十嵐; 理恵上森; 裕司市川
Original assignee: 株式会社Ｄｎｐファインケミカル
Priority date: 2014-12-24
Filing date: 2015-12-22
Publication date: 2016-06-30
Also published as: TWI743635B; TW202022055A; CN111221217A; CN111221217B

Abstract

Provided is coloring material dispersant for a color filter, said coloring material dispersant containing a coloring material, a dispersant and a solvent, wherein the dispersant comprises at least one of a block copolymer (P1) described below and a salt-type block copolymer (P2) described below. P1 is a block copolymer containing an A block, which contains structural units represented by general formula (I), and a B block containing structural units derived from monomers containing a carboxy group. P2 is a salt-type block copolymer in which a salt is formed by at least a portion of the nitrogen sites at the ends of the structural units represented by general formula (I) of the aforementioned block copolymer, and at least one compound selected from the group consisting of the compounds represented by general formulas (1) to (3). The acid value of the dispersant is 1-18 KOH/g, and the glass transition temperature of the dispersant is at least 30°C. (Each symbol in general formula (I) and formulas (1) to (3) is as defined in the description.)

Description

Color material dispersion for color filter, photosensitive colored resin composition for color filter, color filter, liquid crystal display device, and organic light emitting display device

The present invention relates to a color material dispersion for a color filter, a photosensitive colored resin composition for a color filter, a color filter, a liquid crystal display device, and an organic light emitting display device.

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

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

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

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

Here, the color filter is generally formed on a transparent substrate, a transparent layer formed on the transparent substrate, and composed of a colored layer of three primary colors of red, green, and blue, and on the transparent substrate so as to partition each colored pattern. And a light shielding portion formed.

As a method for forming pixels in a color filter, among others, a pigment dispersion method having excellent characteristics on average is most widely adopted from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, and the like.
In a color filter having pixels formed by using a pigment dispersion method, miniaturization of pigments is being studied in order to achieve high brightness and high contrast. By making the pigment finer, it is considered that the scattering of light transmitted through the color filter by the pigment particles is reduced, and high brightness and high contrast are achieved.
However, since the refined pigment particles tend to aggregate, there is a problem that the dispersibility and dispersion stability are lowered.

It is known that a dispersant is effective as a technique for improving the dispersibility of the finely divided pigment. For example, in Patent Document 1, a specific pigment having an amino group or an ammonium base is used as a pigment dispersant for the purpose of providing a color composition for a color filter that has excellent chromaticity characteristics and good developability and storage stability. A color using a block copolymer having an A block containing a repeating unit, a specific repeating unit containing an alkyleneoxy chain in the alcohol-derived portion of the carboxylic acid ester, and a B block containing a repeating unit having an acidic group A filter coloring composition is disclosed.
Patent Document 2 discloses a specific pigment having an amino group or an ammonium base as a pigment dispersant for the purpose of providing a coloring composition for a color filter that has excellent chromaticity characteristics and good developability and storage stability. A repeating unit, a repeating unit containing a carboxylic acid ester, and a repeating unit having an acidic group, the repeating unit containing a carboxylic acid ester as a specific ratio, and the ratio of the weight average molecular weight to the number average molecular weight is a specific ratio A coloring composition for a color filter using the above copolymer is disclosed.

On the other hand, in a color filter, a region connecting three points of red, green, and blue pixels is a limit of colors that can be reproduced. In other words, a color filter having a larger triangle formed by three points of red, green, and blue pixels has a wider range of colors that the display device can reproduce on the screen.
In order to achieve a color space having a wide color reproduction gamut such as AdobeRGB or DCI, the green pixel of the color filter, in particular, has a high color density of green chromaticity {(x = 0.14 to 0.30, y = 0. .55 to 0.75), more preferably (x = 0.14 to 0.30, y = 0.57 to 0.75), and still more preferably (x = 0.14 to 0.30, y = 0.61 to 0.75)}.

Conventional 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 sometimes abbreviated as PG36), C.I. I. Pigment Green 58 (hereinafter sometimes abbreviated as PG58).
However, when a green pixel is produced using PG7 so as to achieve the high color density green chromaticity region, there is a problem that the luminance of the green pixel is lowered. If a green pixel is formed using PG7 as the main green color material, a dark color filter is obtained.
Also, when forming a green pixel so as to achieve the high color density green chromaticity region using PG 36, there is a problem that the luminance of the green pixel is reduced, although not as high as PG7.
Further, when PG58 is used, the luminance is increased, but when a green pixel included in the green chromaticity region having the high color density is manufactured, it is necessary to make the green pixel very thick, which causes a problem in mass productivity. In addition, since only the green pixels are thickened, it is difficult to maintain the color filter performance. Furthermore, even if only PG 58 is used, there are regions that cannot be achieved in the green chromaticity region of the high color density, and there is a limit in producing a green pixel so as to form a larger triangle.

Patent Document 3 discloses highly chlorinated zinc phthalocyanine as a colored resin composition for a color filter that achieves a green target chromaticity with a high color density without forming a thick film and can form a high-luminance green pixel. The use of pigments containing is described. However, higher brightness is required.

On the other hand, Patent Document 4 aims to provide a colored curable resin composition for a color filter in which the occurrence of a foreign matter failure due to a brominated zinc phthalocyanine pigment that has been attracting attention in recent years for forming a green pixel is suppressed. A pigment dispersant which is an amine polymer containing a specific structural unit as a pigment dispersant, a structural unit having a quaternary ammonium base in the side chain as a coagulation inhibitor, and a structure not having a quaternary ammonium base The coloring composition for color filters which uses together the block copolymer containing a unit is disclosed. However, the brominated zinc phthalocyanine pigment described in Patent Document 4 is substantially C.I. I. Only Pigment Green 58 (PG58), and a green pigment dispersion liquid having a bluish green color and high brightness has not been obtained.

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

In Patent Document 5, 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 to not provide a protective layer of transparent resin. As a color filter capable of ensuring performance and corresponding to high color reproducibility, it is disclosed that a colored layer forming a green pixel contains a specific amount or less of PG36 and has a specific dielectric loss tangent (tan δ) value. Yes.
However, with the technique disclosed in Patent Document 5, even if display defects are reduced, luminance is insufficient, and wide color reproducibility is also insufficient.

On the other hand, Patent Document 6 includes PG58 and a yellow organic pigment as a green composition for a color filter that can adjust the luminance without reducing a high contrast, and includes a blue pigment, a red pigment, a purple pigment, and an orange pigment. A green composition containing any one selected is disclosed.
However, the technique disclosed in Patent Document 6 is insufficient in terms of wide color reproducibility.

JP 2011-237769 A JP 2012-32767 A JP 2013-20558 A JP 2012-108266 A JP 2009-162979 A JP 2011-118051 A

In recent color filters, it is necessary to solve various problems in mass production of color filters in accordance with the technology for improving the colorant dispersibility in order to realize the demand for higher brightness and higher contrast. . That is, in order to increase the color material concentration in the resin composition, it is necessary to increase the amount of the dispersant, which causes problems such as generation of a development residue and a delay in development time. Further, when the colorant concentration is increased and the dispersant content is increased, the amount of the binder is relatively decreased, which causes a problem that the colored resin layer is easily peeled off from the base substrate during development. Therefore, although it is calculated | required that it has high image development adhesiveness as a colored resin composition, there existed a problem that it did not reach a practical use level. Furthermore, in the manufacturing process of a color filter, it is calculated | required that the solid content of the colored resin composition once dried is excellent in the property which melt | dissolves in a solvent again, and the re-solubility in a solvent. For example, if the photosensitive colored resin composition adheres to the tip of the die lip when coating with a die coater, a solidified product is generated by drying, but the solidified product dissolves in the photosensitive colored resin composition when coating is resumed. If it is not easy to do, a part of the solidified product on the die lip peels off and easily adheres to the colored layer of the color filter, which causes a foreign matter defect. In particular, when the colorant concentration of the colored resin composition is increased, the solvent re-solubility is likely to be insufficient, and the yield is reduced due to the occurrence of the foreign matter in the color filter manufacturing process.
However, even with the methods described in

Patent Documents

1 and 2, in addition to dispersibility of color materials, all of various problems in mass production of color filters, development residue generation, development adhesion, and solvent resolubility It has been difficult to solve the problem as shown in a comparative example described later.

The present invention has been made in view of the above circumstances, and a photosensitive colored resin composition having excellent colorant dispersion stability and excellent development adhesion and solvent resolubility while suppressing generation of development residues. Color filter capable of forming a colored layer with excellent colorant dispersion, excellent colorant dispersion stability, excellent development adhesion and solvent re-dissolution, and excellent contrast while suppressing development residue generation Photosensitive coloring resin composition, color filter formed using the photosensitive coloring resin composition for color filter, liquid crystal display device excellent in display characteristics by using the color filter, and organic light emitting display device The primary purpose is to provide

In order to achieve high brightness and high contrast without increasing the thickness of the green pixel of the color filter while maintaining the high color density green chromaticity region, the color filter exhibits a bluish green color and brightness. A green pigment dispersion having a high particle size has been desired, but has not existed in the past.
The present invention has been made in view of the above circumstances, and exhibits a bluish green color, is excellent in color material dispersion stability, and has a high luminance. Photosensitive colored resin composition for color filters capable of forming a colored layer having excellent solubility, high luminance and high contrast and excellent color reproducibility, and high luminance and high using the photosensitive colored resin composition for color filters A second object is to provide a color filter having excellent contrast and color reproducibility, and a liquid crystal display device and an organic light emitting display device having high luminance and excellent color reproducibility by using the color filter.

The color material dispersion for a color filter according to the first aspect of the present invention for solving the first object is a color material dispersion containing a color material, a dispersant, and a solvent,
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 following 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 one or more selected compounds form a salt;
The acid value of the dispersant is 1 to 18 mgKOH / g, and the glass transition temperature of the dispersant is 30 ° C. or higher.

(In General Formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, R ² and R ³ are each independently a hydrogen atom or a hydrocarbon that may contain a hetero atom. Represents a group, and R ² and R ³ may be bonded to each other to form a ring structure.
In the general formula (1), R ^a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or benzyl group, or —O—R. It represents ^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 an alkylene having 1 to 4 carbon atoms It represents a (meth) acryloyl group via a group. In the general formula (2), R ^b , R ^{b ′} , and R ^{b ″} each independently represent a hydrogen atom, an acidic group or an ester group thereof, a straight chain having 1 to 20 carbon atoms that may have a substituent, Represents a branched or cyclic alkyl group, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or —O—R ^f , wherein R ^f has 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 benzyl group which may have a substituent, or 1 carbon atom Represents a (meth) acryloyl group via an alkylene group of ˜4, X represents a chlorine atom, a bromine atom, or an iodine atom, wherein R ^c and R ^d are each independently a hydrogen atom; A hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, Represents a vinyl group, an optionally substituted phenyl group or benzyl group, or —O—R ^e , where R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, A phenyl group or benzyl group which may have a substituent, or a (meth) acryloyl group via an alkylene group having 1 to 4 carbon atoms, provided that at least one of R ^c and R ^d contains a carbon atom .)

The color material dispersion for a color filter according to the second aspect of the present invention for solving the second object is a color material dispersion containing a color material, a dispersant, and a solvent,
The color material is C.I. I. Including Pigment Green 59,
The dispersant is a polymer having a structural unit represented by the following general formula (I).

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

Moreover, the photosensitive colored resin composition for a color filter according to the present invention contains the color material dispersion according to the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. .

The color filter according to the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is the color filter photosensitivity according to the present invention. It is a colored layer formed by curing a colored resin composition.

The present invention provides a liquid crystal display device comprising the color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
The present invention also provides an organic light emitting display device comprising the color filter according to the present invention and an organic light emitter.

According to the first aspect of the present invention, a coloring material that is excellent in coloring material dispersion stability and capable of producing a photosensitive colored resin composition excellent in development adhesion and solvent resolubility while suppressing generation of development residue. Photosensitive colored resin for color filters that is excellent in dispersion and color material dispersion stability, has excellent development adhesion and solvent re-dissolution properties, and can form colored layers with excellent contrast while suppressing development residue generation. It is possible to provide a composition, a color filter formed using the photosensitive colored resin composition for a color filter, a liquid crystal display device excellent in display characteristics by using the color filter, and an organic light emitting display device. it can.
Further, according to the second aspect of the present invention, it exhibits a bluish green color, is excellent in colorant dispersion stability, has a high brightness, and is excellent in solvent resolubility using the colorant dispersion. , A photosensitive colored resin composition for color filters capable of forming a colored layer with high brightness and high contrast and excellent color reproducibility, and high brightness and high contrast color using the photosensitive colored resin composition for color filters A color filter having excellent reproducibility, and a liquid crystal display device and an organic light emitting display device having high luminance and excellent color reproducibility can be provided by using the color filter.

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 liquid crystal display device of the present invention. FIG. 3 is a schematic view illustrating an example of the organic light emitting display device of the present invention.

I. Hereinafter, the color material dispersion for color filter, the photosensitive colored resin composition for color filter, the color filter, the liquid crystal display device and the organic light emitting display device according to the first invention will be described in detail below. .
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.
In this specification, unless otherwise specified, the chromaticity coordinates x and y are in the XYZ color system of JIS Z8701 measured using a C light source.

I-1. Colorant dispersion according to the first aspect of the present invention The colorant dispersion for a color filter according to the first aspect of the present invention is a colorant dispersion containing a colorant, a dispersant, and a solvent,
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 following 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 one or more selected compounds form a salt;
The acid value of the dispersant is 1 to 18 mgKOH / g, and the glass transition temperature of the dispersant is 30 ° C. or higher.

The colorant dispersion according to the present invention includes, as a dispersant, a block copolymer (P1) having the specific acid unit and a specific glass transition temperature and including the specific structural unit, and the block copolymer. Since at least one salt-type block copolymer (P2) in which a salt is formed with the specific compound is used, the colorant dispersion stability is excellent, and the development adhesion is suppressed while the generation of development residue is suppressed. A photosensitive colored resin composition having excellent solubility can be produced. Moreover, the photosensitive coloring resin composition for color filters prepared using the said color material dispersion liquid can form the colored layer excellent in contrast.

The block copolymer (P1) having the specific structural unit and having the specific acid value and the specific glass transition temperature, and the salt-type block copolymer in which the block copolymer and the specific compound form a salt By using at least one of the coalesced (P2) as a dispersant, the effect of exerting the above-mentioned effects is unclear but is estimated as follows.
Conventionally, as a pigment dispersant, a block copolymer having an A block containing a specific repeating unit having an amino group or an ammonium base and a B block containing a repeating unit having an acidic group, dispersibility and dispersion stability, It has been known that alkali developability can be improved (for example,

Patent Documents

1, 2, and 4).
However, as a result of investigations by the present inventors, the method described in Patent Document 1 did not particularly achieve the development adhesion at a practical level. In the method described in Patent Document 1, as shown in a comparative example to be described later, since the block copolymer contains a specific repeating unit containing an alkyleneoxy chain in the alcohol-derived portion of the carboxylic acid ester, the glass transition temperature is low. The cause was estimated to be lower. When the glass transition temperature of the block copolymer as the pigment dispersant is lower than or near the temperature of the developer, the molecular motion of the dispersant increases during development, and as a result, the development adhesion decreases. Estimated.
In addition, even with the methods described in Patent Documents 2 and 4, the development adhesiveness has not reached a practical level. In the methods described in Patent Documents 2 and 4, as shown in Comparative Examples described later, the acid value of the dispersant is higher than the value specified in the present application, so the developability is excellent, but the polarity is too high. On the other hand, it was presumed that the peeling was likely to occur. In the methods described in Patent Documents 2 and 4, since there is no idea that the dispersant satisfies a specific low acid value and a specific high glass transition temperature at the same time, the development adhesion does not reach a practical level. Presumed.

As a result of intensive studies, the inventors have not reached a practical level when the acid value of a specific block copolymer or salt-type block copolymer is high, and the solvent resolubility deteriorates. It has been found that when the acid value is not more than a specific value, it has an effect of suppressing the development residue, is less likely to be peeled off, has good development adhesion, and is excellent in solvent resolubility. On the other hand, even if the specific block copolymer or salt-type block copolymer has a low acid value not higher than the specific value, if the glass transition temperature is lower than the predetermined value, the development adhesion does not reach a practical level. However, it has been found that when a block copolymer or a salt-type block copolymer having a glass transition temperature of 30 ° C. or higher, which is higher than the developer temperature, is used, the development adhesiveness is excellent. When a block copolymer or salt type block copolymer having a glass transition temperature of 30 ° C. or higher, which is higher than the developer temperature, is used, molecular movement of the dispersant during development is suppressed, resulting in a decrease in development adhesion. Is estimated to be suppressed.

The color material dispersion according to 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. is there.
Hereinafter, each component of the colorant dispersion according to the present invention will be described in detail in order from the dispersant characteristic of the present invention.

<Dispersant>
In the present invention, the dispersant is at least one of the block copolymer (P1) and the salt-type block copolymer (P2), and the dispersant has an acid value of 1 to 18 mgKOH / g. Thus, a dispersant having a glass transition temperature of 30 ° C. or higher is used.

The structural unit represented by the general formula (I) contained in the A block has basicity and functions as an adsorption site for the coloring material. Further, at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) and one or more compounds selected from the group consisting of the general formulas (1) to (3) are salts. In this case, the salt forming part functions as a stronger adsorption site for the coloring material. On the other hand, the B block containing a structural unit derived from a carboxy group-containing monomer functions as a block having solvophilicity. Therefore, the block copolymer of the present invention functions as a colorant dispersing agent by sharing the function between the colorant and the adsorbing A block and the solvent B compatible block.

[Block copolymer]
{A block}
(Structural unit represented by general formula (I))
In general formula (I), A is a direct bond or a divalent linking group. The direct bond means that A does not have an atom, that is, C (carbon atom) and N (nitrogen atom) in the general formula (I) are bonded without interposing another atom. To do.
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, an ether group having 1 to 10 carbon atoms (—R′—OR). "-: R 'and R" each independently represents an alkylene group) and combinations thereof.
Among these, from the viewpoint of dispersibility, A in the general formula (I) is preferably a direct bond, a -CONH- group, or a divalent linking group containing a -COO- group.

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

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

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

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

In the 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 these, from the viewpoint of improving dispersibility and dispersion stability, it is preferably 3 to 100, more preferably 3 to 50, and even more preferably 3 to 30.

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

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

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

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

In the block copolymer before salt formation, the content ratio of the structural unit derived from the carboxy group-containing monomer may be appropriately set so that the acid value of the block copolymer is within the range of the specific acid value. Although not limited, it is preferably 0.05 to 4.5% by mass and more preferably 0.07 to 3.7% by mass with respect to the total mass of all the structural units of the block copolymer.
The content ratio of the structural unit derived from the carboxy group-containing monomer is greater than or equal to the lower limit value, so that it is excellent in the effect of suppressing development residue, and is less than or equal to the upper limit value, thereby deteriorating development adhesion and solvent resolubility. Can be prevented.
In addition, the structural unit derived from a carboxy group containing monomer should just become said specific acid value, may consist of 1 type, and may contain 2 or more types of structural units.

(Other structural units)
In view of improving the solvophilicity, the B block usually contains a structural unit that further improves the solvophilicity in addition to the structural unit derived from the carboxy group-containing monomer.
Examples of the structural unit constituting the B block include a monomer having an unsaturated double bond copolymerizable with the monomer that derives the structural unit represented by the general formula (I). The structural unit represented by (II) is preferred.

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

In general formula (II), A 'can be the same as A in general formula (I). Of these, a divalent linking group containing a direct bond, a —CONH— group, or a —COO— group is preferable from the viewpoint of solubility in an organic solvent.

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

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

In R ⁵ described above, x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and 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, more preferably an integer of 1 to 2.

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

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

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

The number of structural units constituting the B block is not particularly limited, but is 10 to 300 in terms of improving the dispersibility of the colorant by effectively acting the solvophilic part and the parent colorant part. Preferably, the number is 10 to 100, more preferably 10 to 70.

In the B block in the block copolymer, the content ratio of the structural unit represented by the general formula (II) is based on the total mass of all the structural units of the B block from the viewpoint of improving the solvent affinity and the colorant dispersibility. On the other hand, the content is preferably 50 to 100% by mass, and more preferably 70 to 100% by mass. In addition, the content rate of the said structural unit is computed from the preparation mass at the time of synthesize | combining the B block which has a structural unit derived from a carboxy group containing monomer.

Further, in the block copolymer before salt formation, the content of the structural unit represented by the general formula (II) is the total mass of all the structural units of the block copolymer from the viewpoint of improving the colorant dispersibility. The content is preferably 40 to 95% by mass, more preferably 50 to 90% by mass. In addition, the content rate of the said structural unit is computed from the preparation mass at the time of synthesize | combining the block copolymer before salt formation. *

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

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

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

Moreover, the content rate of the structural unit derived from a hydroxyl-containing monomer in the block copolymer (P1) before salt formation is 1% by mass or more with respect to the total mass of all the structural units of the block copolymer. It is preferably 2% by mass or more, more preferably 3% by mass or more, and particularly preferably 4% by mass or more. When it is at least the above lower limit, the development adhesiveness can be made preferable. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. If it is not more than the above upper limit, it can be made preferable from the viewpoint of increasing the introduction ratio of other useful monomers. In addition, the content rate of the said structural unit is computed from the preparation mass at the time of synthesize | combining the block copolymer before salt formation.

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

In the block copolymer (P1) before salt formation, the content ratio of the structural unit derived from the aromatic group-containing monomer is the total mass of all the structural units of the block copolymer from the viewpoint of improving solvent resolubility. On the other hand, it is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more. Solvent resolubility can be made preferable as it is more than the said lower limit. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. If it is not more than the above upper limit, it can be made preferable from the viewpoint of increasing the introduction ratio of other useful monomers.

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

(I) When the structural unit derived from a hydroxyl group-containing monomer and the structural unit derived from an aromatic group-containing monomer are included, the structural unit derived from a hydroxyl group-containing monomer with respect to 1 part by mass of the structural unit derived from the aromatic group-containing monomer Is preferably contained in an amount of 0.15 parts by mass or more, more preferably 0.5 parts by mass or more. It is because it can be set as the thing excellent in image development adhesiveness as it is more than the said lower limit. Similarly, the structural unit derived from the hydroxyl group-containing monomer is preferably contained in an amount of 15 parts by mass or less, more preferably 7 parts by mass or less, with respect to 1 part by mass of the structural unit of the aromatic group-containing monomer. It is because it can be excellent in solvent resolubility that it is below the above-mentioned upper limit. Among them, the glass transition temperature value (Tgi) of the homopolymer is 10 parts per 1 part by mass of the structural unit derived from the aromatic group-containing monomer having a glass transition temperature value (Tgi) of the homopolymer of 10 ° C. or more. It is particularly preferable that the structural unit derived from a hydroxyl group-containing monomer having a temperature of at least ° C. is contained in the above range. It is because the development adhesiveness can be further improved by containing at the above lower limit or more, and the solvent resolubility can be further improved by containing at the above upper limit or less.

In addition, (ii) the hydroxyl group and aromatic group-containing monomer in the structural unit derived from the hydroxyl group and aromatic group-containing monomer includes, for example, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl- Examples 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, an effect obtained from a structural unit derived from a hydroxyl group-containing monomer, and aromaticity. It is preferably used since any of the effects obtained from the structural unit derived from the group-containing monomer can be obtained. That is, it is preferable in terms of improving the development adhesion, the development speed, and the solvent re-solubility.
(Ii) When a structural unit derived from a hydroxyl group and aromatic group-containing monomer is included, the development adhesion, development speed, and solvent resolubility can be improved by one structural unit. There is also an advantage that the introduction ratio can be increased.

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

In the block copolymer (P1), the ratio m / n of the unit number m of the structural unit of the A block and the unit number n of the structural unit of the B block is in the range of 0.05 to 1.5. In view of the dispersibility and dispersion stability of the colorant, it is more preferable that the ratio be in the range of 0.1 to 1.0.

Further, the amine value of the block copolymer (P1) 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. Moreover, as an upper limit, it is preferable that it is 140 mgKOH / g or less, It is more preferable that it is 130 mgKOH / g or less, It is still more preferable that it is 120 mgKOH / g or less. If it is more than the said lower limit, dispersion stability is more excellent. Moreover, if it is below the said upper limit, it is excellent in compatibility with another component and solvent resolubility becomes favorable.
In the present invention, the amine value of the block copolymer before salt formation refers to potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize 1 g of the solid content of the block copolymer before salt formation. This is a value measured by the method described in JIS K 7237.

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

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

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

[Salt-type block copolymer]
In the present invention, the block copolymer is selected from the group consisting of at least part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the general formulas (1) to (3). You may use the salt type block copolymer in which the 1 or more types of compound formed the salt.
The salt-type block copolymer is preferably used from the viewpoint that the color material adsorbability is further improved and the color material dispersibility is improved at the salt forming site in the structural unit represented by the general formula (I).

(One or more compounds selected from the group consisting of the general formulas (1) to (3))
In the general formulas (1) to (3), R ^a , R ^b , R ^{b ′} , R ^{b ″} , R ^c , R ^d , R ^e , and R ^f are linear or branched chains having 1 to 20 carbon atoms. Alternatively, the cyclic alkyl group may be linear or branched, and may contain a cyclic structure, specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n- Examples thereof include an undecyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a tetradecyl group, an octadecyl group, etc., preferably a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and more preferably a carbon number. 1-8 straight Examples include a chain, branched chain, or cyclic alkyl group.
In R ^a , R ^c , R ^d , and R ^e , examples of the substituent of the phenyl group or benzyl group that may have a substituent include an alkyl group having 1 to 5 carbon atoms and an acyl group. And an acyloxy group.

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

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

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

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

The molecular weight of the one or more compounds selected from the group consisting of the general formulas (1) to (3) is preferably 1000 or less, particularly 50 to 800, from the viewpoint of improving the colorant dispersibility. 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 benzene sulfonic acid, vinyl sulfonic acid, methane sulfonic acid, p-toluene sulfonic acid, monomethyl sulfuric acid, monoethyl sulfuric acid, mono n-propyl sulfuric acid and the like. A hydrate such as p-toluenesulfonic acid monohydrate may be used. Examples of the compound represented by the general formula (2) include methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, n-butyl chloride, hexyl chloride, octyl chloride, dodecyl chloride, Tetradecyl chloride, hexadecyl chloride, phenethyl chloride, benzyl chloride, benzyl bromide, benzyl iodide, chlorobenzene, α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethyl Examples include benzoic acid, 4-iodophenylbenzoic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, methyl α-bromophenylacetate, 3- (bromomethyl) phenylboronic acid, and the like. Examples of the compound represented by the general formula (3) include monobutyl phosphoric acid, dibutyl phosphoric acid, methyl phosphoric acid, dibenzyl phosphoric acid, diphenyl phosphoric acid, phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, and the like. .
The group consisting of phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, dibutyl phosphoric acid, benzyl chloride, benzyl bromide, vinyl sulfonic acid, and p-toluenesulfonic acid monohydrate because of particularly excellent dispersion stability One or more selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, benzyl bromide, and p-toluenesulfonic acid monohydrate are preferably used.
Moreover, from the point which is excellent in dispersion stability and the inhibitory effect of a development residue improves by a combination with the block copolymer (P1) which has an acid value, it is general formula (2) which has an acidic group and its ester group. The compounds represented are also preferably used, among which α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, and 4-iodophenylbenzoic acid. One or more selected from the group consisting of

In the salt type block copolymer, the content of one or more compounds selected from the group consisting of the general formulas (1) to (3) is the terminal end of the structural unit represented by the general formula (I). The group consisting of the above general formulas (1) to (3) with respect to 1 mol of the terminal nitrogen site of the structural unit represented by the general formula (I) because it forms a salt with the nitrogen site. One or more compounds selected from are preferably 0.01 mol or more, more preferably 0.1 mol or more, still more preferably 0.2 mol or more, and 0.3 mol or more. It is particularly preferable that If it is at least the above lower limit value, the effect of improving the colorant dispersibility due to salt formation can be easily obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, further preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. When it is not more than the above upper limit value, it can be excellent in development adhesion and solvent re-solubility.
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 combining 2 or more types, it is preferable that the total content is in the above range.

As a method for preparing the salt type block copolymer, one or more compounds selected from the group consisting of the general formulas (1) to (3) are added to a solvent in which the block copolymer is dissolved or dispersed. And a method of heating, if necessary, and the like.
The terminal nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer, and one or more compounds selected from the group consisting of the general formulas (1) to (3) The formation of a salt and the proportion thereof can be confirmed by a known method such as NMR.

The value of the amine value of the obtained salt-type block copolymer (P2) is smaller by the amount of salt formation than the block copolymer (P1) before salt formation. However, since the salt formation site is the same as the terminal nitrogen site corresponding to the amino group, or rather becomes a strengthened color material adsorption site, the color material dispersibility and color material dispersion stability tend to be improved by salt formation. is there. In addition, like the amino group, if the salt forming site is too much, the solvent resolubility is adversely affected. Therefore, in the present invention, the amine value of the block copolymer (P1) before salt formation can be used as an index for improving colorant dispersion stability and solvent resolubility. The amine value of the obtained salt-type block copolymer (P2) is preferably 0 to 130 mgKOH / g, more preferably 0 to 120 mgKOH / g.
If it is below the above upper limit, the compatibility with other components is excellent, and the solvent resolubility becomes good.

In addition, the amine value of the salt type block copolymer salt-formed with the compound represented by the general formula (2) among the salt type block copolymer (P2) is determined by the method described in JIS K 7237. It can be a measured value. In the compound of the general formula (2), since the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the halogen atom side hydrocarbon form a salt, the salt is also formed by the measurement method. This is because the amine value can be measured without any change.
On the other hand, among the salt-type block copolymer (P2), the amine value of the salt-type block copolymer salt-formed by the compound represented by the general formula (1) or (3) is the salt described above. It calculates | requires by calculating as follows from the amine value of the block copolymer before formation. In the compound represented by the general formula (1) or (3), the terminal nitrogen site and the acidic group of the structural unit represented by the general formula (I) form a salt. This is because when the amine value of the copolymer is measured by the method described in JIS K 7237, the state of salt formation is changed and an accurate value cannot be measured.
First, the amine value of the block copolymer (P1) before salt formation is determined by the method described above. Next, the 13C-NMR spectrum of the salt-type block copolymer was measured using a nuclear magnetic resonance apparatus, and among the obtained spectrum data, the terminal nitrogen contained in the structural unit represented by the general formula (I) From the ratio of the integrated value of the carbon atom peak adjacent to the non-salt-formed nitrogen atom and the carbon atom peak adjacent to the salt-formed nitrogen atom at the site, the general formula (I The reaction rate of one or more compounds selected from the group consisting of the general formula (1) or (3) with respect to the terminal nitrogen site of the structural unit represented by Ratio). The terminal nitrogen moiety of the structural unit represented by the general formula (I) formed by salt formation of one or more compounds selected from the group consisting of the general formula (1) or (3) has an amine value of 0. (The amine number of the pre-salt-form block copolymer (P1) measured by the method described in JIS K 7237) × (the ratio of nitrogen sites at the terminals where salts are formed, calculated from 13C-NMR spectrum) (%) / 100) is calculated by subtracting the amine value consumed by salt formation from the amine value of the block copolymer before salt formation.
Amine value of salt-type block copolymer (P2) = {amine value of block copolymer (P1) before salt formation measured by the method described in JIS K 7237} — {measured by the method described in JIS K 7237 Of the block copolymer (P1) before salt formation} × {the ratio of nitrogen sites (%) / 100} at the terminal of salt formation calculated from 13C-NMR spectrum

The acid value of the dispersant used in the present invention is 1 mg KOH / g or more as a lower limit from the viewpoint of the effect of suppressing development residue. Among them, the acid value of the dispersant is more preferably 2 mgKOH / g or more from the viewpoint of more excellent development residue suppression effect. In addition, the acid value of the dispersant used in the present invention is 18 mg KOH / g or less as an upper limit from the viewpoint that deterioration of development adhesion and deterioration of solvent resolubility can be prevented. Among these, the acid value of the dispersant is more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less, from the viewpoint of improving the development adhesion and the solvent resolubility.
In the dispersant used in the present invention, the acid value of the block copolymer (P1) 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. Further, the upper limit of the acid value of the block copolymer (P1) before salt formation is 18 mgKOH / g or less, more preferably 16 mgKOH / g or less, and still more preferably 14 mgKOH / g or less. . This is because the development adhesiveness and the solvent resolubility are improved.

As described above, the acid value of the block copolymer (P1) before salt formation is 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 a value measured by the method described in JIS K 0070.
Further, the acid value of the salt type block copolymer in which the salt type block copolymer (P2) is salt-formed with the compound represented by the general formula (2) is also measured by the method described in JIS K 0070. Is the value to be In the compound of the general formula (2), since the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the halogen atom side hydrocarbon form a salt, the salt is also formed by the measurement method. This is because it can be measured without change.
On the other hand, when the salt type block copolymer (P2) is a salt type block copolymer that is salt-formed by the compound represented by the general formula (1) or (3), the salt type block copolymer (P2) is used for salt formation. The acid value is calculated by removing the acidic groups. This is because the acidic group used for salt formation does not function as an acidic group that increases the acid value of the dispersant. Therefore, in this application, the acid value of the salt type block copolymer salt-formed with the compound represented by the general formula (1) or (3) is calculated by a value obtained by the following formula. When the acid value of the salt-type block copolymer salt-formed by the compound represented by the general formula (1) or (3) is measured by the method described in JIS K 0070, it changes to a salt-forming state. This is because an accurate value cannot be measured.

Acid value of the salt-type block copolymer (P2) = {total acid value of the compound represented by the general formula (1) or (3) used for salt formation−acid value consumed by salt formation} + salt Acid value of block copolymer (P1) before formation Here, the total acid value of the compound represented by the general formula (1) or (3) used for the salt formation is described in JIS K 0070. It can be measured by the method. 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 determined by measuring the 13C-NMR spectrum of the salt-type block copolymer using a nuclear magnetic resonance apparatus, and at the terminal nitrogen site in the obtained spectrum data. From the ratio of the integrated value of the carbon atom peak adjacent to the non-salt formed nitrogen atom and the carbon atom peak adjacent to the salt formed nitrogen atom, the terminal nitrogen formed as a salt to the total number of nitrogen sites at the end Calculate the ratio of the number of parts. {Amine number of block copolymer (P1) before salt formation (P1) measured by the method described in JIS K 7237} × {Nitrogen site ratio of terminal at which salt is calculated from 13C-NMR spectrum (%) / 100}, the consumed amine value is calculated, and this value is the same as the acid value consumed by salt formation.
However, when 1 mol or less of the compound represented by the general formula (1) is salt-formed with respect to 1 mol of the terminal nitrogen moiety of the structural unit represented by the general formula (I), the acidic group is 1 When the salt of the compound represented by the general formula (3) having 1 mol or less is formed, or the compound represented by the general formula (3) having two acidic groups is salted by 0.5 mol or less. When forming, if the total amount of acidic groups forms a salt with the terminal nitrogen moiety of the structural unit represented by the general formula (I), in the salt-type block copolymer after the salt formation, the acidic group Since does not affect the acid value, it can have the same acid value as the block copolymer before salt formation.
On the other hand, when the compound represented by the general formula (3) having two acidic groups is added in a mole number exceeding the above, there is an acidic group that is not salt-formed in the dispersant even after the salt is formed. Therefore, as shown in the above formula, the acid value of the acidic group that has not formed a salt is added to the acid value of the block copolymer before the salt formation to calculate the acid value of the dispersant.

Moreover, in this invention, the glass transition temperature of a dispersing agent is 30 degreeC or more. That is, regardless of whether the dispersant is the block copolymer (P1) or the salt type block copolymer (P2), the glass transition temperature thereof is 30 ° C. or higher.
When the glass transition temperature of the dispersant is less than 30 ° C., the development adhesiveness is lowered particularly when it is equal to or lower than the developer temperature (usually about 23 ° C.). This is presumed that when the glass transition temperature is equal to or less than or close to the developer temperature, the movement of the dispersant increases during development, resulting in poor development adhesion.
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 is determined by measuring by differential scanning calorimetry (DSC) according to JIS K7121.

However, the glass transition temperature (Tg) of the block copolymer not forming salt can be calculated by the following formula and used as an index.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the block copolymer. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. As the glass transition temperature value (Tgi) of the homopolymer of each monomer, the value of Polymer Handbook (3rd Edition) (by J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.
The glass transition temperature based on the calculated value is almost the same as the value measured by the DSC as shown in the examples described later, and is therefore used as an index of the glass transition temperature of the block copolymer that is not salt-formed. be able to.

In the color material dispersion according to the present invention, as the dispersant, at least one of the block copolymer and the salt type block copolymer is used, the content of which is the type of the color material to be used, and a color filter described later. It is appropriately selected according to the solid content concentration in the photosensitive coloring resin composition for use.
The content of the dispersant is preferably 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 colorant dispersion. If it is more than the said lower limit, it is excellent in the storage stability of the dispersibility and dispersion stability of a color material, and the photosensitive coloring resin composition for color filters. Moreover, if it is below the said upper limit, developability will become favorable.
In particular, when a coating film or a colored layer having a high color material concentration is formed, the content of the dispersant is 3 to 25 parts by mass, more preferably 100 parts by mass of the total solid content in the color material dispersion. It is preferable to blend at a ratio of 5 to 20 parts by mass.
In the present invention, the solid content is everything except the above-mentioned solvent, and includes monomers dissolved in the solvent.

<Color material>
In the present invention, the color material is not particularly limited as long as it can form a desired color when the color layer of the color filter is formed, and various organic pigments, inorganic pigments, and dispersible dyes can be used alone. Or a mixture of two or more. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. Examples of the organic pigment include compounds classified as pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. .) Can be listed with numbers.

C. 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 pigment;
C. I.

Pigment Orange

1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;
C. I. Pigment violet 1, 19, 23, 29, 32, 36, 38;
C. I.

Pigment Red

1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 06,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265;
C. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Pigment green 7, 36, 58, 59;
C. I. Pigment brown 23, 25;
C. I. Pigment Black 1 and 7.

Above all, as a coloring material, C.I. I. When the pigment green 59 is included, it is preferable in that a green color material dispersion having a bluish green color, excellent color material dispersion stability, and high luminance can be obtained. By using the green color material dispersion liquid, it is possible to achieve high brightness and high contrast while making the green pixel of the color filter the green chromaticity region of the high color density without increasing the film thickness. become. C. I. The pigment green 59 will be described in detail in the second description of the present invention. In addition, C.I. I. The pigment yellow 150 pigment will also be described in detail in the second description of the present invention.

Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, and oxidation. Examples thereof include chrome green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

For example, when a pattern of a light shielding layer is formed as a photosensitive color resin composition for a color filter, which will be described later, on a color filter substrate, the color material dispersion according to the present invention, a black pigment having a high light shielding property in the ink. Is blended. As the black pigment having a high light shielding property, for example, an inorganic pigment such as carbon black or iron trioxide or an organic pigment such as cyanine black can be used.

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

The average primary particle size of the color material used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a color layer of a color filter, and varies depending on the type of color material used. Is preferably in the range of 10 to 100 nm, more preferably 15 to 60 nm. When the average primary particle diameter of the color material is in the above range, the display device including the color filter manufactured using the color material dispersion according to the present invention has high contrast and high quality. it can.
The average primary particle diameter of the color material in the present invention represents “volume distribution median diameter (D50)”. The average primary particle size of the colorant is determined by attaching a special bright field STEM sample stage and an optional detector to a field emission 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 photo of 200,000 times, import it into the following software, select 100 color materials on the photo, and select each diameter (pass length) And 50% cumulative particle size by volume from the volume-based distribution.
A measurement sample to be subjected to STEM is prepared by mixing a coloring material and toluene and dropping the mixture onto a collodion film-attached mesh. Further, when obtaining a volume-based particle size distribution or volume distribution median diameter (D50) from a STEM photograph, image analysis type particle size distribution measurement software “Mac-View Ver. 4” manufactured by Mountec Co., Ltd. is used.

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

The color material used in the present invention can be produced by a known method such as a recrystallization method or a solvent salt milling method. Further, a commercially available color material may be used after being refined.

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

<Solvent>
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the colorant dispersion and can dissolve or disperse them. A solvent can be used individually or in combination of 2 or more types.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester solvents such as ethyl lactate and cyclohexanol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc. Tone solvents; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxy Carbitol acetate solvents such as ethoxyethyl acetate and butyl carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene Glycol ether solvents such as glycol diethyl ether, propylene glycol monomethyl ether and dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; γ-butyrolactone, etc. Lactone solvents; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; Examples include organic solvents such as aromatic hydrocarbons such as xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used from the viewpoint of solubility of other components. Among them, the solvent used in the present invention includes propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, In addition, one or more selected from the group consisting of 3-methoxybutyl acetate is preferable from the viewpoints of solubility of other components and coating suitability.

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

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

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

<Method for producing colorant dispersion>
In the present invention, the method for producing a color material dispersion is a method in which a color material dispersion in which the color material is dispersed in a solvent by a dispersant of the block copolymer or salt type block copolymer is obtained. If there is no particular limitation. Especially, it is preferable to set it as either of the following two manufacturing methods from the point which is excellent in the dispersibility and dispersion stability of a coloring material.

That is, a first method for producing a colorant dispersion according to the present invention includes a step of preparing a dispersant for the block copolymer or a salt-type block copolymer, and in the presence of the dispersant in a solvent. And a step of dispersing the color material.

A second method for producing a colorant dispersion according to the present invention in the case of using a dispersant that is a salt type block copolymer includes a solvent, the block copolymer, and the general formulas (1) to ( 3) One or more compounds selected from the group consisting of 3) and a coloring material are mixed, and at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) is combined with the compound. And a step of dispersing the coloring material while forming a salt.

In the case of using the salt type block copolymer, according to the first production method, after preparing the salt type block copolymer, the color material is dispersed using the salt type block copolymer as a dispersant. Therefore, the reaction end point and 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) can be accurately confirmed. preferable.
Further, according to the second production method, the color material is dispersed without preparing the salt type block copolymer by self-aggregation because the color material is dispersed while preparing the dispersant for the salt type block copolymer. A liquid can be prepared efficiently and dispersibility can be improved.

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

Specifically, preliminary dispersion is performed with 2.0 mm zirconia beads having a relatively large bead diameter, and the main dispersion is further performed with 0.1 mm zirconia beads having a relatively small bead diameter. Further, after dispersion, it is preferably filtered through a 0.5 to 2 μm filter.

I-2. Photosensitive colored resin composition for color filter according to the first aspect of the invention The photosensitive colored resin composition for color filter according to the first aspect of the invention comprises the color material dispersion according to the first aspect of the invention and an alkali-soluble composition. It contains a resin, a polyfunctional monomer, and a photoinitiator.
The photosensitive colored resin composition for a color filter according to the first aspect of the present invention is excellent in colorant dispersion stability by using the colorant dispersion according to the first aspect of the present invention, while the generation of development residues is suppressed. Further, it is possible to form a colored layer having excellent development adhesion and solvent resolubility and excellent contrast.

The photosensitive colored resin composition for a color filter of the present invention contains at least a colorant, a dispersant, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. Other components may be contained as long as the effects are not impaired. Hereinafter, although each component contained in the photosensitive colored resin composition for a color filter of the present invention will be described, the dispersant, the color material, and the solvent are the same as those described in the color material dispersion according to the present invention. Therefore, explanation here is omitted.

<Alkali-soluble resin>
The alkali-soluble resin in the present invention has an acidic group, acts as a binder resin, and is suitably selected from developers used for pattern formation, particularly preferably those that are soluble in an alkali developer. Can be used.
A preferred alkali-soluble resin in the present invention is a resin having a carboxy group as an acidic group, specifically, an acrylic copolymer having a carboxy group, a styrene-acrylic copolymer having a carboxy group, and a carboxy group. The epoxy (meth) acrylate resin which has is mentioned. Among these, particularly preferred are those having a carboxy group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. These acrylic copolymers, styrene-acrylic copolymers and epoxy acrylate resins may be used in combination of two or more.

The acrylic copolymer having a carboxy group and the styrene-acrylic copolymer having a carboxy group are 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 JP 2013-029832 A, and specific examples thereof include, for example, methyl (meth) acrylate, ethyl (meth) ) A copolymer composed of a monomer having no carboxy group such as acrylate, and one or more selected from (meth) acrylic acid and anhydrides thereof. In addition, for example, a polymer having an ethylenically unsaturated bond 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 can be exemplified, but the present invention is not limited thereto. Is not to be done.
Among these, the addition of an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is particularly preferable in that the sensitivity and film strength of the colored layer become more stable.

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, when the copolymerization ratio of the carboxy group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the resulting 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, there is a tendency that pattern chipping or film roughness on the pattern surface tends to occur during development with an alkali 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 remarkably lowered. If it exceeds 50,000, pattern formation may be difficult during development with an alkali developer.
The weight average molecular weight (Mw) of the carboxy group-containing copolymer can be measured by a Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.

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

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

Although the exact mechanism of the epoxy (meth) acrylate resin having a carboxy group containing a cardo structure (hereinafter referred to as a cardo resin) is unknown, the fluorene skeleton contains a π-conjugated system, so it is highly sensitive to radicals. The required performance such as sensitivity, developability, and development adhesion can be improved by combining an oxime ester photoinitiator described later and a cardo resin. In addition, cardo resin is preferable from the viewpoint that a colored resin composition free from aggregates can be designed even at high color density because of high solvent re-solubility.

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 ( Preferable examples include a reaction product (polycondensate) of meth) acrylate and polybasic acid.

(Here, in the above general formula (B), X represents a group represented by the following general formula (D), Y each independently represents a residue of a polyvalent carboxylic acid or its acid anhydride, 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 0 to 3, and n is an integer of 1 or more.)

(In the general formula (C), R ⁱⁱ represents a hydrogen atom or a methyl group, and R ⁱⁱⁱ independently represents a hydrogen atom or a methyl group.)

(In the 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 O- is shown.)

The cardo resin used in the present invention is, for example, epoxidizing 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.
Preferred examples of the fluorene bisphenol compound include those in which, in the general formula (D), R ^v is —O—, and —O— is —OH.
Examples of the fluorene bisphenol compound 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- Bisphenol compounds such as 3,5-dibromophenyl) fluorene, and mixtures thereof.

Examples of the polyvalent carboxylic acid used in the reaction of the epoxy (meth) acrylate resin having a fluorene skeleton and the acid anhydride thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid. Dicarboxylic acids such as methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, glutaric acid or their anhydrides; biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, biphenylethertetracarboxylic acid, Biphenylsulfone tetracarboxylic acid, 4- (1,2-dicarboxyethyl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, butanetetracarboxylic acid, tetracarboxylic acid such as pyromellitic acid, or That Dianhydride; trimellitic acid or tricarboxylic acids or their anhydrides of the acid anhydrides and the like. 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 addition product of a fluorene epoxy (meth) acrylic acid derivative and a dicarboxylic acid anhydride and / or tetracarboxylic dianhydride. An acid adduct is mentioned.
As a trade name of a commercially available cardo resin that can be used in the present invention, INR-16M (manufactured by Nagase Chemtech Co., Ltd.) and the like can be mentioned.
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 colored resin composition for color filters may be used singly or in combination of two or more, and the content is not particularly limited. The alkali-soluble resin is preferably in the range of 5 to 60% by mass, more preferably 10 to 40% by mass, based on the total solid content of the photosensitive colored resin composition for filters. If the content of the alkali-soluble resin is less than the above lower limit, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin is more than the above upper limit, the film may be rough during development. Pattern chipping may occur. In the present invention, the solid content is everything except the above-mentioned solvent, and includes a liquid polyfunctional monomer.

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

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

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

As the oxime ester photoinitiator, those having an aromatic ring are preferable from the viewpoint of reducing the contamination of the photosensitive colored resin composition for color filters and the contamination of the apparatus due to decomposition products, and a condensed ring containing an aromatic ring is preferable. It is more preferable to have a condensed ring including a benzene ring and a hetero ring.
Examples of oxime ester photoinitiators include 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime), JP 2000-80068 A, JP 2001-233842 A, Special Table 2010-527339, Special Table 2010-527338, It can be appropriately selected from oxime ester photoinitiators described in JP2013-041153A. Commercially available products include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above BASF), ADEKA OPT-N-1919, Adeka Arkles NCI-930, Adeka Arkles NCI-831 (above, ADEKA) TR-PBG-304, TR-PBG-326, TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), etc. may be used.

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

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

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

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

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

When the antioxidant is used, the amount of the antioxidant is not particularly limited as long as the effect of the present invention is not impaired. The blending amount of the antioxidant is preferably 0.1 to 5.0% by mass of the antioxidant with respect to the total solid content in the photosensitive colored resin composition for a color filter, preferably 0.5 to It is more preferable that it is 4.0 mass%. If it is more than the said lower limit, it is excellent in heat resistance. On the other hand, if it is below the said upper limit, the photosensitive colored resin composition for color filters of this invention can be used as the highly sensitive photosensitive colored resin composition for color filters.

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

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

<Method for Producing Photosensitive Colored Resin Composition for Color Filter>
The method for producing the photosensitive colored resin composition for a color filter of the present invention is not particularly limited. For example, the colorant dispersion according to the present invention includes an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and necessary. Depending on the case, it can be obtained by adding other components and mixing them using a known mixing means.

I-3. The color filter according to the first invention The color filter according to the first invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers. One has a colored layer formed by curing the photosensitive colored resin composition for a color filter according to the first aspect of the present invention.

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

<Colored layer>
At least one colored layer 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 an opening of a light shielding part on a transparent substrate, which will be described later, and is usually composed of three or more colored patterns.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, etc. of the photosensitive colored resin composition for color filters, but is usually preferably in the range of 1 to 5 μm. .

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

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

<Light shielding part>
The light shielding part 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 part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. The light shielding part may be a metal thin film such as chromium by sputtering, vacuum deposition or the like. Alternatively, the light shielding part may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring the photosensitive resist, etc. is there.

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

<Transparent substrate>
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, transparent flexible rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible flexible materials such as transparent resin films, optical resin plates, and flexible glasses. Materials.
The thickness of the transparent substrate is not particularly limited, but for example, a thickness of about 100 μm to 1 mm can be used according to the use of the color filter of the present invention.
The color filter of the present invention is one in which, for example, an overcoat layer, a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, and the like are formed in addition to the transparent substrate, the light shielding portion, and the colored layer. May be.

I-4. The liquid crystal display device according to the first aspect of the invention is the liquid crystal display device of the first aspect of the invention formed between the color filter according to the first aspect of the invention, the counter substrate, and the color filter and the counter substrate. And a liquid crystal layer.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.

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

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, and the liquid crystal is heated to obtain an isotropic liquid, and the liquid crystal is applied to the liquid crystal cell using the capillary effect. The liquid crystal layer can be formed by injecting in this state and sealing with an adhesive. Thereafter, the sealed liquid crystal can be aligned 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. In addition, the liquid crystal layer can be formed by overlapping the color filter and the counter substrate under reduced pressure and bonding them with a sealant. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

I-5. Organic light-emitting display device according to the first aspect of the invention An organic light-emitting display device according to the first aspect of the invention includes the color filter according to the first aspect of the 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 illustrating an example of the organic light emitting display device of the present invention. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

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

II. Second Invention Hereinafter, the color material dispersion for color filter, the photosensitive colored resin composition for color filter, the color filter, the liquid crystal display device and the organic light emitting display device according to the second invention will be described in detail in order. .

II-1. Colorant dispersion according to the second aspect of the present invention (i) First embodiment of the second aspect of the present invention The colorant dispersion for a color filter according to the first embodiment of the second aspect of the present invention comprises a colorant, a dispersion A colorant dispersion containing an agent and a solvent,
The color material is C.I. I. Including Pigment Green 59,
The dispersant is a polymer having a structural unit represented by the following general formula (I).

In the color material dispersion according to the first embodiment of the second invention, the color material is C.I. I. Pigment Green 59 (hereinafter sometimes abbreviated as PG59), and as a dispersant used in combination with a polymer having a structural unit represented by General Formula (I), exhibits a bluish green color, A green color material dispersion having excellent color material dispersion stability and high brightness can be obtained.
In the second aspect of the present invention, since PG59 is used as the color material, a chromaticity region that cannot be achieved with PG58 can be achieved, and a polymer having a structural unit represented by the general formula (I) is used in combination. Therefore, while achieving high brightness and high contrast, a color filter having a large triangle connecting three points of red, green, and blue pixels and having excellent color reproducibility can be created.

In addition, the color material dispersion according to the first embodiment of the second aspect of the present invention combines PG59 with a polymer having a structural unit represented by the general formula (I) as a dispersant. It is possible to produce a photosensitive colored resin composition excellent in solvent resolubility. Since the colorant containing PG59 is combined with the polymer having the structural unit represented by general formula (I) as a dispersant, the colorant containing PG59 is included in the structural unit represented by general formula (I). Color material containing PG59 firmly adsorbed to the nitrogen site and surrounded by the dispersant is easily washed away into the re-dissolvable solvent while adsorbing firmly to the nitrogen site and excellent in color material dispersibility. It is estimated to be. Moreover, when the polymer which has a structural unit represented by general formula (I) as a dispersing agent was combined with the coloring material containing PG59, the tendency for generation | occurrence | production of a development residue to be suppressed was seen. This is because the coloring material including PG59 firmly adsorbed on the nitrogen site and surrounded by the dispersing agent is easily flown while being adsorbed by the dispersing agent during the development, so that the coloring material is not left on the base material, and the development residue It is presumed that the occurrence of this is likely to be suppressed.

(Ii) Second embodiment of the second invention The color material dispersion for a color filter according to the second embodiment of the second invention includes a color material, a dispersant, and a solvent. A dispersion,
The color material is C.I. I. Pigment Green 59, and yellow color material,
It is mentioned that the said dispersing agent is a polymer which has a structural unit represented by the said general formula (I).

In the color material dispersion according to the second embodiment of the second aspect of the present invention, the color material contains PG59 and a yellow color material, and has a structural unit represented by the general formula (I) as a dispersant. Since a combination is used in combination, it is possible to form a colored layer having excellent colorant dispersion stability and high luminance and excellent color reproducibility while suppressing the occurrence of display defects.
PG59 used as a color material in the second aspect of the present invention exhibits a single color and bluish green, has a relatively strong coloring power, and has a high luminance. Therefore, PG59 in the color material can be combined with a yellow color material. Even if the content of S is suppressed, or the P / V ratio ((color material component mass in the composition) / (solid content mass other than color material components in the composition) ratio) is suppressed, the high color A green pixel included in the density green chromaticity region can be produced. It is presumed that the display defect is likely to occur in the green pixel due to the green color material having the phthalocyanine skeleton. However, when the color material dispersion liquid of the present invention is used, the green pixel in the pixel of the green color material having the phthalocyanine skeleton is used. Since the content can be reduced and the P / V ratio can be reduced, it is estimated that a green pixel in which the occurrence of display defects is suppressed can be achieved.
In addition, PG59 used as a color material in the second aspect of the present invention can achieve a chromaticity region that could not be achieved by PG58 in the high color density green chromaticity region. Furthermore, in the second embodiment of the second invention, since PG59 and the yellow color material are combined with the polymer having the structural unit represented by the general formula (I), the color material dispersibility and Because of excellent colorant dispersion stability, it is possible to create a color filter with excellent color reproducibility with a large triangle connecting the three red, green, and blue pixels while achieving high brightness and high contrast. it can.
Further, the color material dispersion of the second embodiment of the second aspect 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. A photosensitive colored resin composition having excellent solubility can be produced. Since PG59 and the yellow color material are combined with the polymer having the structural unit represented by the general formula (I) as a dispersant, the PG59 and the yellow color material which are firmly adsorbed on the nitrogen site and surrounded by the dispersant are It is presumed that the re-dissolvable solvent tends to flow while adsorbed on the dispersant.

In the color material dispersion for a color filter according to the second embodiment of the second aspect of the present invention, the PG59 is contained in the color material in an amount of 5 to 95% by mass while suppressing the occurrence of display defects. From the viewpoint of widening the color reproducibility and increasing the luminance.

In the color material dispersion for a color filter according to the second embodiment of the second invention, the yellow color material is C.I. I. Pigment yellow 138 (hereinafter sometimes abbreviated as PY138), C.I. I. Pigment yellow 139 (hereinafter sometimes abbreviated as PY139), C.I. I. Pigment yellow 185 (hereinafter sometimes abbreviated as PY185), C.I. I. One or more selected from the group consisting of CI Pigment Yellow 150 (hereinafter sometimes abbreviated as PY150) and its derivative pigments, and high color reproduction with high brightness and high contrast while suppressing the occurrence of display defects. It is preferable because it is easy to form a colored layer excellent in.

In the color material dispersion for a color filter according to the second embodiment of the second invention, the color material is C.I. I. Pigment green 58 and C.I. I. It is preferable that at least one pigment green 7 is included. Among them, it is preferable to include PG58 in addition to PG59 from the viewpoint that a high-luminance green pixel can be formed while achieving the target chromaticity and suppressing display defects. On the other hand, it is preferable to include PG7 in addition to PG59 from the viewpoint of reducing the P / V ratio and improving plate making properties such as development resistance while achieving the target chromaticity and suppressing display defects. . In addition to PG59, PG58 and PG7 are included from the viewpoint of the balance between improving luminance and reducing the P / V ratio while achieving target chromaticity and suppressing display defects. Is preferred.

(Iii) Third embodiment of the second aspect of the present invention The color filter dispersion for a color filter according to the third embodiment of the second aspect of the present invention includes a color filter containing a colorant, a dispersant, and a solvent. A colorant dispersion for
The color material is C.I. I. Pigment Green 59, a blue color material, and a yellow color material, and the yellow color material is (Y1) C.I. I. At least one yellow colorant including CI Pigment Yellow 185, or (Y2) C.I. I. Pigment Yellow 139 as an essential component and C.I. I. Pigment yellow 138, C.I. I. Pigment Yellow 150 and at least two kinds of yellow color materials including one or more selected from the group consisting of derivative pigments thereof,
It is mentioned that the said dispersing agent is a polymer which has a structural unit represented by the said general formula (I).

The color material dispersion according to the third embodiment of the second aspect of the present invention is a combination of the specific color material and a polymer having a structural unit represented by the general formula (I) as a dispersant. Since it is used, it is possible to form a colored layer having excellent color material dispersion stability and high brightness and excellent color reproducibility while suppressing the occurrence of display defects.
According to the color material dispersion liquid according to the third embodiment of the second aspect of the present invention, as a yellow color material, by combining either (Y1) or (Y2) above with PG59 and a blue color material, G59 and It is estimated that it is possible to efficiently absorb the wavelength portion that is insufficiently absorbed by the blue color material, and the color can be reproduced by reducing the total amount of the color material, that is, by reducing the P / V ratio. The For this reason, among the high color density green chromaticity, the high color density green (x = 0.14 to 0.30, y = 0.61 to 0.75) region, and further (x = 0). .14 to 0.30, y = 0.66 to 0.75), while suppressing display defects and forming a high-luminance colored layer.
In addition, the specific yellow color material is excellent in dispersibility when combined with a specific dispersant described later, so that it is easy to improve the contrast and a photosensitive colored resin composition excellent in solvent resolubility can be produced. It is.

In the color material dispersion according to the third embodiment of the second invention, the blue color material is C.I. I. Pigment blue 15: 3 and C.I. I. It is preferable from the point of a brightness | luminance to contain at least 1 sort (s) of pigment blue 15: 4.

The colorant dispersion according to the second aspect of the present invention contains at least a colorant, a dispersant, and a solvent, and may further contain other components as long as the effects of the present invention are not impaired. It ’s good.
Hereinafter, each component of the color material dispersion according to the second aspect of the present invention will be described in detail.

<Color material>
In the second aspect of the present invention, the coloring material is C.I. which is a zinc phthalocyanine pigment. I. Pigment Green 59 is included.
PG59 is a color that can display 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 using a C light source alone. The colorant is characterized by being capable of displaying x = 0.13 to 0.20 and y = 0.32 to 0.60.

The PG 59 is characterized in that it can display an xy chromaticity coordinate area surrounded by the following

equations

1, 2 and 3 in the XYZ color system of JIS Z8701 measured by using a C light source alone.
(Equation 1)
y = 6.715 × x-0.286
However, in Equation 1, 0.121 <x <0.133
(Equation 2)
y = 7147.200 × x ⁵ -8466.000 × x ⁴ + 3891.400 × x ³ −854.200 × x ² + 86.380 × x−2.579
However, in Equation 2, 0.133 <x <0.310
(Equation 3)
y = 1189.500 × x ⁶ + 1817.000 × x ⁵ −3011.300 × x ⁴ + 1447.800 × x ³ −307.420 × x ² + 27.628 × 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.

PG59 used in the present invention has a wavelength (Tmax) at which the transmittance of the spectral transmittance spectrum at 400 to 700 nm is maximum at 505 to 535 nm when the transmittance at 450 nm is 5%. Furthermore, the transmittance at the wavelength (Tmax) is 70% or more. Further, 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 of 5% or less.

In order to measure the color of PG59 by coating it alone, prepare a coating solution by blending PG59 with an appropriate dispersant, binder component and solvent, apply it on a transparent substrate and dry it. It may be cured accordingly. As a binder component, a non-curable thermoplastic resin composition may be used as long as a transparent coating film capable of performing colorimetry can be formed, or a photo-curable (photosensitive) or thermosetting resin composition. May be used. Moreover, in the photosensitive coloring resin composition of this invention mentioned later, the coating film which contains only PG59 as a coloring material can be formed by using the composition which contains only PG59 as a coloring material, and can also perform colorimetry.
As a transparent coating film including a dispersant and a binder component that can perform colorimetry, for example, the film thickness is 2.0 μm, and the transmittance of the spectral transmittance spectrum at 380 to 780 nm is 95% or more. can do.
The spectral transmittance spectrum can be measured using a spectroscopic measurement device (for example, an Olympus microscope OSP-SP200). The measurement condition is a C light source.

In the color material dispersion according to the present invention, only PG59 may be used alone as the color material. On the other hand, as long as the effect of the present invention is not impaired, a color material different from PG59 exemplified in the color material section of the color material dispersion according to the first invention is combined with PG59 as another color material. May be used. As other color materials, for example, other green color materials, yellow color materials, and blue color materials are preferably used.

In the color material dispersion according to the second aspect of the present invention, when another color material different from PG59 is used, the content of PG59 may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Especially, it is preferable to contain 5 mass% or more with respect to the whole coloring material containing PG59, and it is more preferable to contain 10 mass% or more from the point which makes color reproducibility wide and raises a brightness | luminance.

Further, in the color material dispersion according to the second aspect of the present invention, it is possible to use PG59 as a color material in combination with a yellow color material, while suppressing the occurrence of display failure of the green pixel and increasing the color with high brightness. It is preferable from the point which can form the colored layer excellent in reproducibility (2nd embodiment of 2nd this invention).
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 pigment.

C. I. Specific examples of pigment yellow 150 pigment pigments include mono-, di-, tri- and tetra-azo compounds of the azo compound according to the following chemical formula (i) or one of its tautomeric structures that serve as a host for at least one guest compound. Examples of the metal complex include an anion and a metal. Examples of the metal include Li, Cs, Mg, Cd, Co, Al, Cr, Sn, and Pb, preferably Na, K, Ca, Sr, Ba, Zn, and Fe. , Ni, Cu, Mn and La. Ni is preferable as the metal, and more preferably, the C.I. containing Ni and Zn. I. Pigment Yellow 150 derivative pigment, and the C.I. I. At least one pigment pigment of pigment yellow 150 is desirable. Among them, the C.I. containing Ni and Zn at a ratio (molar ratio) of Ni: Zn = 8: 2 to 2: 8. I. Pigment Yellow 150 derivative pigment, and said C.I. containing Ni and Zn in a ratio (molar ratio) of Ni: Cu = 5: 5 to 9.8: 0.2. I. At least one pigment pigment of pigment yellow 150 is preferred.

(In the chemical formula (i), each R is independently OH, NH ₂ , NH—CN, acylamino or arylamino, and each R ′ is independently —OH or —NH ₂ )

C. I. Pigment Yellow 150 and derivative pigments thereof are disclosed in JP-A No. 2001-354869, JP-A No. 2005-325350, JP-A No. 2007-25687, JP-A No. 2007-23287, JP-A No. 2007-23288, and It can be obtained by referring to Japanese Patent Application Laid-Open No. 2008-24927.
Moreover, a commercial item can be used suitably for the said yellow color material.

In the color material dispersion of the second aspect 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 colored resin composition for color filter described later.

In addition, in the color material dispersion liquid of the second embodiment of the second present invention, as long as the effects of the present invention are not impaired, the PG59 and the yellow color material may be other than those exemplified in the photosensitive colored resin composition described later. These color materials may be used in combination. As other color materials, for example, other green color materials, blue color materials, orange color materials and the like are preferably used. Examples of other green color materials different from PG59 include phthalocyanine green pigments such as PG58, PG7, and PG36. As other suitable color materials, other similar color materials are preferably used for the same reason as described in the photosensitive coloring resin composition for color filters described later.
In the color material dispersion liquid of the second aspect of the present invention, when other green color material is further included, the yellow color material is used in combination with at least one of PY150 and its derivative pigments and PY138. From the viewpoint of easily achieving a high-luminance colored layer while suppressing the occurrence of display defects.

In the color material dispersion liquid of the second embodiment of the second invention, the content ratio of PG59 to the entire color material, the content ratio of the yellow color material to PG59, and PG59, the yellow color material, and other color materials When used, the content ratio is preferably the same as the photosensitive colored resin composition described later. However, since the photosensitive coloring resin composition can be produced by mixing two or more kinds of coloring material dispersions as appropriate, it is not necessary to have the same content ratio as the photosensitive coloring resin composition described later. Used for.

In the color material dispersion according to the second aspect of the present invention, as the color material, PG59 is combined with a blue color material and a yellow color material, and the yellow color material contains at least one kind of (Y1) PY185. It is a yellow color material, or (Y2) at least two kinds of yellow color materials containing PY139 as an essential component and further including one or more selected from the group consisting of PY138, PY150 and PY150 derivative pigments Preferred (third embodiment of the second invention).

In the present invention, the blue color material is a color material having a peak top in a range from 435 nm to 490 nm when a spectral transmittance spectrum is measured in the same manner as described for PG59.
Examples of the blue color material include C.I. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 60, and the like. From among the dispersible dyes described in the photosensitive coloring resin composition described later, a color material that falls within the range of the blue color material may be appropriately selected and used.
In the color material dispersion according to the third embodiment of the second aspect of the present invention, the blue color material is appropriately selected and used alone or in combination of two or more.

Among these, as the blue color material used in the third embodiment of the second aspect of the present invention, the combination of PG59 and the specific yellow color material can suppress a decrease in luminance, and the specific dispersion. From the viewpoint of excellent dispersibility when combined with an agent, a β-type copper phthalocyanine pigment is preferable. I. Pigment blue 15: 3 and C.I. I. It is preferable to include at least one of Pigment Blue 15: 4, and it is preferable to include these β-type copper phthalocyanine pigments in an amount of 60% by mass to 100% by mass in the total amount of the blue color material.
Among these, the blue color material is C.I. I. Pigment blue 15: 3 and C.I. I. It is preferably at least one of pigment blue 15: 4.

In the third embodiment of the second aspect of the present invention, (Y1) at least one yellow color material containing PY185 may further contain another yellow color material in addition to PY185, and as the yellow color material, Is, for example, PY1, 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, and PY150 derivative pigments.
In the third embodiment of the second aspect of the present invention, the yellow color material combined with PY185 is at least one selected from the group consisting of PY139, PY150 and derivative pigments, and has excellent color material dispersion stability. From the viewpoint of easily achieving a colored layer having high luminance and excellent color reproducibility while suppressing the occurrence of display defects.

In the third embodiment of the second aspect of the present invention, (Y2) at least two yellow colorants containing PY139 as an essential component and further including one or more selected from the group consisting of PY138, PY150 and derivative pigments thereof. In addition to the at least two kinds of yellow color materials, other yellow color materials may be further included. Examples of the yellow color materials include PY1, 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, 151, 152, 153, 154, 155, 156, 166, 168, and 175. That.

In the third embodiment of the second aspect of the present invention, when (Y1) is used as the yellow color material, it is preferable from the viewpoint that higher luminance can be easily achieved. On the other hand, when (Y2) is used as the yellow color material, it is preferable from the viewpoint of easily achieving high contrast.
In the third embodiment of the second aspect of the present invention, the (Y2) PY139 is an essential component, and at least two kinds of yellow color materials further including one or more selected from the group consisting of PY138, PY150 and derivative pigments thereof. Among them, at least two kinds of yellow color materials containing PY139 as an essential component and further including one or more selected from the group consisting of PY150 and its derivative pigments have a high brightness and a high brightness while suppressing the occurrence of display defects. It is preferable from the viewpoint of easily achieving a contrast colored layer.

Further, in the color material dispersion of the third embodiment of the second invention, the photosensitive coloring resin described later is added to PG59, the blue color material, and the specific yellow color material, as long as the effects of the invention are not impaired. Other colorants such as those exemplified in the composition may be used in combination. As other color materials, for example, other green color materials, orange color materials, and the like are preferably used. As other suitable color materials, other similar color materials are preferably used for the same reason as described in the photosensitive coloring resin composition for color filters described later. In the present invention, the green color material is a color material having a peak top in the range of more than 490 nm and less than 580 nm when the spectral transmittance spectrum is measured in the same manner as described above.

In the color material dispersion liquid according to the third embodiment of the second invention, each content ratio of PG59, blue color material, and yellow color material, and the content ratio when other color materials are used are the photosensitive coloring described later. The content ratio is preferably the same as that of the resin composition. However, since the photosensitive coloring resin composition can be produced by mixing two or more kinds of coloring material dispersions as appropriate, it is not necessary to have the same content ratio as the photosensitive coloring resin composition described later. Used for.

As the average primary particle size of the color material used in the second invention and the average dispersion particle size of the color material in the color material dispersion, the term of the color material of the color material dispersion according to the first invention described above. Since it may be the same as that described in FIG.
In the color material dispersion according to the second aspect of the invention, the content of the color material may be the same as that described in the section of the color material of the color material dispersion according to the first aspect of the invention. The description here is omitted.

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

The structural unit represented by the general formula (I) may be the same as that described in the section of the dispersant for the colorant dispersion according to the first aspect of the present invention, and the description thereof is omitted here. .

In the polymer having the structural unit represented by the general formula (I), at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the following general formulas (1) to ( 3) that one or more compounds selected from the group consisting of the compounds represented by the salt form a salt, the colorant adsorbability is further improved at the salt-forming site, the colorant dispersion stability, and It is preferable from the viewpoint of excellent solvent resolubility.
One or more compounds selected from the group consisting of the following general formulas (1) to (3) are described in the section of the salt-type block copolymer of the dispersant for the colorant dispersion according to the first aspect of the present invention. Since it may be the same as that described above, description thereof is omitted here.

(The symbols in general formulas (1) to (3) are as described above.)

Further, in the dispersant used in the second present invention, one kind selected from the group consisting of the general formulas (1) to (3) in the polymer having the structural unit represented by the general formula (I) The content of the above compound may be the same as that described in the section of the salt-type block copolymer of the dispersant of the colorant dispersion according to the first aspect of the invention, and the description thereof is omitted here. To do.

The polymer having the structural unit represented by the general formula (I) preferably further includes a portion having solvent affinity from the viewpoint of improving dispersibility. As the solvent affinity site, a monomer having an ethylenically unsaturated bond that can be polymerized with a monomer that derives the structural unit represented by the general formula (I) is selected depending on the solvent so as to have solvent affinity. It is preferable to select and use as appropriate. As a standard, it is preferable to introduce a solvent-affinity site so that the solubility of the polymer at 23 ° C. is 20 (g / 100 g solvent) or more with respect to the solvent used in combination.
As the polymer having the structural unit represented by the general formula (I) used in the second aspect of the present invention, the dispersibility and dispersion stability of the coloring material and the heat resistance of the resin composition are improved. Among these, a block copolymer or a graft copolymer is preferable, and a block copolymer is particularly preferable because a contrast colored layer can be formed. Hereinafter, particularly preferred block copolymers will be described in detail.

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

The dispersant used in the second invention is a block copolymer having a structural unit represented by the general formula (I), and the amine value of the block copolymer is 40 mgKOH / g or more and 130 mgKOH / g. That C. I. It is preferable from the viewpoint of improving the dispersibility and dispersion stability of CI Pigment Green 59.
In the dispersant used in the second invention, the lower limit is more preferably 50 mgKOH / g or more, and even more preferably 60 mgKOH / g or more, from the viewpoint of colorant dispersibility and dispersion stability. preferable. Moreover, as an upper limit, it is still more preferable that it is 120 mgKOH / g or less. If it is more than the said lower limit, dispersion stability is more excellent. Moreover, if it is below the said upper limit, it is excellent in compatibility with another component and solvent resolubility becomes favorable.
In the case of the salt type block copolymer, the amine value becomes smaller by the amount of salt formation than the block copolymer before salt formation. However, since the salt formation site is the same as the terminal nitrogen site corresponding to the amino group, or rather becomes a strengthened color material adsorption site, the color material dispersibility and color material dispersion stability tend to be improved by salt formation. is there. In addition, like the amino group, if the salt forming site is too much, the solvent resolubility is adversely affected. Therefore, in the present invention, the amine value of the block copolymer before salt formation can be used as an index for improving the colorant dispersion stability and solvent resolubility. The amine value of the obtained salt-type block copolymer (P2) is preferably from 0 mgKOH / g to 130 mgKOH / g, and more preferably from 0 mgKOH / g to 120 mgKOH / g.
If it is below the above upper limit, the compatibility with other components is excellent, and the solvent resolubility becomes good.

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

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

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

Examples of the structural unit constituting the B block include a monomer having an unsaturated double bond copolymerizable with the monomer that derives the structural unit represented by the general formula (I). The structural unit represented by (II) is preferred.
The structural unit represented by the following general formula (II) may be the same as that described in the section of the dispersant of the colorant dispersion according to the first aspect of the present invention, and the description thereof is omitted here. .

(The symbols in general formula (II) are as described above.)

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

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

Moreover, the content ratio of the structural unit represented by the general formula (II) in the block copolymer before salt formation improves the color material dispersibility and dispersion stability. The amount is preferably 40 to 95% by mass, more preferably 50 to 90% by mass based on the total mass of the units. In addition, the content rate of the said structural unit is computed from the preparation mass at the time of synthesize | combining the block copolymer before salt formation.

The dispersant is at least one of the following block copolymer (P1) and the following salt-type block copolymer (P2),
P1: a block copolymer containing an A block containing the structural unit represented by the general formula (I) and a B block containing a structural unit derived from a carboxy group-containing monomer;
P2: From the group consisting of 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 general formulas (1) to (3) A salt-type block copolymer in which one or more selected compounds form a salt;
Use of a dispersant having an acid value of 1 mgKOH / g or more and 18 mgKOH / g or less and a glass transition temperature of 30 ° C or more of the dispersant is excellent in colorant dispersion stability and suppresses development residue generation. Although it is excellent in the effect, it is excellent in solvent re-solubility, and it is preferable from the viewpoint of having high development adhesiveness when a colored resin composition is obtained.
When the colorant concentration is increased and the dispersant content is increased, the amount of the binder is relatively decreased. Therefore, the colored resin layer is easily peeled off from the base substrate during development. When the dispersant contains a B block containing a structural unit derived from a carboxy group-containing monomer and has the specific acid value and glass transition temperature, the development adhesion is improved. If the acid value is too high, the developability is excellent, but it is presumed that the polarity is too high and peeling easily occurs during development.
Such a dispersant may be the same as that described in the section of the dispersant used in the color material dispersion according to the first aspect of the present invention, and thus description thereof is omitted here.

In the color material dispersion according to the second aspect of the present invention, as the dispersant, at least one polymer having the structural unit represented by the general formula (I) is used, and the content thereof is determined by the color material used. It is appropriately selected according to the type and the solid content concentration in the photosensitive colored resin composition for color filter described later.
The content of the dispersant in the color material dispersion according to the second aspect of the present invention may be the same as that described in the dispersant used in the color material dispersion according to the first aspect of the present invention. The description of is omitted.

In the color material dispersion according to the second aspect of the present invention, the solvent used and the content thereof, other components that may be blended as necessary, and the method for producing the color material dispersion are the first Since it may be the same as that described in the color material dispersion according to the present invention, description thereof is omitted here.

The colorant dispersion according to the second aspect of the present invention is used as a preliminary preparation for preparing a photosensitive colored resin composition for a color filter according to the second aspect of the present invention described later. That is, the color material dispersion is preliminarily prepared in the previous stage of preparing a photosensitive colored resin composition for a color filter described later, (color material component mass in the composition) / (color material component in the composition). Is a colorant dispersion having a high solid content mass ratio. Specifically, the ratio of (mass of color material component in composition) / (mass of solid content other than color material component in composition) is usually 1.0 or more. It is possible to prepare a photosensitive colored resin composition for a color filter according to the second invention excellent in dispersibility by mixing the colorant dispersion according to the second invention and each component described later. it can.

II-2. Photosensitive colored resin composition for color filters according to the second aspect of the present invention (i) First embodiment of the second aspect of the invention Photosensitive colored resin composition for a color filter according to the first aspect of the second aspect of the present invention Is a photosensitive colored resin composition for a color filter containing a coloring material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent,
The color material is C.I. I. Including Pigment Green 59,
The dispersant is a polymer having a structural unit represented by the general formula (I).
In the photosensitive colored resin composition for a color filter according to the first embodiment of the second invention, the color material is C.I. I. By including the pigment green 59, it is possible to form a colored layer that can achieve high luminance and high contrast while maintaining the green chromaticity region of high color density. The photosensitive colored resin composition for a color filter according to the first embodiment of the second aspect of the present invention has the same effect as that described in the color material dispersion of the first embodiment of the second aspect of the present invention. A colored layer having excellent solubility, high luminance, high contrast, and excellent color reproducibility can be formed.

(Ii) Second Embodiment of the Second Invention As the photosensitive colored resin composition for a color filter according to the second embodiment of the second invention, a coloring material, a dispersant, an alkali-soluble resin, A photosensitive colored resin composition for a color filter containing a polyfunctional monomer, a photoinitiator, and a solvent,
The color material is C.I. I. Pigment Green 59, and yellow color material,
It is mentioned that the said dispersing agent is a polymer which has a structural unit represented by the following general formula (I).

In the photosensitive colored resin composition for color filters according to the second embodiment of the second invention, the colorant is C.I. I. Since the pigment green 59 and the yellow color material are used, and the polymer having the structural unit represented by the general formula (I) is used in combination as a dispersant, the color of the second embodiment of the second invention is used. By the same action as described in the material dispersion liquid, it is possible to form a colored layer having excellent color material dispersion stability and high luminance and excellent color reproducibility while suppressing the occurrence of display defects.

(Iii) Third embodiment of the second invention As the photosensitive colored resin composition for a color filter according to the third embodiment of the second invention, a coloring material, a dispersant, an alkali-soluble resin, A photosensitive colored resin composition for a color filter containing a polyfunctional monomer, a photoinitiator, and a solvent,
The color material is C.I. I. Pigment Green 59, a blue color material, and a yellow color material, and the yellow color material is (Y1) C.I. I. At least one yellow colorant including CI Pigment Yellow 185, or (Y2) C.I. I. Pigment Yellow 139 as an essential component and C.I. I. Pigment yellow 138, C.I. I. Pigment Yellow 150 and at least two kinds of yellow color materials including one or more selected from the group consisting of derivative pigments thereof,
It is mentioned that the said dispersing agent is a polymer which has a structural unit represented by the following general formula (I).

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second invention, the color material is C.I. I. Since the pigment green 59, the blue color material, and the specific yellow color material are used in combination with a polymer having a structural unit represented by the general formula (I), the second aspect of the present invention is used. In the same manner as described in the color material dispersion liquid of the third embodiment, a colored layer having excellent color material dispersion stability and high brightness and excellent color reproducibility is formed while suppressing the occurrence of display defects. Is possible.

The photosensitive colored resin composition for a color filter according to the second aspect of the present invention contains at least a colorant, a dispersant, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. Further, other components may be contained as long as the effects of the present invention are not impaired. Hereinafter, although each component contained in the photosensitive coloring resin composition for color filters of 2nd this invention is demonstrated, C. which is an essential component among color materials. I. Since the pigment green 59 and the dispersant are the same as those described in the color material dispersion of the second invention, the description thereof is omitted here. Moreover, about a solvent, since it may be the same as that of what was demonstrated by the color material dispersion liquid of said 1st this invention, description here is abbreviate | omitted. The alkali-soluble resin, the polyfunctional monomer, the photoinitiator, and other components may be the same as those described in the photosensitive color resin composition for color filters according to the first aspect of the present invention. Therefore, explanation here is omitted.

<Color material>
The coloring material in the photosensitive colored resin composition for a color filter according to the second aspect of the present invention includes C.I. I. Pigment Green 59 is included, but other color materials may be used in combination in order to adjust the color tone.
It is not particularly limited as long as it can form a desired color when forming the color layer of the color filter, and various organic pigments, inorganic pigments, dispersible dyes may be used alone or in combination of two or more. Can be used. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. Examples of the organic pigment include compounds classified as pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. .) Can be listed with numbers.
As other color materials, color materials different from PG59 exemplified in the color material section of the color material dispersion according to the first aspect of the present invention may be used in combination as other color materials. Of these, yellow color materials, other green color materials, and blue color materials are preferably used.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, it is possible to use PG59 in combination with a yellow color material as a color material, while suppressing the occurrence of display defects of green pixels. It is preferable from the viewpoint that a colored layer having high luminance and excellent color reproducibility can be formed (second embodiment of the second invention). The yellow color material used in the second embodiment of the second invention may be the same as that described in the color material dispersion of the second embodiment of the second invention. As other color materials used in the second embodiment of the second invention, other green color materials, blue color materials, and orange color materials are preferably used.

Especially, in the photosensitive coloring resin composition for color filters of 2nd embodiment of 2nd this invention, it is preferable to contain at least 1 sort (s) of PG58 and PG7 in addition to PG59. Among them, it is preferable to include PG58 in addition to PG59 from the viewpoint that a high-luminance green pixel can be formed while achieving the target chromaticity and suppressing display defects. When PG59 and PG58 are used in combination, the color reproducibility can be broadened, the P / V ratio can be reduced, and the luminance can be improved as compared with using PG58 alone. On the other hand, PG7 is included in addition to PG59 from the viewpoint of reducing the P / V ratio and improving plate making properties such as development resistance while achieving the target chromaticity and suppressing display defects. Is preferred. In addition to PG59, PG58 and PG7 are included from the viewpoint of the balance between improving luminance and reducing the P / V ratio while achieving target chromaticity and suppressing display defects. Is preferred.

In the photosensitive colored resin composition for a color filter according to the second embodiment of the second invention, the content ratio of PG59 with respect to the entire color material is not particularly limited as long as it is appropriately adjusted according to the desired chromaticity. Among them, it is preferable to contain 5 to 95% by mass of PG59 with respect to the entire color material including PG59 from the viewpoint of widening the color reproducibility and increasing the luminance while suppressing the occurrence of display defects. The content is more preferably 90% by mass, and still more preferably 20 to 80% by mass.

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

In the photosensitive colored resin composition for a color filter according to the second embodiment of the second invention, the yellow color material is appropriately selected and used alone or in combination of two or more. Among them, PY138, PY139 Using one or more selected from the group consisting of PY185, PY150 and its derivative pigments makes it easy to achieve a colored layer with high brightness, high contrast and excellent color reproducibility while suppressing the occurrence of display defects It is preferable from the point.
In the second embodiment of the second aspect of the present invention, PY150 and its derivative pigment are used particularly when displaying a chromaticity region of y = 0.550 to 0.610 and x = 0.205 to 0.324. It is preferable that the P / V ratio is more easily reduced in the chromaticity region.
PY138 is preferably used to achieve high luminance in the chromaticity region of y = 0.550 to 0.610 and x = 0.205 to 0.324. It is preferably used when high luminance is achieved in the 324 chromaticity region.
PY185 is suitable for widening the color reproduction range, and is preferable for displaying a chromaticity region of x = 0.205 to 0.324 even when y = 0.610 to 0.626. It is preferable to use when displaying a chromaticity region of y = 0.659.

In the photosensitive colored resin composition for a color filter according to the second embodiment of the second aspect of the present invention, in particular, when PY138 is used in combination with at least one of PY150 and its derivative pigment, the desired chromaticity, The ratio of the total amount of at least one of PY150 and its derivative pigment and PY138 and PY138 is preferably 5:95 to 95: 5. In particular, from the viewpoint of luminance 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. From the point of V, it is more preferably 20:80 to 80:20.

Moreover, in the photosensitive coloring resin composition for color filters of 2nd embodiment of 2nd this invention, when it contains further green color materials other than PG59, the content rate of the green color material containing PG59 with respect to the whole color material is There is no particular limitation as long as it is appropriately adjusted according to the desired chromaticity. Among them, it is preferable to contain 10 to 90% by mass of a green color material including PG59 with respect to the entire color material from the viewpoint of widening color reproducibility and increasing luminance while suppressing the occurrence of display defects. More preferably, the content is 20 to 80% by mass.
Further, the content ratio of the yellow color material to the green color material containing PG59 is not particularly limited as long as it is appropriately adjusted according to the desired chromaticity. Among them, from the viewpoint of widening the color reproducibility and increasing the luminance while suppressing the occurrence of display defects, the green color material containing PG59 is contained in 10 to 900 parts by mass with respect to 100 parts by mass. The content is preferably 20 to 400 parts by mass.

Moreover, in the photosensitive coloring resin composition for color filters of 2nd embodiment of 2nd this invention, when further containing at least 1 sort (s) of PG58 and PG7, with respect to the whole green color material containing PG59, PG58 and It is preferable to contain 5 to 50% by mass of at least one kind of PG7. Among them, it is more preferable to contain 5 to 40% by mass from the viewpoint of display failure, luminance, and P / V ratio. From the viewpoint of the V ratio, it is more preferable to further contain 5 to 30% by mass.

Moreover, in the photosensitive coloring resin composition for color filters of 2nd embodiment of 2nd this invention, in the range which does not impair the effect of this invention, in a color material, other than a green color material and a yellow color material Other color materials may further be included, but the total content of the green color material including PG59 and the yellow color material is preferably 70 to 100% by mass with respect to the entire color material, More preferably, it is 80 to 100% by mass.

Further, in the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, as a color material, a blue color material and a yellow color material are combined with PG59, and the yellow color material is (Y1) C.I. I. At least one yellow colorant including CI Pigment Yellow 185, or (Y2) C.I. I. Pigment Yellow 139 as an essential component and C.I. I. Pigment yellow 138, C.I. I. It is preferably at least two kinds of yellow color materials including at least one selected from the group consisting of CI Pigment Yellow 150 and derivative pigments thereof (third embodiment of the second invention). The blue color material and the specific yellow color material used in the third embodiment of the second invention are the same as those described in the color material dispersion of the third embodiment of the second invention. good. As other color materials used in the third embodiment of the second invention, other green color materials and orange color materials are preferably used.

Among them, in the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, while achieving the target chromaticity and suppressing display defects, the P / V ratio is further reduced. It is preferable that PG7 is further included from the viewpoint of improving the development residue suppression, development adhesion, and plate making.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, the content ratio of PG59 with respect to the entire color material may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, it is preferable to contain 5 to 80% by mass of PG59 with respect to the total amount of the color material including PG59 from the viewpoint of widening the color reproducibility and increasing the luminance while suppressing the occurrence of display defects. The content is more preferably 70% by mass, and still more preferably 10 to 60% by mass.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second invention, the content ratio of the blue color material with respect to PG59 may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, it is preferable to contain 10 to 300 parts by mass of a blue color material with respect to 100 parts by mass of PG59 from the viewpoint of increasing the color reproducibility and increasing the luminance while suppressing the occurrence of display defects. More preferably, it is contained in an amount of ˜200 parts by mass.
In addition, the blue color material is preferably contained in an amount of 3 to 60% by mass, more preferably 5 to 50% by mass, and still more preferably 10 to 40% by mass based on the total amount of the color material.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, the content ratio of the yellow color material relative to PG59 may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, it is preferable to contain 10 to 800 parts by mass of a yellow color material with respect to 100 parts by mass of PG59 from the viewpoint of widening color reproducibility and increasing luminance while suppressing occurrence of display defects. It is more preferable to contain ˜600 parts by mass.
Further, the yellow color material is preferably contained in an amount of 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 30 to 70% by mass based on the total amount of the color material.

In the photosensitive colored resin composition for a color filter of the third embodiment of the second invention, the content ratio of the yellow color material to the blue color material may be appropriately adjusted according to the desired chromaticity, and is particularly limited. Not. Among them, it is preferable to contain 10 to 800 parts by mass of the yellow color material with respect to 100 parts by mass of the blue color material from the viewpoint of widening the color reproducibility and increasing the luminance while suppressing the occurrence of display defects. 20 to 600 parts by mass is more preferable.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second invention, (Y1) C.I. I. When at least one yellow color material including Pigment Yellow 185 is used, the content of PY185 is preferably 10 to 100% by mass and more preferably 20 to 100% by mass with respect to the total amount of the yellow color material. preferable. PY185 has a strong coloring power and has an effect of reducing the P / V ratio even if it is contained in an amount of about 10% by mass based on the total amount of the yellow color material.
In addition, when (Y1) contains PY139 in addition to PY185, it shall correspond to (Y1), but the content of PY139 is 10 to 90% by mass with respect to the total amount of the yellow color material. It is preferably 20 to 80% by mass.

Further, in the photosensitive colored resin composition for a color filter according to the third embodiment of the second invention, (Y2) C.I. I. Pigment Yellow 139 as an essential component and C.I. I. Pigment yellow 138, C.I. I. In the case of using at least two kinds of yellow color materials including one or more selected from the group consisting of CI Pigment Yellow 150 and its derivative pigment, the content of PY139 is 5 to 95% by mass with respect to the total amount of the yellow color material It is preferable that the content is 10 to 90% by mass. In addition, C.I. I. Pigment yellow 138, C.I. I. The content of one or more selected from the group consisting of CI Pigment Yellow 150 and its derivative pigment is preferably 5 to 95% by mass, and more preferably 10 to 90% by mass.

Among the above-mentioned (Y2), at least two kinds of yellow color materials containing PY139 as an essential component and further including one or more selected from the group consisting of PY150 and its derivative pigments can be used while suppressing the occurrence of display defects. From the viewpoint of easily achieving a high-luminance and high-contrast colored layer. Further, when (Y2) is combined with at least two kinds of yellow color materials including PY139 and at least one selected from the group consisting of PY150 and its derivative pigments to the PG59 and the blue color material, the P / This is also preferable from the viewpoint that the V ratio can be further reduced and development residue can be suppressed, development adhesion, and plate making can be improved.
Among the above combinations, at least two kinds of yellow color materials containing PY139 as an essential component and further containing a PY150 derivative pigment containing a nickel complex are preferable from the viewpoint of improving luminance and easily reducing the P / V ratio.
When (Y2) is combined with PY139 and at least one selected from the group consisting of PY150 and its derivative pigments, it is composed of PY150 and its derivative pigments from the viewpoint of easily achieving a colored layer with high brightness and high contrast. The content of one or more selected from the group is preferably larger than the content of PY139, preferably 150 to 700 parts by mass, and 200 to 600 parts by mass with respect to 100 parts by mass of PY139. It is more preferable.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second invention, the specific yellow color material is appropriately selected and used alone or in combination of two or more.
In the second aspect of the present invention, PY185 is suitable for expanding the color gamut, and displays a chromaticity region of y = 0.610 to 0.720 and x = 0.140 to 0.230. Even when y = 0.720 to 0.750, it is preferably used when displaying a chromaticity region of x = 0.140 to 0.210.
PY139 is preferably used when displaying a chromaticity region of y = 0.570 to 0.710 and x = 0.180 to 0.265.

Moreover, in the photosensitive coloring resin composition for color filters of 3rd embodiment of 2nd this invention, when further containing green color materials other than PG59, the content rate of the green color material containing PG59 with respect to the whole color material is There is no particular limitation as long as it is appropriately adjusted according to the desired chromaticity.
Even when a green color material other than PG59 is further contained, the content ratio of the green color material including PG59 to the entire color material, the content ratio of the blue color material to the green color material including PG59, and the blue color relative to the entire color material The content ratio of the material, the content ratio of the yellow color material relative to the green color material including PG59, and the content ratio of the yellow color material relative to the entire color material are respectively the content ratio of PG59 relative to the entire color material, and the blue color material relative to PG59. The content ratio, the content ratio of the blue color material relative to the entire color material, the content ratio of the yellow color material relative to PG59, and the content ratio of the yellow color material relative to the entire color material are preferably the same.

Further, in the photosensitive colored resin composition for a color filter according to the third embodiment of the second invention, when PG7 is further contained, 5 to 50% by mass of PG7 is contained with respect to the total amount of the green color material including PG59. In particular, from the viewpoint of display failure, luminance, and P / V ratio, it is more preferable to contain 5 to 45% by mass.

Further, in the photosensitive colored resin composition for a color filter according to the third embodiment of the second invention, a green color material, a blue color material, and a yellow color material are included in the color material as long as the effects of the present invention are not impaired. Although a color material other than the color material may be further included, the total content of the green color material including PG59, the blue color material, and the specific yellow color material is 70 to The content is preferably 100% by mass, and more preferably 80 to 100% by mass.

In the photosensitive colored resin composition for color filters of the second aspect of the present invention, the P / V ratio ((mass of coloring material component in composition) / (mass of solid content other than coloring material component in composition) ratio) Is preferably 0.1 or more from the viewpoint of degassing and heat shrinkage, and more preferably 0.2 or more, on the other hand, it is excellent in display defects and manufacturing convenience, that is, solvent resolubility, From the viewpoint of excellent development residue, development adhesion, development resistance, water stain generation suppression effect, etc., it is preferably 0.7 or less, more preferably 0.6 or less, and 0.5 or less. Even more preferred.

<Hardened film of photosensitive colored resin composition for color filter>
The photosensitive colored resin composition for a color filter according to the second embodiment of the second invention has a chromaticity coordinate in the XYZ color system of JIS Z8701 measured using a C light source, where x = 0.180 to It is preferable that a cured film having a range of 0.330 and y = 0.500 to 0.750 can be formed.
Among these, from the point of improving color reproducibility, the photosensitive colored resin composition for a color filter according to the second embodiment of the second invention is based on the XYZ color system of JIS Z8701 measured using a C light source. It is preferable that a cured film having chromaticity coordinates in the range of x = 0.188 to 0.324 and y = 0.550 to 0.750 can be formed, and x = 0.200 to 0.324, y It is more preferable that a cured film in the range of 0.570 to 0.750 can be formed, and a cured film in the range of x = 0.205 to 0.324 and y = 0.580 to 0.750 is formed. Even more preferably, it can be formed.

The photosensitive colored resin composition for a color filter according to the second embodiment of the second invention has an XYZ of JIS Z8701 having a film thickness of 2.8 μm or less and colorimetric with a C light source with a single pixel. In the chromaticity coordinates in the color system, it is preferable to display a color space where x = 0.200 to 0.300, y = 0.570 to 0.750, and the stimulus value Y is in the range of 37 ≦ Y. More preferably, it is possible to display a color space in a range of = 0.200 to 0.300, y = 0.570 to 0.750, and a stimulus value Y in a range of 40 ≦ Y.
As a favorable blending ratio or combination for displaying a color space in the range of 37 ≦ Y, the total content of the coloring material is 20 to 45 mass with respect to the total solid content of the photosensitive colored resin composition for color filters. As a combination in the color material, 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. In the above, it is preferable that the content ratio of PG59 with respect to the green color material (G) containing PG59 is 30% by mass or more. In addition, the film thickness of the cured film here is the film thickness after post-baking for 30 minutes in a 230 ° C. clean oven after coating, drying, exposing and curing the photosensitive colored resin composition for color filter. Say.

The photosensitive colored resin composition for a color filter of the third embodiment of the second invention has a chromaticity coordinate in the XYZ color system of JIS Z8701 measured using a C light source, where x = 0.140 to It is preferable that a cured film having a range of 0.330 and y = 0.500 to 0.750 can be formed.
Among these, from the point of improving color reproducibility, the photosensitive colored resin composition for a color filter according to the third embodiment of the second invention is based on the XYZ color system of JIS Z8701 measured by using a C light source. It is preferable that a cured film having a chromaticity coordinate in the range of x = 0.140 to 0.280 and y = 0.570 to 0.730 can be formed, and x = 0.140 to 0.265, y It is more preferable that a cured film in the range of = 0.610 to 0.720 can be formed, and a cured film in the range of x = 0.180 to 0.230 and y = 0.690 to 0.710 Even more preferably, it can be formed.

The cured film of the photosensitive colored resin composition for color filters according to the third embodiment of the second aspect of the present invention has a thickness of 2.8 μm or less, and JIS colorimetrically measured with a C light source with a single pixel. In the chromaticity coordinates in the XYZ color system of Z8701, it is preferable that a color space in which x = 0.140 to 0.265, y = 0.570 to 0.720, and the stimulus value Y is in the range of 16 ≦ Y can be displayed. Further, it is more preferable that a color space in which x = 0.140 to 0.230, y = 0.610 to 0.720, and the stimulus value Y is in the range of 18 ≦ Y can be displayed. The film thickness of the cured film here is that after the photosensitive colored resin composition for color filter is applied, dried, exposed to cure the polyfunctional monomer, and then post-baked in a clean oven at 230 ° C. for 30 minutes. The film thickness.
In the chromaticity coordinates in the XYZ color system of JIS Z8701 with a film thickness of 2.8 μm or less and color measurement with a C light source with a single pixel, x = 0.140 to 0.230, y = 0.610 It is preferable to use (Y1) as a yellow color material as a good blending ratio or combination for displaying a color space in the range of .about.0.720 and a stimulus value Y of 18 ≦ Y. , C.I. I. The green color material including Pigment Green 59 is preferably 10 to 70% by mass, the blue color material is preferably 5 to 50% by mass, and the yellow color material is preferably 10 to 70% by mass. . I. It is preferable that the green color material including pigment green 59 is 15 to 60% by mass, the blue color material is 10 to 40% by mass, and the yellow color material is 20 to 60% by mass.
Further, yellow is a preferable blending ratio or combination for displaying a color space in which x = 0.180 to 0.265, y = 0.570 to 0.710, and stimulus value Y is in the range of 16 ≦ Y. The (Y2) is preferably used as the material, and C.I. I. The green color material including Pigment Green 59 is preferably 10 to 70% by mass, the blue color material is preferably 5 to 50% by mass, and the yellow color material is preferably 10 to 70% by mass. . I. It is preferable that the green color material including pigment green 59 is 15 to 60% by mass, the blue color material is 10 to 40% by mass, and the yellow color material is 20 to 60% by mass.

<Method for Producing Photosensitive Colored Resin Composition for Color Filter>
The method for producing the photosensitive colored resin composition for a color filter of the second invention is not particularly limited. For example, the colorant dispersion of the second invention includes an alkali-soluble resin, a polyfunctional monomer, and light. It can be obtained by adding an initiator and other components as required and mixing them using a known mixing means. Alternatively, in the case of including another color material different from PG 59 as in the second embodiment or the third embodiment, the color material dispersion liquid of PG 59 and the color material dispersion of the yellow color material are dispersed using the dispersant. A liquid material and, if necessary, a color material dispersion liquid of another color material, respectively, a color material dispersion liquid containing PG59, a color material dispersion liquid containing a yellow color material, and further if necessary For color filters by mixing other colorant dispersions, alkali-soluble resins, polyfunctional monomers, photoinitiators, and other components as necessary using known mixing means You may obtain the photosensitive coloring resin composition.

II-3. The color filter according to the second aspect of the invention The color filter according to the second aspect of the invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers. One has a colored layer formed by curing the photosensitive colored resin composition for a color filter according to the second aspect of the present invention.
In the color filter according to the second aspect of the present invention, at least one of the colored layers has a colored layer formed by curing the photosensitive colored resin composition for a color filter according to the second aspect of the present invention. Thus, a color filter having high luminance and high contrast and excellent color reproducibility can be obtained.

If the color filter according to the second aspect of the present invention has a colored layer formed by curing the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, the other constitution is Since it may be the same as that described in the color filter according to one aspect of the present invention, description thereof is omitted here.

II-4,5. A liquid crystal display device and an organic light emitting display device according to a second aspect of the present invention include a color filter according to the second aspect of the present invention, a counter substrate, the color filter, and the counter substrate. And a liquid crystal layer formed between the two.
An organic light emitting display device according to a second aspect of the present invention includes the color filter according to the second aspect of the present invention and an organic light emitter.
In the second aspect of the present invention, by using the second color filter, it is possible to provide a liquid crystal display device and an organic light emitting display device having high luminance and excellent color reproducibility.

If the liquid crystal display device and the organic light emitting display device according to the second aspect of the present invention include the color filter according to the second aspect of the present invention, the other configurations are the liquid crystal display device and the organic matter according to the first aspect of the present invention. Since it may be the same as that described in the light-emitting display device, description thereof is omitted here.

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 and the acid value of the salt-type block copolymer salt-formed with the compound represented by the general formula (2) are in accordance with the method described in JIS K 0070. Determined by the method.
The amine value of the block copolymer before salt formation and the amine value of the salt-type block copolymer salt-formed with the compound represented by the general formula (2) are in accordance with the method described in JIS K 7237. Determined by the method.
The glass transition temperature (Tg) of the block copolymer before salt formation and after salt formation is determined by differential scanning calorimetry (DSC) (EXSTAR DSC 7020, manufactured by SII Nanotechnology Co., Ltd.) according to the method described in JIS K7121. It measured using.
The weight average molecular weight (Mw) of the block copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method of the present invention described above.

Further, the glass transition temperatures (Tg) of the block copolymers A-1 and A-26 of the following synthesis examples and the block copolymers A-22 and A-24 of the comparative examples were calculated by the following formula. . As a result, the block copolymer A-1 was 37 ° C. (DSC measured value 38 ° C.), the block copolymer A-26 was 64 ° C. (DSC measured value 66 ° C.), and the block copolymer A-22. Was found to be 0 ° C. (DSC measurement value 2 ° C.), and for block copolymer A-24, it was determined to be 20 ° C. (DSC measurement value 20 ° C.), indicating that it was almost the same as the DSC measurement value.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the block copolymer. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. The homopolymer glass transition temperature (Tgi) of each monomer was the value of Polymer Handbook (3rd Edition) (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)). Specifically, the homopolymer glass transition temperature values (Tgi) of the monomers used in the examples and comparative examples are as follows.
Methacrylic acid (MAA): 185 ° C
2-hydroxyethyl methacrylate (HEMA): 55 ° C
2-ethylhexyl methacrylate (EHMA): -10 ° C
N-Butyl methacrylate (BMA): 20 ° C
Benzyl methacrylate (BzMA): 54 ° C
Methyl methacrylate (MMA): 105 ° C
Cyclohexyl methacrylate (CHMA): 83 ° C
Dimethylaminoethyl methacrylate (DMMA): 18 ° C
Dimethylaminopropyl methacrylamide (DMAPMA): 96 ° C
Methoxypolyethyleneglycol monomethacrylate (trade name: PME-100, manufactured by NOF Corporation, BLEMMER PME-100, ethyleneoxy group repeat number = 2): -26 ° C
Methoxypolyethylene glycol monomethacrylate (trade name: PME-200, manufactured by NOF Corporation, BLEMMER PME-200, ethyleneoxy group repeat number = 4): -59 ° C
2-hydroxy-3-phenoxypropyl acrylate (HPhPA) (trade name; M-600A, manufactured by Kyoeisha Chemical Co., Ltd.): 17 ° C.

Example I Series: First Invention (Synthesis Example 1: Production of Block Copolymer A-1)
Add 250 parts by weight of THF and 0.6 parts by weight of lithium chloride to a 500 mL round bottom 4-neck separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and perform sufficient nitrogen replacement. It was. After cooling the reaction flask to −60 ° C., 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine and 1.0 part by mass of methyl isobutyrate were injected using a syringe. B block monomer 1-ethoxyethyl methacrylate (EEMA) 0.37 parts by weight, 2-ethylhexyl methacrylate (EHMA) 18.6 parts by weight, n-butyl methacrylate (BMA) 15.4 parts by weight, methacrylic acid 9.5 mass parts of benzyl (BzMA) and 29.3 mass parts of methyl methacrylate (MMA) were dripped over 60 minutes using the addition funnel. After 30 minutes, 27.0 parts by weight of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, diluted with PGMEA to obtain a solid content solution of 30% by mass. 32.5 parts by mass of water was added, the temperature was raised to 100 ° C., and the mixture was allowed to react for 7 hours. The structural unit derived from EEMA was deprotected to obtain a structural unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, purified by filtration and vacuum drying, and a structural unit derived from a block containing a structural unit represented by the general formula (I) and a carboxy group-containing monomer A block copolymer A-1 (acid value: 1 mgKOH / g, Tg: 38 ° C.) containing B block having solvophilic property and containing B was obtained. The block copolymer A-1 thus obtained was confirmed by GPC (gel permeation chromatography). The weight average molecular weight Mw was 7600. The amine value was 96 mgKOH / g.

(Synthesis Examples 2 to 3: Synthesis of block copolymers A-2 to A-3)
Block copolymers A-2 to A-3 were synthesized in the same manner as in Synthesis Example 1 except that the content in Synthesis Example 1 was changed to the content shown in Table 1. In Synthesis Example 2, 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used, and in Synthesis Example 3, 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 block copolymer.

(Synthesis Example 4: Synthesis of salt type block copolymer A-4)
First, in the same manner as in Synthesis Example 2, a block copolymer A-2 (the block copolymer A-2 before the salt formation of the salt type block copolymer A-4 is the same as the block copolymer A-2) is synthesized. did.
10.0 parts by mass of block copolymer A-2 was dissolved in 41.93 parts by mass of PGMEA in a 100 mL round bottom flask, and phenylphosphinic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) which is a compound represented by the general formula (3) 0.48 parts by mass (the compound represented by the general formula (3) is 0.20 mol per 1 mol of the DMMA unit of the block copolymer A-2) and stirred at a reaction temperature of 30 ° C. for 20 hours. As a result, a salt type block copolymer A-4 solution having a solid content of 20% by mass was obtained. Although the acid value of the block copolymer after salt formation is the same as that of the block copolymer A-2, the amine value after salt formation was specifically calculated as follows.
An NMR sample tube was charged with 1 g of a mixed solution of 9 parts by mass of salt-type block copolymer A-4 (solid after reprecipitation) and 91 parts by mass of chloroform-D1 NMR, and the 13C-NMR spectrum was measured by nuclear magnetic resonance. Using an apparatus (manufactured by JEOL Ltd., FT NMR, JNM-AL400), the measurement was performed under conditions of room temperature and 10,000 times of integration. Of the obtained spectral data, the integrated value of the carbon atom peak adjacent to the non-salt-formed nitrogen atom and the carbon atom peak adjacent to the salt-formed nitrogen atom at the terminal nitrogen site (amino group) From the ratio, the ratio of the number of amino groups that are salt-formed to the total number of amino groups is calculated, and is not different from the theoretical salt formation ratio (the total phenylphosphinic acid and the nitrogen site at the end of DMMA of the block copolymer A-2) Salt formation).
The amine value after salt formation was calculated as 76 mgKOH / g by subtracting the amine value (19 mgKOH / g) of 0.20 mol of DMMA unit from the amine value 95 mgKOH / g before salt formation. Table 1 also shows Tg of the block copolymer before and after salt formation.

(Synthesis Examples 5 to 10: Synthesis of salt type block copolymers A-5 to A-10)
Salt type block copolymers A-5 to A-10 solutions were obtained in the same manner as in Synthesis Example 4 except that the salt forming compounds were changed to the compounds and amounts shown in Table 1 in Synthesis Example 4.
In the salt type block copolymers A-5 to A-10, the acid value, Tg, amine value of the block copolymer before salt formation, and the acid value of the salt type block copolymer (after salt formation), amine The values and Tg are shown in Table 1.
In Table 1, the amount of one or more compounds selected from the group consisting of the compounds represented by the general formulas (1) to (3) has the structural unit represented by the general formula (I). Expressed in moles of the compound per mole of nitrogen moiety (DMMA).

(Synthesis Examples 11 to 12: Synthesis of block copolymers A-11 to A-12)
Block copolymers A-11 to A-12 used in Comparative Examples were synthesized in the same manner as in Synthesis Example 1 except that the content shown in Table 1 was changed in Synthesis Example 1. Table 1 shows the acid value, Tg, and amine value of the obtained block copolymer.

(Synthesis Example 13: Production of block copolymer A-13)
In a 500 mL round bottom four-necked separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer and digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and initiator dimethylketenemethyltrimethylsilylacetal 5.81 Part by mass was added through an addition funnel, and nitrogen substitution was sufficiently performed. 0.5 parts by mass of a 1 mol / L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 18.7 parts by mass of BEMA monomer for block B, 12.8 parts by mass of EHMA, 13.7 parts of BMA Part by mass, 9.5 parts by mass of BzMA, and 19.5 parts by mass of MMA were added dropwise using an addition funnel over 60 minutes. The temperature was kept below 40 ° C. by cooling the reaction flask with an ice bath. After 1 hour, 25.8 parts by mass of DMMA, which is a monomer for the A block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and the A block containing the structural unit represented by the general formula (I) and the B block having solvophilicity, A block copolymer A-13 (Tg 37 ° C.) containing was obtained. The block copolymer A-13 thus obtained was confirmed by GPC (gel permeation chromatography), and the weight average molecular weight Mw was 7320. The amine value was 92 mgKOH / g.

(Synthesis Examples 14 to 17: Synthesis of salt type block copolymers A-14 to A-17)
In Synthesis Example 4, the block copolymer A-13 of Synthesis Example 13 (the block copolymer before salt formation of the salt-type block copolymers A-14 to A-17, as the block copolymer before salt formation; The salt type block copolymers A-14 to A- were used in the same manner as in Synthesis Example 4 except that the block copolymer A-13 was the same and the salt forming compounds were changed to the compounds and amounts shown in Table 1. 17 solutions were obtained.
In the salt type block copolymers A-14 to A-17, the acid value, Tg, amine value of the block copolymer before salt formation, and the acid value of the salt type block copolymer (after salt formation), amine The values and Tg are shown in Table 1.

(Synthesis Examples 18 to 34: Synthesis of block copolymers A-18 to A-34)
Block copolymers A-18 to A-34 used in Examples or Comparative Examples were synthesized in the same manner as in Synthesis Example 1 except that the content shown in Table 2 or Table 3 was changed in Synthesis Example 1. The acid value, Tg, and amine value of the resulting block copolymer are shown in Table 2 or Table 3.

(Synthesis Examples 35 to 37: Synthesis of salt type block copolymers A-35 to A-37)
In Synthesis Example 4, the block copolymer A-33 of Synthesis Example 33 (the block copolymer before salt formation of salt-type block copolymers A-35 to A-37, and the block copolymer before salt formation; The salt type block copolymers A-35 to A- were used in the same manner as in Synthesis Example 4 except that the block copolymer A-33 was the same and the salt forming compounds were changed to the compounds and amounts shown in Table 3. 37 solutions were obtained.
In the salt type block copolymers A-35 to A-37, the acid value, Tg, amine value of the block copolymer before salt formation, and the acid value of the salt type block copolymer (after salt formation), amine Table 3 shows the values and Tg.

(Synthesis Examples 38 to 40: Synthesis of block copolymers A-38 to A-40)
With reference to Synthesis Examples 1, 2, and 5 (B-1, B-2, and B-5) of Patent Document 2, block copolymers A-38 to A-40 used in Comparative Examples were similarly obtained. Each was synthesized. Table 4 shows the acid value, Tg, and amine value of the obtained block copolymer.

Synthesis Example 41 (Synthesis of alkali-soluble resin A solution)
A polymerization vessel was charged with 300 parts by mass of PGMEA and heated to 100 ° C. in a nitrogen atmosphere, and then 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA) and perbutyl. 6 parts by mass of O (manufactured by NOF Corporation) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Thereafter, the reaction was continued while maintaining 100 ° C., and after 2 hours from the completion of dropping of the main chain forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization.
Next, while blowing air, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added and the temperature was raised to 110 ° C., then 0.8 parts by mass of triethylamine was added, and the mixture was heated at 110 ° C. for 15 hours. By addition reaction, an alkali-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH / g, solid content 40% by mass) was obtained.
The weight average molecular weight was measured by a Shodex GPC System-21H (Shorex GPC System-21H) using polystyrene as a standard substance and THF as an eluent. The acid value was measured based on JIS K 0070.

(Example 1)
(1) Production of colorant dispersion G-1
3.25 parts by mass of the block copolymer A-1 of Synthesis Example 1 as a dispersant and C.I. I. Pigment Green 58 (PG58) in 11.7 parts by mass, C.I. I. 1.3 parts by weight of Pigment Yellow 138 (PY138), 16.25 parts by weight of the alkali-soluble resin A solution obtained in Synthesis Example 41, 67.5 parts by weight of PGMEA, and 100 parts by weight of zirconia beads having a particle size of 2.0 mm Is put into a mayonnaise bin and shaken with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour as a preliminary crushing, then the zirconia beads having a particle size of 2.0 mm are taken out and 200 parts by mass of zirconia beads having a particle size of 0.1 mm In the same manner, as this crushing, dispersion was performed for 4 hours with a paint shaker to obtain a colorant dispersion G-1.

(2) Production of photosensitive colored resin composition G-1 for color filter 11.40 parts by mass of colorant dispersion G-1 obtained in (1) above, alkali-soluble resin A obtained in Synthesis Example 41 0.64 parts by mass of a solution, 0.60 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morphol 0.09 parts by mass of linopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1 (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) 0.04 parts by mass, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- , 1 -(O-acetyloxime) (photoinitiator: trade name Irgacure OXE02, manufactured by BASF Japan Ltd.) 0.02 parts by mass, fluorosurfactant (trade name: Megafac R-08MH, manufactured by DIC Corporation ) And 7.14 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition G-1 for color filters.

(Examples 2 to 26)
(1) Production of Color Material Dispersions G-2 to G-26 In Example 1 (1), instead of the block copolymer A-1, Synthesis Example 2 was carried out as shown in Tables 5 to 7, respectively. Block copolymers A-2 to A-3, salt type block copolymers A-4 to A-10 solutions of Synthesis Examples 4 to 10, block copolymers A-18 to Synthesis Examples 18 to 21 A-21, block copolymers A-26 to A-32 of Synthesis Examples 26 to 32, block copolymers A-33 to A-34 of Synthesis Examples 33 to 34, and salt-type blocks of Synthesis Examples 35 to 37 The copolymer A-35 to A-37 solution was used so that the solid content was the same as that of the block copolymer A-1, and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass. In the same manner as in Example 1, (1), colorant dispersions G-2 to G-26 were obtained.
(2) Production of photosensitive colored resin compositions G-2 to G-26 for color filters In (2) of Example 1, instead of the color material dispersion G-1, the above color material dispersion G-2 Photosensitive colored resin compositions G-2 to G-26 for color filters were obtained in the same manner as (2) of Example 1 except that to G-26 was used.

(Example 35)
(1) Production of colorant dispersion G-27
3.25 parts by mass of the block copolymer A-2 of Synthesis Example 2 as a dispersant and C.I. I. Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 manufactured by DIC Corporation) 13 parts by mass, alkali-soluble resin A solution obtained in Synthesis Example 41 16.25 parts by mass, PGMEA 67.5 parts by mass, particle size 100 parts by weight of 2.0 mm zirconia beads are placed in a mayonnaise bin, shaken for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as a pre-crush, then the 2.0 mm zirconia beads are taken out and the particle size is 0 200 parts by weight of 1 mm zirconia beads were added, and similarly disintegrated for 4 hours using a paint shaker to obtain a colorant dispersion G-27.
(2) Production of Photosensitive Colored Resin Composition G-27 for Color Filter Except that the color material dispersion G-27 was used in place of the color material dispersion G-1 in Example 1 (2). In the same manner as in Example 1, (2), a photosensitive colored resin composition G-27 for color filters was obtained.

(Examples 36 to 38)
(1) Production of Color Material Dispersions G-28 to G-30 In Example 35 (1), instead of the block copolymer A-2, as shown in Table 8, the salt form of Synthesis Example 8 was used. The block copolymer A-8 solution, the block copolymer A-33 of Synthesis Example 33, and the salt-type block copolymer A-35 solution of Synthesis Example 35 have the same solid content as the block copolymer A-2. Colorant dispersions G-28 to G-30 were obtained in the same manner as in Example 35 (1) except that the PGMEA amount was adjusted so that the total amount would be 100 parts by mass. It was.
(2) Production of Photosensitive Colored Resin Compositions G-28 to G-30 for Color Filter In (2) of Example 35, instead of the color material dispersion G-27, the color material dispersion G-28 was used. Photosensitive colored resin compositions G-28 to G-30 for color filters were obtained in the same manner as (2) of Example 35 except that ~ G-30 was used.

(Example 39)
In Example 1 (1), C.I. I. Instead of CI Pigment Green 58 (PG58), C.I. I. Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 manufactured by DIC Corporation) is used, and the block copolymer A-2 of Synthesis Example 2 is used instead of the block copolymer A-1 of Synthesis Example 1 as a dispersant. A colorant dispersion G-31 was obtained in the same manner as (1) of Example 1 except that.
(2) Production of Photosensitive Colored Resin Composition G-31 for Color Filter Except that the color material dispersion G-31 was used in place of the color material dispersion G-1 in Example 1 (2). In the same manner as in Example 1, (2), a photosensitive colored resin composition G-31 for color filters was obtained.

(Examples 40 to 42)
(1) Production of Color Material Dispersions G-32 to G-34 In (1) of Example 39, instead of the block copolymer A-2, as shown in Table 8 respectively, the salt form of Synthesis Example 8 was used. The block copolymer A-8 solution, the block copolymer A-33 of Synthesis Example 33, and the salt-type block copolymer A-35 solution of Synthesis Example 35 have the same solid content as the block copolymer A-2. Color material dispersions G-32 to G-34 were obtained in the same manner as in Example 39 (1) except that 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 G-32 to G-34 for Color Filter In Example 39 (2), instead of the color material dispersion G-31, the color material dispersion G-32 was used. Except for using G-34, photosensitive colored resin compositions G-32 to G-34 for color filters were obtained in the same manner as in Example 39 (2).

(Comparative Examples 1 to 14)
(1) Production of Comparative Color Material Dispersions G-1 to G-14 In Example 1 (1), instead of the block copolymer A-1, synthesis examples are shown as shown in Tables 5 to 7, respectively. 11 to 13 block copolymers A-11 to A-13, salt type block copolymer A-14 to A-17 solutions of Synthesis Examples 14 to 17, and block copolymers A- of Synthesis Examples 22 to 25 The block copolymers A-38 to A-40 of 22 to A-25 and Synthesis Examples 38 to 40 were used so that the solid content was the same as the mass parts of the block copolymer A-1, and the total was 100 masses. Comparative colorant dispersions G-1 to G-14 were obtained in the same manner as in Example 1 (1) except that the amount of PGMEA was adjusted so as to be part.
(2) Production of Photosensitive Colored Resin Compositions G-1 to G-14 for Comparative Color Filter In Example 1 (2), instead of the color material dispersion G-1, each of the above comparison color material dispersions G was used. Photosensitive colored resin compositions G-1 to G-14 for comparative color filters were obtained in the same manner as (2) of Example 1 except that -1 to G-11 were used.

(Example 27)
(1) Production of Color Material Dispersion R-1 3.25 parts by mass of block copolymer A-1 of Synthesis Example 1 as a dispersant and C.I. I. Pigment Red 177 (PR177) 6.5 parts by mass, C.I. I. 6.5 parts by weight of Pigment Red 254 (PR254), 16.25 parts by weight of the alkali-soluble resin A solution obtained in Synthesis Example 41, 67.5 parts by weight of PGMEA, and 100 parts by weight of 2.0 mm zirconia beads mayonnaise Place in a bottle and shake for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for preliminary crushing, then take out 2.0 mm zirconia beads and add 200 parts by mass of 0.1 mm zirconia beads. In the same manner, as this crushing, dispersion was performed for 4 hours with a paint shaker to obtain a colorant dispersion R-1.

(2) Production of photosensitive colored resin composition R-1 for color filter 11.40 parts by mass of colorant dispersion R-1 obtained in (1) above, alkali-soluble resin A obtained in Synthesis Example 41 0.64 parts by mass of a solution, 0.60 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morphol 0.09 parts by mass of linopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1 (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) 0.04 parts by mass, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- , 1 -(O-acetyloxime) (photoinitiator: trade name Irgacure OXE02, manufactured by BASF Japan Ltd.) 0.02 parts by mass, fluorosurfactant (trade name: Megafac R-08MH, manufactured by DIC Corporation) ) And 7.14 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition R-1 for color filters.

(Examples 28 to 30)
(1) Production of Color Material Dispersions R-2 to R-4 In Example 27 (1), instead of the block copolymer A-1, each of Synthesis Examples 27, 3, And 4 block copolymers A-27 and A-3, and salt type block copolymer A-4 solution, respectively, so that the solid content is the same by weight as the block copolymer A-1, Except that the amount of PGMEA was adjusted to 100 parts by mass, colorant dispersions R-2 to R-4 were obtained in the same manner as in Example 27 (1).
(2) Production of photosensitive colored resin compositions R-2 to R-4 for color filter In (2) of Example 27, instead of the color material dispersion R-1, the color material dispersion R-2 was used. Except for using R-4, photosensitive color resin compositions R-2 to R-4 for color filters were obtained in the same manner as in (2) of Example 27.

(Comparative Examples 15 to 18)
(1) Production of Comparative Color Material Dispersions R-1 to R-4 In Example 27 (1), instead of the block copolymer A-1, Synthesis Examples 11 and 13 were used as shown in Table 9 respectively. , 24, and 25, block copolymers A-11, A-13, A-24, and A-25, respectively, were used so that the solid content was the same by weight as the block copolymer A-1, and the total Comparative colorant dispersions R-1 to R-4 were obtained in the same manner as in Example 27 (1) except that the amount of PGMEA was adjusted so as to be 100 parts by mass.
(2) Production of Photosensitive Colored Resin Compositions R-1 to R-4 for Comparative Color Filter In Example 27 (2), each of the above comparative color material dispersions R was used instead of the color material dispersion R-1. Photosensitive colored resin compositions R-1 to R-4 for comparative color filters were obtained in the same manner as (2) of Example 27 except that -1 to R-4 were used.

(Example 31)
(1) Production of Colorant Dispersion B-1 3.25 parts by mass of block copolymer A-1 of Synthesis Example 1 as a dispersant and C.I. I. Pigment Blue 15: 6 (PB15: 6) 10.4 parts by mass, C.I. I. 2.6 parts by weight of Pigment Violet 23 (PV23), 16.25 parts by weight of the alkali-soluble resin A solution obtained in Synthesis Example 41, 67.5 parts by weight of PGMEA, and 100 parts by weight of 2.0 mm zirconia beads mayonnaise Place in a bottle and shake for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for preliminary crushing, then take out 2.0 mm zirconia beads and add 200 parts by mass of 0.1 mm zirconia beads. In the same manner, as this crushing, dispersion was performed for 4 hours with a paint shaker to obtain a colorant dispersion B-1.

(2) Production of photosensitive colored resin composition B-1 for color filter 8.59 parts by mass of colorant dispersion B-1 obtained in (1) above, alkali-soluble resin A obtained in Synthesis Example 41 1.05 parts by mass of the solution, 0.98 parts by mass of polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morphol 0.15 parts by mass of linopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1 (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) 0.07 parts by mass, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- , 1- 0.03 parts by mass of (O-acetyl oxime) (photoinitiator: trade name Irgacure OXE02, manufactured by BASF Japan Ltd.), fluorosurfactant (trade name: Megafuck R-08MH, manufactured by DIC Corporation) Of 0.07 parts by mass and 9.06 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition B-1 for color filters.

(Examples 32 to 34)
(1) Production of Color Material Dispersions B-2 to B-4 In Example 31 (1), instead of the block copolymer A-1, each of Synthesis Examples 27, 3, And 4 block copolymers A-27 and A-3, and salt type block copolymer A-4 solution, respectively, so that the solid content is the same by weight as the block copolymer A-1, Except that the amount of PGMEA was adjusted so as to be 100 parts by mass, colorant dispersions B-2 to B-4 were obtained in the same manner as (1) of Example 31.
(2) Production of Photosensitive Colored Resin Compositions B-2 to B-4 for Color Filter In (2) of Example 31, instead of the color material dispersion B-1, the above color material dispersion B-2 Except for using B-4, photosensitive colored resin compositions B-2 to B-4 for color filters were obtained in the same manner as in (2) of Example 31.

(Comparative Examples 19-22)
(1) Production of Comparative Color Material Dispersions B-1 to B-4 In Example 31 (1), instead of the block copolymer A-1, Synthesis Examples 11 and 13 were used as shown in Table 10 respectively. , 24, and 25, block copolymers A-11, A-13, A-24, and A-25, respectively, were used so that the solid content was the same by weight as the block copolymer A-1, and the total Comparative colorant dispersions B-1 to B-4 were obtained in the same manner as in Example 31 (1) except that the amount of PGMEA was adjusted so as to be 100 parts by mass.
(2) Production of Photosensitive Colored Resin Compositions B-1 to B-4 for Comparative Color Filter In (2) of Example 31, instead of the color material dispersion B-1, the above-mentioned comparison color material dispersion B Photosensitive colored resin compositions B-1 to B-4 for comparative color filters were obtained in the same manner as (2) of Example 31 except that -1 to B-4 were used.

[Evaluation methods]
<Evaluation of dispersibility of colorant dispersion>
For the colorant dispersions obtained in Examples and Comparative Examples, the viscosity immediately after preparation and after storage for 30 days at 25 ° C. are measured, the rate of change in viscosity is calculated from the viscosity before and after storage, and the viscosity stability is evaluated. did. The viscosity was measured at 25.0 ± 0.5 ° C. using a vibration viscometer. The results are shown in Tables 5-10.
(Dispersion stability evaluation criteria)
A: Change rate of viscosity before and after storage is less than 15% B: Change rate of viscosity before and after storage is 15% or more and less than 25% C: Change rate of viscosity before and after storage is 25% or more and less than 40% D: Before and after storage Viscosity change rate is 40% or more However, this is a value when the color material is 13% by mass with respect to the total mass including the solvent of the color material dispersion.
Even if the evaluation result is C, the color material dispersion can be used practically. However, if the evaluation result is B, the color material dispersion is better. If the evaluation result is A, the color material dispersion is excellent in dispersion stability. Are better.

<Optical performance evaluation, contrast evaluation>
The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each spinned on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After coating using a coater, the colored layer was formed by drying at 80 ° C. for 3 minutes using a hot plate. This colored layer was irradiated with 60 mJ / cm ² of ultraviolet rays using an ultrahigh pressure mercury lamp.
Next, the colored substrate is post-baked for 30 minutes in a clean oven at 230 ° C., and the contrast, chromaticity (x, y), and luminance (Y) of the obtained colored substrate are compared with a contrast measuring device CT-1B manufactured by Aisaka Electric. And an Olympus microspectrophotometer OSP-SP200. The results are also shown in Tables 5 to 10.
(Contrast evaluation criteria)
A: Green is over 7000, Red is over 5000, Blue is over 5000 B: Green is 6300-7000, Red is 4300-5000, Blue is 4300-5000
C: Green is less than 6300, Red is less than 4300, and Blue is less than 4300. However, in Examples 1 to 26 and Comparative Examples 1 to 11, Green is y = 0.570, and Green in Examples 35 to 38 is C light source. y = 0.420, Green of Examples 39 to 42 is y = 0.480, Red of Examples 27 to 30 and Comparative Examples 12 to 15 is x = 0.650, Examples 31 to 34 and Comparative Examples 16 to Blue of 19 is a value when y = 0.107.

<Development residue evaluation>
The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each spinned on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After applying using a coater, the coating was dried at 80 ° C. for 3 minutes using a hot plate to form a colored layer having a thickness of 2.5 μm. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. After observing the unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer by visual observation, the glass substrate is thoroughly wiped with a lens cleaner (trade name Toraysee MK Clean Cloth, manufactured by Toray Industries, Inc.), The coloring degree of the lens cleaner was visually observed. The results are shown in Tables 5-10.
(Development residue evaluation criteria)
A: The development residue was not visually confirmed and the lens cleaner was not colored at all. B: The development residue was not visually confirmed and the lens cleaner was slightly colored. C: The development residue was slightly confirmed visually. D: The color of the lens cleaner was slightly confirmed D: The development residue was slightly confirmed by visual observation, and the color of the lens cleaner was confirmed E: The development residue was confirmed by visual observation, and the color of the lens cleaner was confirmed. If the development residue evaluation standard is A, B, or C, it is evaluated that the generation of the development residue is sufficiently suppressed, and it can be used practically without any problem.

<Development adhesion evaluation>
The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each spinned on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After applying using a coater, the coating was dried at 80 ° C. for 3 minutes using a hot plate to form a colored layer having a thickness of 2.5 μm. This colored layer was irradiated with ultraviolet rays of 60 mJ / cm ² using a super high pressure mercury lamp through a photomask having a mask opening width of 2 to 80 μm. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. The substrate after development was observed with an optical microscope, and the presence or absence of a colored layer with respect to the mask opening line width was observed. The results are also shown in Tables 5 to 10.
(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. The photosensitive colored resin composition for a color filter can be used practically, but if the evaluation result is B, the photosensitive colored resin composition for the color filter is suitable for higher definition, and if the evaluation result is A, the color The photosensitive colored resin composition for filters is more suitable for higher definition.

<Solvent resolubility evaluation>
The tip of a glass substrate having a width of 0.5 cm and a length of 10 cm was immersed in the photosensitive colored resin composition for a color filter obtained in Examples and Comparative Examples and applied to a 1 cm portion of the glass substrate. The pulled-up glass substrate was put into 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 30 minutes. Next, the glass substrate to which the dried coating film was adhered was immersed in PGMEA for 15 seconds. At this time, the redissolved state of the dried coating film was visually discriminated and evaluated. The results are also shown in Tables 5 to 10.
(Solvent re-solubility evaluation criteria)
A: The dried coating film was completely dissolved. B: A slice of the dried coating film was formed in the solvent, and the slice was dissolved in time. C: A slice of the dried coating film was formed in the solvent, and the solution was colored. D: In the solvent. The dried coating film flakes were formed and the solution was not colored E: The dried coating film flakes were not formed in the solvent and the solution was not colored If the development residue evaluation criteria were A, B or C, the solvent It is evaluated as having good re-solubility and can be used without any practical problems.

[Summary of results]
From the results of Tables 1 to 10, the dispersant contains an A block containing the structural unit represented by the general formula (I) and a B block containing a structural unit derived from a carboxy group-containing monomer and having solvophilicity. Block copolymer, and at least part of the 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) One or more compounds selected from the group consisting of at least one salt-type block copolymer that forms a salt, and the dispersant has an acid value of 1 to 18 mgKOH / g, It was revealed that the color material dispersions of Examples 1 to 42 using a dispersant having a glass transition temperature of 30 ° C. or higher are excellent in color material dispersibility. In addition, the photosensitive colored resin compositions for color filters of Examples 1 to 42 prepared using the color material dispersions of Examples 1 to 42 are excellent in color material dispersion stability, and generation of development residues is suppressed. However, it was excellent in development adhesion and solvent resolubility.
Among them, Examples 4 to 10 and 24-26, 30, 34, 36, 38, 40, and 42 using the salt-type block copolymer are particularly excellent in colorant dispersibility, and are further obtained color layers. Excellent contrast.
On the other hand, Comparative Examples 1, 2, 12 to 14, 15 and 19 in which the dispersant has a glass transition temperature of 30 ° C. or higher, but the acid value is higher than the specific value of the present application, the development adhesion is poor, and the acid value Comparative Examples 2 and 12 to 14 having high values also deteriorated the solvent resolubility. On the other hand, Comparative Examples 3 to 7, 16, and 20 in which the glass transition temperature of the dispersant was 30 ° C. or higher but the acid value was lower than the specific value of the present application were all poor in developing residue evaluation. Although the acid value of the dispersant is the specific value of the present application, Comparative Examples 8 to 10, 17 and 21 in which the glass transition temperature of the dispersant is lower than the specific value of the present application had poor development adhesion. Further, Comparative Examples 11, 18 and 22 having a glass transition temperature of 23 ° C. and an acid value higher than the specific value of the present application had poor development adhesion.

Example II series: First embodiment of the second invention (Synthesis Example II-1: Preparation of Dispersant a)
A 500 ml 4-neck separable flask was decompressed and dried, and then replaced with Ar (argon).
While flowing Ar, 100 g of dehydrated THF, 2.0 g of methyltrimethylsilyldimethylketene acetal, 0.15 ml of 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), and 0.2 g of mesitylene were added. Thereto, 36.7 g of methyl methacrylate (MMA) was dropped over 45 minutes using a dropping funnel. As the reaction progressed, heat was generated, so the temperature was kept below 40 ° C. by cooling with ice. After 1 hour, 13.3 g of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 15 minutes. After reacting for 1 hour, 5 g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain block copolymer II-A1. The mass average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 6,000, and the amine value was 95 mgKOH / g.
In a 100 mL round bottom flask, 29.35 parts by mass of block copolymer A-1 was dissolved in 29.35 parts by mass of PGMEA, and phenylphosphonic acid (PPA, Tokyo Chemical Industry Co., Ltd.), which is the compound represented by the general formula (3), was dissolved. 3.17 parts by mass (the compound represented by the general formula (3) is 0.20 mol based on 1 mol of the DMMA unit of the block copolymer 1) and stirred at a reaction temperature of 30 ° C. for 20 hours. As a result, a salt type block copolymer II-A1 (dispersant a) solution was obtained. Specifically, the amine value after salt formation was calculated as follows.
Into an NMR sample tube, 1 g of a mixed solution of 9 parts by mass of salt-type block copolymer II-A1 (solid after reprecipitation) and 91 parts by mass of chloroform-D1 NMR was added, and the 13C-NMR spectrum was subjected to nuclear magnetic resonance. Using an apparatus (manufactured by JEOL Ltd., FT NMR, JNM-AL400), the measurement was performed under conditions of room temperature and 10,000 times of integration. Of the obtained spectral data, the integrated value of the carbon atom peak adjacent to the non-salt-formed nitrogen atom and the carbon atom peak adjacent to the salt-formed nitrogen atom at the terminal nitrogen site (amino group) From the ratio, the ratio of the number of amino groups that are salt-formed to the total number of amino groups is calculated, and is not different from the theoretical salt-forming ratio (the two acidic groups of all phenylphosphonic acids are in DMMA of the block copolymer II-A1). It was confirmed that a salt was formed with the terminal nitrogen site).
The amine value after salt formation was calculated to be 57 mgKOH / g by subtracting the amine value (38 mgKOH / g) of 0.40 mol of DMMA unit from the amine value of 95 mgKOH / g before salt formation. Table 11 also shows Tg of the block copolymer before and after salt formation.

(Synthesis Example II-2: Production of Dispersant b)
A salt type block copolymer II-A2 (dispersant b) solution was obtained in the same manner as the salt type block copolymer A-8 of Synthesis Example 8 of Example I series. The acid value of the block copolymer after salt formation is the same as that of the block copolymer II-A2 before salt formation, but the amine value after salt formation was specifically calculated in the same manner as in Synthesis Example II-1. .

(Synthesis Example II-3: Production of Dispersant c)
A 500 ml 4-neck separable flask was decompressed and dried, and then replaced with Ar (argon).
While flowing Ar, 100 g of dehydrated THF, 2.0 g of methyltrimethylsilyldimethylketene acetal, 0.15 ml of 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), and 0.2 g of mesitylene were added. Using a dropping funnel, 33 g of methyl methacrylate was dropped over 45 minutes. As the reaction progressed, heat was generated, so the temperature was kept below 40 ° C. by cooling with ice. After 1 hour, 17 g of dimethylaminoethyl methacrylate was added dropwise over 15 minutes. After reacting for 1 hour, 5 g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain block copolymer II-A3. The mass average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 6,000, and the amine value was 120 mgKOH / g.
In a 100 mL round bottom flask, 24.15 parts by mass of block copolymer II-A3 was dissolved in 24.15 parts by mass of PGMEA, and phenylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a compound represented by the above general formula (3). Add 3.5 parts by mass (the compound represented by the general formula (3) is 0.20 mol per 1 mol of the DMMA unit of the block copolymer II-A3) and stir at a reaction temperature of 30 ° C. for 20 hours. Thus, a salt type block copolymer II-A3 (dispersant c) solution having a solid content of 20% by mass was obtained. The amine value after salt formation was calculated in the same manner as in Synthesis Example II-1.

(Synthesis Example II-4: Synthesis of Dispersant d)
In Synthesis Example II-2, except that the content is changed to the content shown in Table 11, in the same manner as in Synthesis Example II-2, the salt copolymer before salt formation II-A4 and the salt type block copolymer (dispersant) d) A solution was synthesized. In Synthesis Example II-4, 4.6 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used. Table 11 shows the acid value, Tg, and amine value of the obtained salt copolymer before salt formation and the salt-type block copolymer.

(Synthesis Example II-5: Synthesis of Dispersant e)
Block copolymer II-A5 (dispersant e) was synthesized in the same manner as in block copolymer II-A2 (acid value 8 mgKOH / g, Tg 38 ° C.) before salt formation in Synthesis Example II-2.

(Synthesis Examples II-6 to II-7: Synthesis of Dispersant f and Dispersant g)
In the same manner as in Synthesis Example II-5 except that the monomers and contents shown in Table 11 were changed in Synthesis Example II-5, block copolymer II-A6 (dispersant f) and block copolymer II were used. -A7 (dispersant g) was synthesized. Table 11 shows the acid value, Tg, and amine value of the obtained block copolymer.

(Synthesis Example II-8: Synthesis of Dispersant h)
A block copolymer II-A8 before salt formation was synthesized in the same manner as in Synthesis Example II-2 except that the monomers and contents shown in Table 11 were changed in Synthesis Example II-2. The salt-type block copolymer II-A8 (synthetic example II-2) was used except that the block copolymer II-A8 before salt formation was changed to the amount shown in Table 11 as the salt-forming compound. Dispersant h) solution was obtained. Table 11 shows the acid value, Tg, and amine value of the obtained salt copolymer before salt formation and the salt-type block copolymer.

(Synthesis Example II-9: Synthesis of alkali-soluble resin A solution)
A mixed solution of 40 parts by mass of BzMA, 15 parts by mass of MMA, 25 parts by mass of MAA, and 3 parts by mass of AIBN was dropped into a polymerization tank containing 150 parts by mass of PGMEA at 100 ° C. for 3 hours in a nitrogen stream. did. After completion of dropping, the mixture was further heated at 100 ° C. for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution was 7000.
Next, 20 parts by mass of GMA, 0.2 part by mass of triethylamine and 0.05 part by mass of p-methoxyphenol were added to the obtained polymer solution and heated at 110 ° C. for 10 hours, whereby main chain methacrylic acid was added. A 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 through the reaction solution in order 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 the main chain formed by copolymerization of BzMA, MMA, and MAA using GMA, and has a solid content of 40% by mass. The acid value was 74 mgKOH / g, and the weight average molecular weight was 12,000.

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

Example II-1
(1) Production of colorant dispersion II-G1
6.18 parts by mass of the dispersant a solution of Synthesis Example II-1 as a dispersant and C.I. I. Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 manufactured by DIC Corporation) is 13.00 parts by mass, the alkali-soluble resin A solution obtained in Synthesis Example 9 is 14.63 parts by mass, and PGMEA is 66.19 parts by mass. Put 100 parts by mass of 2.0 mm zirconia beads into a mayonnaise bin, shake as a preliminary crushing with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour, then take out the 2.0 mm zirconia beads and remove the particles. 200 parts by mass of zirconia beads having a diameter of 0.1 mm was added, and similarly, this dispersion was dispersed for 4 hours with a paint shaker to obtain a colorant dispersion II-G1.

(2) Production of photosensitive colored resin composition II-G1 for color filter 11.40 parts by mass of colorant dispersion II-G1 obtained in (1) above, alkali-soluble obtained in Synthesis Example II-9 0.64 parts by mass of the resin A solution, 0.60 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2 -0.09 parts by mass of morpholinopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Corporation), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- 0.04 parts by mass of butanone-1 (photoinitiator: trade name Irgacure 369, manufactured by BASF), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- , 1- (O-ace Chill oxime) (photoinitiator: trade name Adeka Arcles NCI-831, manufactured by ADEKA) 0.02 parts by mass, fluorosurfactant (trade name Megafak F559, manufactured by DIC Corporation) 0.07 parts by mass And 7.14 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition II-G1 for color filters.
(3) Formation of colored layer The photosensitive colored resin composition II-G1 obtained in the above (2) is a glass substrate having a thickness of 0.7 mm and a size of 100 mm × 100 mm (manufactured by NH Techno Glass Co., Ltd., “NA35 ]) After applying using a spin coater, it was dried at 80 ° C. for 3 minutes using a hot plate, irradiated with 60 mJ / cm ² of ultraviolet light using an ultra-high pressure mercury lamp, and further in a 230 ° C. clean oven. By post-baking for 30 minutes, the colored layer II-G1 was formed by adjusting the film thickness so that the chromaticity was y = 0.4 and x = 0.2 with a C light source.

(Examples II-2 to II-10, Comparative Examples II-C1 to II-C4)
(1) Production of Color Material Dispersions II-G2 to II-G10 and II-CG1 to II-CG4 In Example II-1 (1), as shown in Table 12, respectively, instead of the dispersant a solution In addition, except that the type and amount of the dispersant are changed so that the solid content is the same part by mass, the color material is partially changed in the comparative example, and the amount of PGMEA is adjusted so that the total becomes 100 parts by mass. In the same manner as in Example II-1 (1), colorant dispersions II-G2 to II-G10 and II-CG1 to II-CG4 were obtained.
(2) Production of photosensitive colored resin compositions II-G2 to II-G10 and II-CG1 to II-CG4 for color filters In Examples II-2 to II-10 and Comparative Examples II-C1 to II-C4 Example II, except that the colorant dispersions II-G2 to II-G10 and II-CG1 to II-CG4 were used in place of the colorant dispersion II-G1 in (2) of Example II-1, respectively. In the same manner as II-1 (2), photosensitive colored resin compositions II-G2 to II-G10 and II-CG1 to II-CG4 for color filters were obtained.
(3) Formation of colored layer In (3) of Example II-1, instead of the photosensitive colored resin composition II-G1, the photosensitive colored resin compositions II-G2 to II-G10 and II-CG1 were used, respectively. Colored layers II-G2 to II-G10 and II-CG1 to II-CG4 were obtained in the same manner as (3) of Example II-1 except that .about.II-CG4 was used.

(Examples II-11 to II-14)
(1) Production of photosensitive colored resin compositions II-G11 to II-G14 for color filters In Examples II-11 to II-14, the coloring material dispersion II-G1 in (2) of Example II-1 was used. Instead of the above colorant dispersion II-G2, and the photoinitiator changed to those shown in Table 12, photosensitive coloring for color filters was performed in the same manner as in (2) of Example II-1. Resin compositions II-G11 to II-G14 were obtained.
In Example II-13, ethanone in Example II-1 (2), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O— Instead of 0.02 part by mass of acetyloxime) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Corporation) IRG907) 0.10 parts by mass, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name Irgacure 369, manufactured by BASF, IRG369) 0.05 mass A photosensitive colored resin composition II-G13 for a color filter was obtained in the same manner as (2) of Example II-1 except that the components were changed.
(3) Formation of colored layer In Example II-1 (3), except that the above-described photosensitive colored resin compositions II-G11 to II-G14 were used in place of the photosensitive colored resin composition II-G1, respectively. In the same manner as in Example II-1 (3), colored layers II-G11 to II-G14 were obtained.

(Example II-15, Comparative Example II-C5)
Example II-15 was the same as Example II-1 except that the colored layer was formed by adjusting the film thickness so that the chromaticity was y = 0.50 with a C light source in (3) of Example II-1. A colored layer II-G15 was formed in the same manner as in (3) of -1.
In Comparative Example II-C5, instead of the photosensitive colored resin composition II-G1 in Example II-1 (3), the photosensitive colored resin composition II- obtained in Comparative Example II-C2 was used. A colored layer was formed in the same manner as (3) of Example II-1 except that the colored layer was formed by using CG2 and adjusting the film thickness so that the chromaticity of y = 0.50 was obtained with a C light source. II-CG5 was formed.

Here, each abbreviation in the table is as follows.
G58: C.I. I. Pigment Green 58 (trade name: FASTOGEN GREEN A110, manufactured by DIC Corporation)
G7: C.I. I. Pigment Green 7 (trade name: Chromo Fine Green 6428EC, manufactured by Dainichi Seika Kogyo)
byk-2000: Disperbyk-2000 (manufactured by BYK Chemie, a polymer having a structural unit represented by the general formula (I), wherein the compound represented by the general formula (2) forms a salt. Coalescence, solid content 40% by mass)
N21116: Disperbyk-LPN21116 (produced by Big Chemie, a polymer having a structural unit represented by the general formula (I), wherein the compound represented by the general formula (2) forms a salt, (Solid content 40% by mass)
byk-161: Disperbyk-161 (by Big Chemie, urethane-based dispersant, solid content: 30% by mass)
PB822: Ajisper PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd., polyester dispersant, solid content 30% by mass)
NCI-831: Oxime ester photoinitiator (Adeka Arcles NCI-831, manufactured by ADEKA)
TR-PBG-304: Oxime ester photoinitiator (Changzhou Power Electronics New Materials Co., Ltd.)
OXE03: Oxime ester photoinitiator (Irgacure OXE-03, manufactured by BASF)
NCI-930: Oxime ester photoinitiator (Adeka Arcles NCI-930, manufactured by ADEKA)

[Evaluation methods]
<Evaluation of dispersibility of colorant dispersion>
For the colorant dispersions obtained in Examples and Comparative Examples, the viscosity immediately after preparation and after storage for 30 days at 25 ° C. are measured, the rate of change in viscosity is calculated from the viscosity before and after storage, and the viscosity stability is evaluated. did. The viscosity was measured at 25.0 ± 0.5 ° C. using a vibration viscometer. The results are shown in Table 12.
(Dispersion stability evaluation criteria)
A: Change rate of viscosity before and after storage is less than 10% B: Change rate of viscosity before and after storage is 10% or more and less than 15% C: Change rate of viscosity before and after storage is 15% or more and less than 25% D: Before and after storage Viscosity change rate is 25% or more However, this is a value when the color material is 13 mass% with respect to the total mass including the solvent of the color material dispersion.
Even if the evaluation result is C, the color material dispersion can be used practically. However, if the evaluation result is B, the color material dispersion is better. If the evaluation result is A, the color material dispersion is excellent in dispersion stability. Are better.

<Optical performance evaluation, contrast evaluation>
The contrast, chromaticity (x, y), and luminance (Y) of the colored layers obtained in the examples and comparative examples were measured using the contrast measuring device CT-1B manufactured by Osaka Co., Ltd. and the microspectroscopy measuring device OSP-SP200 manufactured by Olympus. It was measured.
In Comparative Example 1 using PG58 as the pigment, the chromaticity of y = 0.4 and x = 0.2 could not be realized with the C light source.
The results are also shown in Table 12.
(Color gamut evaluation criteria)
A value when y = 0.4 to 0.5 with a C light source A: x is less than 0.21 B: x = 0.21 to 0.23
C: x = 0.23 (brightness evaluation standard)
-Value when C light source is y = 0.4 and x = 0.2 A: Exceeding 50.0 B: 47.5 to 50.0
C: Less than 47.5. Value when C = light source and y = 0.5 A: Exceeding 30.0 B: 30.0 to 25.0
C: Less than 25.0 (contrast evaluation standard)
-Value when C light source is y = 0.4 and x = 0.2 A: Exceed 15000 B: 13500-15000
C: Less than 13500 · Value when y = 0.5 with C light source A: Exceeding 3500 B: 2500-3500
C: Less than 2500

<Solvent resolubility evaluation>
The tip of a glass substrate having a width of 0.5 cm and a length of 10 cm was immersed in the photosensitive colored resin composition for a color filter obtained in Examples and Comparative Examples and applied to a 1 cm portion of the glass substrate. The pulled glass substrate was placed in a thermo-hygrostat so that the glass surface was horizontal, and dried at a temperature of 23 ° C. and a humidity of 80% RH for 10 minutes. Next, the glass substrate to which the dried coating film was adhered was immersed in PGMEA for 15 seconds. At this time, the redissolved state of the dried coating film was visually discriminated and evaluated. The results are also shown in Table 12.
(Solvent re-solubility evaluation criteria)
A: The dried coating film was completely dissolved. B: The dried coating film flakes were formed in the solvent, and the solution was colored. C: The dried coating film flakes were not formed in the solvent, and the solution was not colored. Is A or B, it can be used practically, but if the evaluation result is A, the effect is more excellent.

<Development residue evaluation>
The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each spinned on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After applying using a coater, the coating was dried at 60 ° C. for 3 minutes using a hot plate to form a colored layer having a thickness of 2.5 μm. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. After observing the unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer by visual observation, the glass substrate is thoroughly wiped with a lens cleaner (trade name Toraysee MK Clean Cloth, manufactured by Toray Industries, Inc.), The coloring degree of the lens cleaner was visually observed. The results are shown in Table 12.
(Development residue evaluation criteria)
A: The development residue was not visually confirmed and the lens cleaner was not colored at all. B: The development residue was not visually confirmed and the lens cleaner was slightly colored. C: The development residue was slightly confirmed visually. D: Color development of the lens cleaner was confirmed D: Development residue was visually confirmed, and color of the lens cleaner was confirmed E: Development residue was confirmed visually, and the color of the lens cleaner was confirmed If it is A, B or C, it can be used practically, but if the evaluation result is B and further A, the effect is more excellent.

<Development adhesion evaluation>
The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each spinned on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After applying using a coater, the coating was dried at 60 ° C. for 3 minutes using a hot plate to form a colored layer having a thickness of 2.5 μm. This colored layer was irradiated with ultraviolet rays of 60 mJ / cm ² using a super high pressure mercury lamp through a photomask having a mask opening width of 2 to 80 μm. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. The substrate after development was observed with an optical microscope, and the presence or absence of a colored layer with respect to the mask opening line width was observed. The results are also shown in Table 12.
(Development adhesion evaluation criteria)
A: A colored layer was observed in a portion having a mask opening line width of less than 10 μm B: A colored layer was observed in a portion having a mask opening line width of 10 μm or more and less than 20 μm C: A portion having a mask opening line width of 20 μm or more and less than 50 μm A colored layer was observed in D: A colored layer was observed in a portion having a mask opening line width of 50 μm or more and less than 80 μm. E: A colored layer was not observed in a portion having a mask opening line width of 80 μm or less.
If the above evaluation criteria are A, B or C, they can be used practically, but if the evaluation result is B and further A, the photosensitive colored resin composition for color filters is suitable for higher definition.

<Development resistance evaluation>
The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each coated on a glass substrate having a thickness of 0.7 mm (NH Techno Glass Co., Ltd., “NA35”) using a spin coater. did. After heating and drying on an 80 ° C. hot plate for 3 minutes, ultraviolet rays of 40 mJ / cm ² were irradiated using an ultrahigh pressure mercury lamp. The film thickness at this point is measured and set to T1 (μm). Thereafter, shower development was performed using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. The film thickness after development is measured and set to T2 (μm). T2 / T1 × 100 (%) was calculated. The results are shown in Table 12.
(Development resistance evaluation criteria)
A: 95% or more B: 90% or more and less than 95% C: less than 90% If the evaluation result is B, it can be used practically, but if the evaluation criterion is A, the effect is more excellent.

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

[Summary of results]
From the results in Table 12, C.I. I. The colorant dispersions of Examples II-1 to II-10, in which Pigment Green 59 is combined with a dispersant that is a polymer having a structural unit represented by the general formula (I), have good viscosity stability. It was revealed. On the other hand, C.I. I. It was revealed that the colorant dispersions of Comparative Examples II-C3 to II-C4, in which Pigment Green 59 was combined with a urethane dispersant or a polyester dispersant, had poor viscosity stability. In addition, C.I. I. It was revealed that the color material dispersion of Comparative Example II-C2 in which Pigment Green 7 was combined with a dispersant that is a polymer having a structural unit represented by the general formula (I) had poor viscosity stability. .
C. I. The photosensitive colored resin compositions for color filters of Examples II-1 to II-15 in which Pigment Green 59 is combined with a dispersant that is a polymer having a structural unit represented by the general formula (I) are y = When 0.40, x = 0.20 area, or when y = 0.50, x = 0.16 area can be displayed. It was. In addition, C.I. I. The photosensitive colored resin compositions for color filters of Examples II-1 to II-15 in which CI Pigment Green 59 is combined with a dispersant that is a polymer having a structural unit represented by the general formula (I) It has been clarified that the dispersion stability is good, the contrast is excellent, the solvent re-dissolvability is excellent, and the development residue is suppressed.
Among them, as a dispersant, a block copolymer containing an A block containing the structural unit represented by the general formula (I) and a B block containing a structural unit derived from a carboxy group-containing monomer and having a solvophilic property, or A salt-type block copolymer that forms a salt 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 Examples II-2, 4, 5, 8, and 11 to 14 in which the dispersant having a glass transition temperature of 30 ° C. or higher is used, generation of development residue is particularly suppressed, and development adhesion is It was excellent.
On the other hand, as shown in Comparative Example II-C1, C.I. I. When using Pigment Green 58, the region of x = 0.2 could not be displayed when y = 0.4. Further, as shown in Comparative Example II-C2, C.I. I. When CI Pigment Green 7 was used, the region of x = 0.2 could be displayed when y = 0.4, but the luminance was low. As shown in Comparative Example II-C5, C.I. I. When CI Pigment Green 7 was used, an area of x = 0.16 could be displayed when y = 0.50, but the luminance was low. Although not shown in the table, C.I. I. With Pigment Green 58, when y = 0.50, the region of x = 0.16 could not be displayed.
Further, as shown in Comparative Example II-C2, C.I. I. When CI Pigment Green 7 is used, the dispersibility is poor even when combined with a dispersant that is a polymer having the structural unit represented by the general formula (I), so the contrast is low, the resolubility and the residue are poor. It was.
On the other hand, C.I. I. The photosensitive colored resin compositions for color filters of Comparative Examples II-C3 to II-C4, in which Pigment Green 59 is combined with a urethane-based dispersant or a polyester-based dispersant, are inferior in dispersibility. The brightness was low, the contrast was low, the re-solubility and the residue were inferior.

In addition, among the examples, it was clarified that the examples using the oxime ester photoinitiator as the photoinitiator have higher development resistance and water stain generation suppressing effect.

Example III Series: Second Embodiment of the Second Invention In the Example III series, the dispersants a to h solutions were obtained in the same manner as in Synthesis Examples II-1 to II-8 of Example II series, respectively. . An alkali-soluble resin A solution was also obtained in the same manner as in Synthesis Example II-9 of Example II series.

Example III-1
(1) Production of colorant dispersion III-G1
6.22 parts by mass of the dispersant a solution as a dispersant and C.I. I. Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 manufactured by DIC Corporation) 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.) 7.67 parts by mass, alkali-soluble resin A solution 14.59 parts by mass, PGMEA 66.20 parts by mass, granules Place 100 parts by mass of 2.0 mm zirconia beads in a mayonnaise bin, shake for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as a preliminary crush, then take out the 2.0 mm zirconia beads and remove the particle size 200 parts by mass of 0.1 mm zirconia beads was added, and similarly, this dispersion was dispersed for 4 hours with a paint shaker to obtain a colorant dispersion III-G1.

(2) Production of photosensitive colored resin composition III-G1 for color filter 11.40 parts by mass of colorant dispersion III-G1 obtained in (1) above and 0.64 parts by mass of alkali-soluble resin A solution 0.60 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ( Photoinitiator: 0.09 parts by mass of trade name Irgacure 907, manufactured by BASF Corporation, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: product Name Irgacure 369, manufactured by BASF) 0.04 parts by mass, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Hikari Initiator: 0.02 parts by mass of Adeka Arkles NCI-831 (trade name, manufactured by ADEKA), 0.07 parts by mass of a fluorosurfactant (trade names: Megafuck F559, manufactured by DIC Corporation), and PGMEA 7.14 parts by mass was added to obtain photosensitive colored resin composition III-G1 for color filters.
(3) Formation of Colored Layer The photosensitive colored resin composition III-G1 obtained in (2) above is a 0.7 mm thick 100 mm × 100 mm glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.). Then, after applying using a spin coater, it is dried at 80 ° C. for 3 minutes using a hot plate, irradiated with 60 mJ / cm ² of ultraviolet light using an ultra-high pressure mercury lamp, and further applied in a clean oven at 230 ° C. for 30 minutes. By performing post-baking for a minute, the color layer III-G1 was formed by adjusting the film thickness so that the chromaticity was y = 0.570 and x = 0.260 with a C light source.

(Examples III-2 to III-10, Comparative Examples III-C1 to III-C5)
(1) Production of Color Material Dispersions III-G2 to III-G10 and III-CG1 to III-CG5 In Example III-1 (1), as shown in Table 13, instead of Dispersant a Solution The type and amount of the dispersant were changed so that the solid content was the same mass part, and the color materials were changed in Comparative Examples III-C1 to III-C3, and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass Except for the adjustment, colorant dispersions III-G2 to III-G10 and III-CG1 to III-CG5 were obtained in the same manner as (1) of Example III-1.
(2) Production of photosensitive colored resin compositions III-G2 to III-G10 and III-CG1 to III-CG5 for color filters In Examples III-2 to III-10 and Comparative Examples III-C1 to III-C5, The color material dispersions III-G2 to III-G10 and III-CG1 to III-CG5 were used in place of the color material dispersion III-G1 in Example III-1 (2), respectively. For color filters, the same as (2) of Example III-1 except that the amount of the alkali-soluble resin was adjusted so that the P / V ratio would be the value shown in Table 13 in order to obtain 35 μm. Photosensitive colored resin compositions III-G2 to III-G10 and III-CG1 to III-CG5 were obtained.
(3) Formation of colored layer In Example III-1 (3), instead of the photosensitive colored resin composition III-G1, the photosensitive colored resin compositions III-G2 to III-G10 and III-CG1 were used. Colored layers III-G2 to III-G10 and III-CG1 to III-CG5 were obtained in the same manner as (3) of Example III-1 except that to III-CG5 was used.

(Examples III-11 to III-14, III-33)
(1) Production of photosensitive colored resin compositions III-G11 to III-G14 and III-G33 for color filters In Examples III-11 to III-12 and III-33, Example III-1 (2) Example III-1 (2) except that the colorant dispersion III-G2 was used instead of the colorant dispersion III-G1 and the photoinitiator was changed to that shown in Table 13. Thus, photosensitive colored resin compositions III-G11 to III-12, III-G33 for color filters were obtained.
In Example III-13, the above-mentioned color material dispersion III-G2 was used instead of the color material dispersion III-G1 in (2) of Example III-1, and further, (2) of Example III-1 ) Instead of 0.02 parts by mass of ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) in -1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Corporation) 0.10 parts by mass, and 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name Irgacure 369, manufactured by BASF) Same as (2) of Example III-1, except for changing to 0.05 parts by mass Photosensitive wear for color filters To obtain a resin composition III-G13.
In Example III-14, the colorant dispersion III-G2 is used in place of the colorant dispersion III-G1 in (2) of Example 1, and the alkali-soluble resin A solution is used as an alkali-soluble resin. The solution is changed to an alkali-soluble resin B 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 becomes the same mass part. A photosensitive colored resin composition III-G14 for color filters was obtained in the same manner as in (2) of Example III-1, except that the amount used was adjusted.
(3) Formation of colored layer In Example III-1 (3), instead of the photosensitive colored resin composition III-G1, the photosensitive colored resin compositions III-G11 to III-G14 and III-G33, respectively, were used. Colored layers III-G11 to III-G14 and III-G33 were obtained in the same manner as (3) of Example III-1 except that was used.

Here, each abbreviation in the table is as follows.
G36: C.I. I. Pigment Green 36 (trade name: FASTOGEN GREEN 2YK-50, manufactured by DIC Corporation)
Y138: C.I. I. Pigment Yellow 138 (trade name: Chromo Fine Yellow 6206EC, manufactured by Dainichi Seika Kogyo Co., Ltd.)
Note that G58, G7, byk-2000, N21116, byk-161, PB822, NCI-831, TR-PBG-304, OXE03, and NCI-930 are the same as the Example II series.

(Examples III-15 to III-20, Comparative Examples III-C6 to III-C8)
(1) Production of Coloring Material Dispersions III-G15 to III-G20 and III-CG6 to III-CG8 In Example III-1 (1), as shown in Table 14 respectively, the types and amounts of coloring materials used In Example III-1, except that the type and amount used of the dispersant were changed so that the solid content was the same part by mass, and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass. In the same manner as in 1), colorant dispersions III-G15 to III-G20 and III-CG6 to III-CG8 were obtained.
(2) Production of photosensitive colored resin compositions III-G15 to III-G20 and III-CG6 to III-CG8 for color filters, respectively, instead of colorant dispersion III-G1 in (2) of Example III-1 In order to make the film thickness 2.80 μm using the above-mentioned colorant dispersions III-G15 to III-G20 and III-CG6 to III-CG8, the P / V ratio is set to the values shown in Table 14, respectively. Except for adjusting the amount of the alkali-soluble resin, in the same manner as in (2) of Example III-1, photosensitive color resin compositions III-G15 to III-G20 and III-CG6 to III-CG8 for color filters were prepared. Obtained.
(3) Formation of colored layer In Example III-1 (3), instead of the photosensitive colored resin composition III-G1, the photosensitive colored resin compositions III-G15 to III-G20 and III-CG6 were used, respectively. Colored layers III-G15 to III-G20 and III-CG6 to III-CG8 were obtained in the same manner as (3) of Example III-1 except that to III-CG8 was used. In Comparative Example III-C8 using PG58 as the color 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 (trade name: LEVASCREEN YELLOW G04, manufactured by LANXESS)
Ni-azo-1: C.I. I. Pigment Yellow 150 derivative pigment (Ni: Zn = 1: 1 (molar ratio) azo pigment)
(Preparation example)
23.1 g diazobarbituric acid and 19.2 g barbituric acid were introduced into 550 g distilled water. Subsequently, it adjusted so that it might become azobarbituric acid (0.3 mol) using potassium hydroxide aqueous solution, and mixed with 750 g of distilled water. 5 g of 30% hydrochloric acid was added dropwise. Thereafter, 38.7 g of melamine was introduced. Subsequently, 0.3 mol nickel chloride solution and 0.3 mol zinc chloride solution were mixed and added, and stirred at a temperature of 80 ° C. for 8 hours. The pigment is isolated by filtration, washed, dried at 120 ° C., ground in a mortar, C.I. I. A pigment pigment of CI Pigment Yellow 150 was obtained.

(Examples III-21 to III-25, Comparative Example III-C9)
Production of Coloring Material Dispersions III-G21 to III-G25, III-CG9 In Example III-1 (1), as shown in Table 15, the type and amount of coloring material were changed, and further dispersed Except for changing the type and amount of the agent so that the solid content is the same part by mass and adjusting the amount of PGMEA so that the total is 100 parts by mass, in the same manner as in (1) of Example III-1, Colorant dispersions III-G21 to III-G25 and III-CG9 were obtained.
(2) Production of photosensitive colored resin compositions III-G21 to III-G25 and III-CG9 for color filters In place of the color material dispersion III-G1 in (2) of Example III-1 In order to obtain a film thickness of 2.80 μm using liquids III-G21 to III-G25 and III-CG9, the amount of the alkali-soluble resin was adjusted so that the P / V ratio was the value shown in Table 15, respectively. Except for the above, Photosensitive Colored Resin Compositions III-G21 to III-G25 and III-CG9 for Color Filter were obtained in the same manner as (2) of Example III-1.
(3) Formation of colored layer In Example III-1 (3), instead of the photosensitive colored resin composition III-G1, the photosensitive colored resin compositions III-G21 to III-G25 and III-CG9 were used. Colored layers III-G21 to III-G25 and III-CG9 were obtained in the same manner as (3) of Example III-1 except that was used. In Comparative Example III-C9 using PG58 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 (trade name: Paliotol (registered trademark) Yellow D1155, manufactured by BASF Corporation)

(Examples III-26 to III-28, Comparative Example III-C10)
Production of Coloring Material Dispersions III-G26 to III-G28, III-CG10 In Example III-1 (1), as shown in Table 16, the type and amount of coloring material were changed, and further dispersed. Except for changing the type and amount of the agent so that the solid content is the same part by mass and adjusting the amount of PGMEA so that the total is 100 parts by mass, in the same manner as in (1) of Example III-1, Colorant dispersions III-G26 to III-G28 and III-CG10 were obtained.
(2) Production of photosensitive colored resin compositions III-G26 to III-G28 and III-CG10 for color filters In place of the color material dispersion III-G1 in (2) of Example III-1 In order to obtain a film thickness of 3.30 μm using liquids III-G26 to III-G28 and III-CG10, the amount of the alkali-soluble resin was adjusted so that the P / V ratio was the value shown in Table 16, respectively. Except for the above, in the same manner as in Example III-1 (2), photosensitive colored resin compositions III-G26 to III-G28 and III-CG10 for color filters were obtained.
(3) Formation of colored layer In Example III-1 (3), instead of the photosensitive colored resin composition III-G1, the photosensitive colored resin compositions III-G26 to III-G28 and III-CG10 were used. Colored layers III-G26 to III-G28 and III-CG10 were obtained in the same manner as (3) of Example III-1 except that was used.

(Examples III-29 to III-31, Comparative Example III-C11)
Production of Color Material Dispersions III-G29 to III-G31, III-CG11 In Example III-1 (1), as shown in Table 17, the type and amount of color material were changed, and the dispersion was further performed. Except for changing the type and amount of the agent so that the solid content is the same part by mass and adjusting the amount of PGMEA so that the total is 100 parts by mass, in the same manner as in (1) of Example III-1, Colorant dispersions III-G29 to III-G31 and III-CG11 were obtained.
(2) Production of photosensitive colored resin compositions III-G29 to III-G31, III-CG11 for color filters In place of the color material dispersion III-G1 in (2) of Example III-1 In order to obtain a film thickness of 3.30 μm using liquids III-G29 to III-G31 and III-CG11, the amount of the alkali-soluble resin was adjusted so that the P / V ratio was the value shown in Table 17, respectively. Except for the above, the photosensitive colored resin compositions III-G29 to III-G31 and III-CG11 for color filters were obtained in the same manner as (2) of Example III-1.
(3) Formation of colored layer In Example III-1 (3), instead of the photosensitive colored resin composition III-G1, the photosensitive colored resin compositions III-G29 to III-G31 and III-CG11 were used. Colored layers III-G29 to III-G31 and III-CG11 were obtained in the same manner as (3) of Example III-1 except that was used.

(Example III-32)
(1) Production of colorant dispersion
6.22 parts by mass of the dispersant b solution as a dispersant and C.I. I. Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 manufactured by DIC Corporation) 13 parts by mass, alkali-soluble resin A solution 14.59 parts by mass, PGMEA 66.20 parts by mass, particle size 2.0 mm zirconia beads 100 The mass part is put into a mayonnaise bin, shaken for 1 hour as a preliminary crushing with a paint shaker (manufactured by Asada Tekko Co., Ltd.), then the zirconia beads 200 having a particle size of 0.1 mm are taken out. Mass parts were added, and similarly, this dispersion was dispersed for 4 hours with a paint shaker to obtain a green color material dispersion g.
6.22 parts by mass of the dispersant b solution as a dispersant and C.I. I. 13 parts by weight of Pigment Yellow 138 (PY138, trade name: Chromofine Yellow 6206EC, manufactured by Dainichi Seika Kogyo Co., Ltd.), 14.59 parts by weight of the alkali-soluble resin A solution, 66.20 parts by weight of PGMEA, and particle size 2 Put 100 parts by weight of 0.0 mm zirconia beads in a mayonnaise bin, shake as a preliminary crushing with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour, then take out the 2.0 mm zirconia beads, 200 parts by mass of 1 mm zirconia beads were added, and similarly, this dispersion was dispersed for 4 hours with a paint shaker to obtain a yellow color material dispersion liquid y.

(2) Production of photosensitive colored resin composition III-G32 for color filter 4.67 parts by mass of green color material dispersion g obtained in (1) above and 6.73 parts by mass of yellow color material dispersion y 0.64 parts by mass of alkali-soluble resin A solution, 0.60 parts by mass of polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) ) -2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Corporation) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholino) 0.04 parts by mass of phenyl) -butanone-1 (photoinitiator: trade name Irgacure 369, manufactured by BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Il]-, 1 0.02 parts by mass of-(O-acetyloxime) (photoinitiator: trade name Adeka Arcles NCI-831, manufactured by ADEKA), fluorosurfactant (trade name: MegaFuck F559, manufactured by DIC Corporation) 0.07 part by mass and 7.14 parts by mass of PGMEA were added to obtain photosensitive colored resin composition III-G32 for color filters.
(3) Formation of colored layer Example III-1 was the same as Example III-1 (3) except that the photosensitive colored resin composition III-G32 was used instead of the photosensitive colored resin composition III-G1. The colored layer III-G32 was obtained in the same manner as in (3) of -1.
The resulting photosensitive colored resin composition III-G32 for color filters had the same composition as the photosensitive colored resin composition III-G2 for color filters of Example III-2, and the photosensitive colored resin for color filters The evaluation results of composition III-G32 and colored layer III-G32 were the same as the evaluation results of photosensitive colored resin composition III-G2 for color filter and colored layer III-G2.

[Evaluation method of Example III series]
Optical performance evaluation, contrast evaluation, and display defect evaluation were performed as follows. The dispersibility evaluation of the colorant dispersion, the solvent resolubility evaluation, the development residue evaluation, the development adhesion evaluation, the development resistance evaluation, and the water stain evaluation were evaluated in the same manner as in Example II series.

<Optical performance evaluation, contrast evaluation>
The contrast, chromaticity (x, y), and luminance (Y) of the colored layers obtained in the examples and comparative examples were measured using the contrast measuring device CT-1B manufactured by Osaka Co., Ltd. and the microspectroscopy measuring device OSP-SP200 manufactured by Olympus. It was measured.
In Comparative Example 8 using PG58 as the color material, the chromaticity of y = 0.610 and x = 0.210 could not be realized with the C light source. In Comparative Example 9 using PG58 as the color material, the chromaticity of y = 0.626 and x = 0.205 could not be realized with the C light source.
(Contrast evaluation criteria)
Value when C = 0 and y = 0.570, x = 0.260 A: over 12,000 B: 12000 to 10000
C: Less than 10,000

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

[Summary of results of Example III series]
From the results shown in Tables 13 to 17, the colorant dispersions of Examples in which PG59 and a yellow colorant are combined with a dispersant that is a polymer having a structural unit represented by the general formula (I) have viscosity stability. It was shown to be good. On the other hand, it was revealed that the colorant dispersions of Comparative Examples III-C4 to III-C5, in which PG59 was combined with a urethane dispersant or a polyester dispersant, had poor viscosity stability. Further, the colorant dispersions of Comparative Examples III-C1, III-C2, and III-C3, in which PG58, PG7, and PG36 are combined with a dispersant that is a polymer having a structural unit represented by the general formula (I), It was revealed that the viscosity stability was inferior to that of Example III-1 in which the same dispersant was combined. Further, the colorant dispersions of Comparative Examples III-C2 and III-C3, in which PG7 and PG36 were combined with a dispersant that is a polymer having a structural unit represented by the general formula (I), had poor dispersibility. .

From Table 13, the photosensitive properties for color filters of Examples III-1 to III-14 in which PG59 is combined with a dispersant, which is a polymer having a structural unit represented by the general formula (I), with the yellow color material PY138. It is clear that the colored resin composition can display the region of x = 0.260 when y = 0.570, while suppressing the occurrence of display defects and forming a high-luminance colored layer. It was done. In addition, the photosensitive color resin for color filters of Examples III-1 to III-14, in which PG59 is combined with a yellow color material PY138 and a dispersant that is a polymer having a structural unit represented by the general formula (I) It was revealed that the composition has good colorant dispersion stability, excellent contrast, excellent solvent resolubility, and further suppresses development residue.
Among them, as a dispersant, a block copolymer containing an A block containing the structural unit represented by the general formula (I) and a B block containing a structural unit derived from a carboxy group-containing monomer and having a solvophilic property, or A salt-type block copolymer that forms a salt 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 Examples III-2, III-4, III-8, III-11 to III-14, and III-33 using a dispersant having a glass transition temperature of 30 ° C. or higher, the development residue Generation was suppressed, and the development adhesion was excellent. Further, as an alkali-soluble resin in the photosensitive colored resin composition, Example III-14 using an epoxy (meth) acrylate resin having a carboxy group containing a cardo structure is more closely related to development adhesion than Example III-2, Excellent development resistance and water stain generation suppression effect.
Further, among the examples, from the comparison of Examples III-2, III-11, III-12, III-13, and III-33, Examples using an oxime ester photoinitiator as a photoinitiator It was revealed that the development resistance and the effect of suppressing the occurrence of water stain were increased.

Further, from Tables 14 and 15, when PG59 is combined with a yellow colorant and a dispersant that 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, a chromaticity region of x = 0.205 to 0.324 can be displayed, and further, a chromaticity region of y = 0.659 can be displayed, but a display defect occurs. It was clarified that a colored layer with high brightness can be formed.
Further, in Example III-27 of Table 16, when PG59 is further combined with PG59 and a yellow color material, Example III-26 using PG59 alone as a green color material, or PG58 and Y138 are combined. It was also clarified that the luminance was further improved while reducing the P / V ratio as compared with Comparative Example III-C10. In Example III-28, it was revealed that the P / V ratio could be further reduced by combining PG59 and PG58 as the green color material and PY138 and PY150 as the yellow color material.
Further, in Example III-30 in Table 17, when PG59 is further combined with PG59 and a yellow color material, the P / V ratio is reduced as compared with Comparative Example III-C11 in which PG58 and Y138 are combined. It was clarified that the brightness could be improved. In Example III-31, it has also been clarified that the P / V ratio can be further reduced by combining PG59 and PG7 as the green color material and PY138 and PY150 as the yellow color material.
On the other hand, when PG58 is used as shown in Comparative Example III-C1, an area of x = 0.260 can be displayed when y = 0.570, but a display defect occurs, and compared with the case where PG59 is used. The brightness was inferior. The development residue was also bad. Further, when PG7 or PG36 is used as shown in Comparative Examples III-C2 and III-C3, an area of x = 0.260 can be displayed when y = 0.570, but the luminance is low. . Further, even when 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 re-solubility and the development residue are inferior.
On the other hand, the photosensitive colored resin compositions for color filters of Comparative Examples III-C4 to III-C5 in which PG59 is combined with a urethane dispersant or a polyester dispersant are inferior in dispersibility. In comparison, the brightness was low, the contrast was low, the redissolving property and the development residue were poor.

Example IV Series: Third Embodiment of the Second Invention In the Example IV series, the dispersants a to h solutions were obtained in the same manner as in Synthesis Examples II-1 to II-8 of Example II series, respectively. . An alkali-soluble resin A solution was also obtained in the same manner as in Synthesis Example II-9 of Example II series.

Example IV-1
(1) Production of colorant dispersion IV-G1
6.22 parts by mass of the dispersant a solution as a dispersant and C.I. I. CI Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC Co., Ltd.) 6.42 parts by mass, blue color material C.I. I. Pigment Blue 15: 4 (PB15: 4, trade name Cyanine Blue CP-1 manufactured by Dainichi Seika Kogyo Co., Ltd.) 1.39 parts by weight, C.I. I. Pigment Yellow 139 (PY139, trade name: IRGAPHOR YELLOW 2R-CF manufactured by BASF) 1.40 parts by mass; I. Pigment Yellow 150 (PY150, trade name: LEVASCREEN YELLOW G04, manufactured by LANXESS) 3.80 parts by mass, alkali-soluble resin A solution 14.59 parts by mass, PGMEA 66.20 parts by mass, particle size 2.0 mm 100 parts by weight of zirconia beads are put into a mayonnaise bin, shaken for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as a pre-crush, then the zirconia beads having a particle size of 2.0 mm are taken out, 200 parts by mass of zirconia beads were added, and similarly, this dispersion was dispersed for 4 hours with a paint shaker to obtain a colorant dispersion IV-G1.

(2) Production of photosensitive colored resin composition IV-G1 for color filter 11.41 parts by mass of colorant dispersion IV-G1 obtained in (1) above and 2.75 parts by mass of alkali-soluble resin A solution 0.60 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ( Photoinitiator: 0.09 parts by mass of trade name Irgacure 907, manufactured by BASF Corporation, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: product Name Irgacure 369, manufactured by BASF) 0.04 parts by mass, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Hikari Agent: 0.02 parts by mass of Adeka Arkles NCI-831 (trade name, manufactured by ADEKA), 0.07 parts by mass of a fluorosurfactant (trade names: Megafuck F559, manufactured by DIC Corporation), and 9 PGMEA .72 parts by mass was added to obtain photosensitive colored resin composition IV-G1 for color filters.
(3) Formation of Colored Layer The photosensitive colored resin composition IV-G1 obtained in (2) above is a 0.7 mm thick 100 mm × 100 mm glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.). Then, after applying using a spin coater, it is dried at 80 ° C. for 3 minutes using a hot plate, irradiated with 60 mJ / cm ² of ultraviolet light using an ultra-high pressure mercury lamp, and further applied in a clean oven at 230 ° C. for 30 minutes. The colored layer IV-G1 was formed by adjusting the film thickness so that the film thickness after curing was 2.80 μm by post-baking for minutes.

(Examples IV-2 to IV-10, IV-15 to IV-17, Comparative Examples IV-C1 to IV-C4)
(1) Production of Color Material Dispersions IV-G2 to IV-G10, IV-G15 to IV-G17, IV-CG1 to IV-CG4 Examples IV-2 to IV-10 and Comparative Examples IV-C3 to IV- In C4, in Example IV-1 (1), as shown in Table 18, instead of the dispersant a solution, the type and amount of dispersant were changed so that the solid content was the same part by mass. In the same manner as in (1) of Example IV-1, except that the amount of PGMEA was adjusted so that the total amount was 100 parts by mass, the colorant dispersions IV-G2 to IV-G10 and IV-CG3 to IV were used. -Obtained CG4. In Examples IV-15 to IV-17, the dispersant b solution was used in place of the dispersant a solution in Example IV-1 (1), and the coloring material was further changed to a total of 100 parts by mass. Except for adjusting the amount of PGMEA, color material dispersions IV-G15 to IV-G17 were obtained in the same manner as (1) of Example IV-1. In Comparative Examples IV-C1 to IV-C2, IV-CG1 to IV- were prepared in the same manner as in Example IV-1 (1) except that the color material was changed in (1) of Example IV-1. CG2 was obtained.
(2) Production of photosensitive colored resin compositions IV-G2 to IV-G10, IV-G15 to IV-G17, and IV-CG1 to IV-CG4 for color filters Colorant dispersion in (2) of Example IV-1 In order to make the film thickness 2.8 μm by using the colorant dispersions IV-G2 to IV-G10, IV-G15 to IV-G17, and IV-CG1 to IV-CG4, respectively, instead of the liquid IV-G1 Photosensitive colored resin composition for color filters in the same manner as (2) of Example IV-1, except that the amount of the alkali-soluble resin was adjusted so that the P / V ratio was the value shown in Table 18, respectively. The products IV-G2 to IV-G10, IV-G15 to IV-G17, and IV-CG1 to IV-CG4 were obtained.
(3) Formation of colored layer In Example IV-1, (3), instead of the photosensitive colored resin composition IV-G1, the photosensitive colored resin compositions IV-G2 to IV-G10 and IV-G15 were used. Colored layers IV-G2 to IV-G10, IV-G15 to IV-G17, in the same manner as in (3) of Example IV-1, except that to IV-G17 and IV-CG1 to IV-CG4 were used IV-CG1 to IV-CG4 were obtained.

(Examples IV-11 to IV-14, Example IV-36)
(1) Production of photosensitive colored resin compositions IV-G11 to IV-G14 and IV-G36 for color filters Examples IV-11 to IV-12 and IV-36 are the same as those in Example IV-1 (2). Example IV-1 (2) except that the color material dispersion IV-G2 was used instead of the color material dispersion IV-G1 and the photoinitiator was changed to that shown in Table 18. Thus, photosensitive colored resin compositions IV-G11 to IV-12 and IV-G36 for color filters were obtained.
In Example IV-13, the color material dispersion IV-G2 was used in place of the color material dispersion IV-G1 in (2) of Example IV-1. Further, in Example IV-1, (2) ) Instead of 0.02 parts by mass of ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) in -1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Corporation) 0.10 parts by mass, and 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name Irgacure 369, manufactured by BASF) Same as (2) of Example IV-1, except for changing to 0.05 parts by mass Photosensitive color resin for color filters It was obtained Narubutsu IV-G13.
In Example IV-14, the color material dispersion IV-G2 is used in place of the color material dispersion IV-G1 in (2) of Example IV-1, and an alkali-soluble resin A solution is further used as an alkali-soluble resin. Instead of the alkali-soluble resin B solution (epoxy (meth) acrylate resin having a carboxy group containing cardo structure, product number INR-16M manufactured by Nagase Chemtech Co., Ltd.), the solid content becomes the same mass part A photosensitive colored resin composition IV-G14 for color filters was obtained in the same manner as (2) of Example IV-1 except that the amount used was adjusted as described above.
(3) Formation of colored layer In (3) of Example IV-1, instead of the photosensitive colored resin composition IV-G1, the photosensitive colored resin compositions IV-G11 to IV-G14 and IV-G36, respectively, were used. Colored layers IV-G11 to IV-G14 and IV-G36 were obtained in the same manner as (3) of Example IV-1 except that was used.

Here, each abbreviation in the table is as follows.
PB15: 4: C.I. I. Pigment Blue 15: 4 (trade name: Cyanine Blue CP-1 manufactured by Dainichi Seika Kogyo Co., Ltd.)
PB15: 3: C.I. I. Pigment Blue 15: 3 (trade name: Chromo Fine Blue A-220JC, manufactured by Dainichi Seika Kogyo Co., Ltd.)
G36, G58, Ni-azo-1, Y138, byk-2000, N21116, byk-161, PB822, NCI-831, TR-PBG-304, OXE03, and NCI-930 are the same as those in Example II or III series. The same.

(Examples IV-18 to IV-19, Comparative Examples IV-C5 to IV-C13)
(1) Production of Color Material Dispersions IV-G18 to IV-G19, IV-CG5 to IV-CG13 In Example IV-1 (1), as shown in Table 19, the types and amounts of color materials used In Example IV-1 except that the type and amount of dispersant were changed so that the solid content was the same mass part, and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass. In the same manner as in 1), colorant dispersions IV-G18 to IV-G19 and IV-CG5 to IV-CG13 were obtained.
(2) Production of photosensitive colored resin compositions IV-G18 to IV-G19 and IV-CG5 to IV-CG13 for color filters, respectively, instead of the color material dispersion IV-G1 in (2) of Example IV-1 Using the above-mentioned colorant dispersions IV-G18 to IV-G19, IV-CG6, IV-CG7, and IV-CG12 to IV-CG13, the P / V ratios are shown in order to obtain a film thickness of 2.8 μm. Except that the amount of the alkali-soluble resin was adjusted to the value shown in 19, the same as in (2) of Example IV-1, photosensitive colored resin compositions IV-G18 to IV-G19 for color filters IV-CG6, IV-CG7, and IV-CG12 to IV-CG13 were obtained.
In the case of the combination of the color materials of Comparative Examples IV-C5 and IV-C8 to IV-C11, the photosensitivity is such that the film thickness is 2.8 μm and the chromaticity of x = 0.200 and y = 0.710 can be realized. The colored resin composition could not be prepared.
(3) Formation of colored layer In Example IV-1 (3), instead of the photosensitive colored resin composition IV-G1, the photosensitive colored resin compositions IV-G18 to IV-G19 and IV-CG6 were used, respectively. The colored layers IV-G18 to IV-G19, IV-CG6, and IV-CG7 are the same as in (3) of Example IV-1 except that IV-CG7 and IV-CG12 to IV-CG13 are used. And IV-CG12 to IV-CG13 were obtained.

PB15: 6: C.I. I. Pigment Blue 15: 6 (trade name: FASTOGEN BLUE A510, manufactured by DIC Corporation)

(Examples IV-20 to IV-34, Comparative Examples IV-C14 to IV-C16)
Production of Coloring Material Dispersions IV-G20 to IV-G34 and IV-CG14 to IV-CG16 In Example IV-1 (1), as shown in Table 20, the type and amount of coloring material were changed. Furthermore, except that the type and amount of the dispersant were changed so that the solid content was the same mass part, and the amount of PGMEA was adjusted so that the total was 100 parts by mass, and (1) of Example IV-1 Similarly, colorant dispersions IV-G20 to IV-G34 and IV-CG14 to IV-CG16 were obtained.
(2) Production of photosensitive colored resin compositions IV-G20 to IV-G34 and IV-CG14 to IV-CG16 for color filters, instead of the color material dispersion IV-G1 in (2) of Example IV-1 Using the above color material dispersions IV-G20 to IV-G34 and IV-CG14 to IV-CG16, the P / V ratio is set to the values shown in Table 20 in order to obtain a film thickness of 2.8 μm. Except for adjusting the amount of the alkali-soluble resin, in the same manner as in (2) of Example IV-1, photosensitive color resin compositions IV-G20 to IV-G34, IV-CG14 to IV-CG16 for color filters were prepared. Obtained.
(3) Formation of colored layer In (3) of Example IV-1, instead of the photosensitive colored resin composition IV-G1, the photosensitive colored resin compositions IV-G20 to IV-G34 and IV-CG14 were used. Colored layers IV-G20 to IV-G34 and IV-CG14 to IV-CG16 were obtained in the same manner as (3) of Example IV-1 except that .about.IV-CG16 was used.

G7 and Y185 are the same as those in Example III series.

(Example IV-35)
(1) Production of colorant dispersion
6.22 parts by mass of the dispersant b solution as a dispersant and C.I. I. Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 manufactured by DIC Corporation) 13 parts by mass, alkali-soluble resin A solution 14.59 parts by mass, PGMEA 66.20 parts by mass, particle size 2.0 mm zirconia beads 100 The mass part is put into a mayonnaise bin, shaken for 1 hour as a preliminary crushing with a paint shaker (manufactured by Asada Tekko Co., Ltd.), then the zirconia beads 200 having a particle size of 0.1 mm are taken out. Mass parts were added, and similarly, this dispersion was dispersed for 4 hours with a paint shaker to obtain a green color material dispersion g.
In the green color material dispersion g, C.I. I. Instead of using 13 parts by mass of Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 manufactured by DIC Corporation), C.I. I. Blue color material dispersion liquid in the same manner as the green color material dispersion liquid g except that 13 parts by mass of Pigment Blue 15: 4 (PB 15: 4, trade name Cyanine Blue CP-1 manufactured by Dainichi Seika Kogyo Co., Ltd.) was used. b was obtained.
In the green color material dispersion g, C.I. I. Instead of using 13 parts by mass of Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 manufactured by DIC Corporation), C.I. I. A yellow color material dispersion y1 was obtained in the same manner as the green color material dispersion g except that 13 parts by mass of Pigment Yellow 139 (PY139, trade name: IRGAPHOR YELLOW 2R-CF BASF) was used.
In the green color material dispersion g, C.I. I. Instead of using 13 parts by mass of Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 manufactured by DIC Corporation), C.I. I. A yellow color material dispersion y2 was obtained in the same manner as in the green color material dispersion g except that 13 parts by mass of Pigment Yellow 150 (PY150, trade name: LEVASCREEN YELLOW G04, manufactured by LANXESS) was used.

(2) Production of photosensitive colored resin composition IV-G35 for color filter 5.63 parts by mass of green color material dispersion g obtained in (1) above and 1.22 parts by mass of blue color material dispersion b 1.23 parts by mass of the yellow color material dispersion y1, 3.33 parts by mass of the yellow color material dispersion y2, 2.75 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 9, and a polyfunctional monomer ( 0.60 parts by mass of Aronix M-403 (trade name, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: product) 0.09 parts by mass of Irgacure 907 (manufactured by BASF Corporation), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name Irgacure 369, BASF) 0.04 parts by mass, 1,1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (photoinitiator: trade name Adeka Arcles NCI-831, 0.02 parts by mass of ADEKA (manufactured by ADEKA), 0.07 parts by mass of fluorine-based surfactant (trade name: Megafac F559, manufactured by DIC Corporation), and 9.72 parts by mass of PGMEA are added, and the sensitivity for color filters A colored resin composition IV-G35 was obtained.
(3) Formation of colored layer Example IV-1 is the same as Example IV-1 (3) except that the photosensitive colored resin composition IV-G35 was used instead of the photosensitive colored resin composition IV-G1. The colored layer IV-G35 was obtained in the same manner as in (3) of -1.
The resulting photosensitive colored resin composition IV-G35 for color filter had the same composition as the photosensitive colored resin composition IV-G2 for color filter of Example IV-2, and the photosensitive colored resin for color filter The evaluation results of the composition IV-G35 and the colored layer IV-G35 were the same as the evaluation results of the photosensitive colored resin composition IV-G2 for the color filter and the colored layer IV-G2.

[Example IV Series Evaluation Method]
Optical performance evaluation and contrast evaluation were performed as follows. Evaluation of dispersibility evaluation, display defect evaluation, solvent resolubility evaluation, development residue evaluation, development adhesion evaluation, development resistance evaluation, and water stain evaluation of the colorant dispersion is performed in the same manner as in Example II series. It was.

<Optical performance evaluation, contrast evaluation>
The contrast, chromaticity (x, y), and luminance (Y) of the colored layers obtained in the examples and comparative examples were measured using the contrast measuring device CT-1B manufactured by Osaka Co., Ltd. and the microspectroscopy measuring device OSP-SP200 manufactured by Olympus. It was measured.
(Contrast evaluation criteria)
Value when C = 0 and y = 0.670, x = 0.210 A: Exceeding 8000 B: 6000 to 8000
C: Less than 6000

[Summary of results of Example IV series]
From the results of Tables 18 to 20, the colorant dispersions of Examples in which PG59, a blue colorant, and the specific yellow colorant are combined with a dispersant that is a polymer having a structural unit represented by the general formula (I) The liquid was found to have good viscosity stability. On the other hand, it was revealed that the color material dispersions of Comparative Examples IV-C3 to IV-C4, in which PG59 was combined with a urethane dispersant or a polyester dispersant, had poor viscosity stability. Further, the colorant dispersions of Comparative Examples IV-C1 and IV-C2 in which PG58 and PG36 are combined with a dispersant that is a polymer having the structural unit represented by the general formula (I) are combined with the same dispersant. It was revealed that the viscosity stability was inferior to that of Example IV-1. Further, the colorant dispersion of Comparative Example IV-C2 in which PG36 is combined with a dispersant that is a polymer having the structural unit represented by the general formula (I) has poor dispersibility.

From Table 18, Examples IV-1 to IV- in which PG59 is combined with a blue color material, the specific yellow color material, and a dispersant that is a polymer having a structural unit represented by the general formula (I) The photosensitive colored resin compositions for color filters 17 and IV-36 are capable of displaying the region of x = 0.210 when y = 0.670, while suppressing the occurrence of display defects and high brightness. It was revealed that a colored layer can be formed. In addition, the photosensitive colored resin compositions for color filters of Examples IV-1 to IV-17 and IV-36 have good colorant dispersion stability, excellent contrast, and excellent solvent resolubility. Further, it has been clarified that generation of development residue is suppressed.
Among them, as a dispersant, a block copolymer containing an A block containing the structural unit represented by the general formula (I) and a B block containing a structural unit derived from a carboxy group-containing monomer and having a solvophilic property, or A salt-type block copolymer that forms a salt 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. Thus, it has been clarified that when a dispersant having a glass transition temperature of 30 ° C. or higher is used, the occurrence of development residue is particularly suppressed and the development adhesion is excellent (the P / V ratio is the same). Examples IV-2, IV-4, IV-8, IV-11 to IV-17 and IV-36 in Examples IV-1 to IV-17 and IV-36). In addition, Example IV-14 using an epoxy (meth) acrylate resin having a carboxy group containing a cardo structure as an alkali-soluble resin in the photosensitive colored resin composition has a development adhesion even when compared with Example IV-2. Excellent development resistance and water stain generation suppression effect.
Further, among the examples, from the comparison of Examples IV-2, IV-11, IV-12, IV-13, and IV-36, Examples using oxime ester photoinitiators as photoinitiators are It has been clarified that the development resistance and the effect of suppressing the occurrence of water stain are increased.

Further, from Table 19 and Table 20, when a PG59 is combined with a blue color material, the specific yellow color material, and a dispersant that is a polymer having a structural unit represented by the general formula (I), a color reproduction range is obtained. Even when y = 0.570 to 0.720, a chromaticity region of x = 0.140 to 0.265 can be displayed, and a chromaticity region of y = 0.750 can be displayed. However, it has been clarified that the occurrence of display defects can be suppressed and a colored layer having a higher luminance than before can be formed.
Further, in Example IV-33 of Table 20, when PG59 is further combined with PG59 in combination with the blue color material and the specific yellow color material, compared to Example IV-32 which achieves the same color, It has been clarified that the P / V ratio can be reduced and the luminance can be improved.

On the other hand, as shown in Comparative Example IV-C1, even when a blue color material and a specific yellow color material are combined in the same manner as in the example, when PG58 is used, when y = 0.670, x = 0.210 However, the display defect occurred, and the luminance was inferior compared with the case of using PG59. Moreover, the development residue and the development adhesion were also poor. Further, as shown in Comparative Example IV-C2, even when a blue color material and a specific yellow color material are combined as in the example, when PG36 is used, when y = 0.670, x = 0.210 Although this area can be displayed, a display defect has occurred and the luminance is low. Further, even when combined with a dispersant that is a polymer having the structural unit represented by the general formula (I), the dispersibility is poor, so the contrast is low, and the re-solubility, the development residue, and the development adhesion are inferior. It was.
On the other hand, photosensitive color resin compositions for color filters of Comparative Examples IV-C3 to IV-C4, in which a blue color material and a specific yellow color material are combined with PG59 and a urethane dispersant or a polyester dispersant is combined. Since the product was inferior in dispersibility, the brightness was lower than in the Examples, the contrast was low, the re-solubility and the development residue were inferior.

As shown in Comparative Examples IV-C5, IV-C8 and IV-C11 in Table 19, with G58, a composition in which a yellow color material is combined without using a blue color material has a film thickness of 2.8 μm. It was not possible to prepare a photosensitive colored resin composition that can realize chromaticity of x = 0.200 and y = 0.710. Further, even with the combination of coloring materials of Comparative Examples IV-C9 and IV-C10, a photosensitive colored resin composition capable of realizing chromaticity of x = 0.200 and y = 0.710 with a film thickness of 2.8 μm. The product could not be prepared.
As shown in Comparative Examples IV-C6 and IV-C13, when G58 is combined with a yellow color material containing PY139 and a blue color material, the film thickness is 2.8 μm, and x = 0.200 and y = 0.710. Although chromaticity could be realized, display failure occurred, luminance was poor, and development residue and development adhesion were also poor.
As shown in Comparative Examples IV-C7 and IV-C12, when a green color material is not used and a blue color material and a yellow color material are combined, the film thickness is 2.8 μm, and x = 0.200 and y = 0. .. Although 710 chromaticity can be realized and display failure does not occur, Comparative Example IV-C7, which has a large blue color material, is extremely inferior in brightness so that it does not reach the practical level. Comparative Example IV-C12 was poor in development residue and development adhesion.

Comparative Example IV-C14 in Table 20 is an example in which the color corresponding to Example IV-24 was realized using G36, but display failure occurred, the luminance was inferior, and further, re-solubility, development residue, The development adhesion was also poor.
Comparative Example IV-C15 was an example in which the color corresponding to Example IV-34 was realized using G36, but the luminance was inferior and the re-solubility, development residue, and development adhesion were poor.
Comparative Example IV-C16 is an example in which the color corresponding to Examples IV-32 and IV-33 was realized using G58, but the luminance was inferior and the re-solubility, development residue, and development adhesion were poor. .

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

Claims

A color material dispersion containing a color material, a dispersant, and a solvent,
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 following 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 one or more selected compounds form a salt;
A color material dispersion for color filters, wherein the dispersant has an acid value of 1 to 18 mg KOH / g and the dispersant has a glass transition temperature of 30 ° C. or higher.

(In General Formula (I), R 1 is a hydrogen atom or a methyl group, A is a divalent linking group, R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon that may contain a hetero atom. Represents a group, and R 2 and R 3 may be bonded to each other to form a ring structure.
In the general formula (1), R a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or benzyl group, or —O—R. It represents 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 an alkylene having 1 to 4 carbon atoms It represents a (meth) acryloyl group via a group. In the general formula (2), R b , R b ′ , and R b ″ each independently represent a hydrogen atom, an acidic group or an ester group thereof, a straight chain having 1 to 20 carbon atoms that may have a substituent, Represents a branched or cyclic alkyl group, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or —O—R f , wherein R f has 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 benzyl group which may have a substituent, or 1 carbon atom Represents a (meth) acryloyl group via an alkylene group of ˜4, X represents a chlorine atom, a bromine atom, or an iodine atom, wherein R c and R d are each independently a hydrogen atom; A hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, Represents a vinyl group, an optionally substituted phenyl group or benzyl group, or —O—R e , where R e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, A phenyl group or benzyl group which may have a substituent, or a (meth) acryloyl group via an alkylene group having 1 to 4 carbon atoms, provided that at least one of R c and R d contains a carbon atom .)
The color material dispersion for a color filter according to claim 1, wherein the block copolymer (P1) in the dispersant contains a structural unit derived from a hydroxyl group-containing monomer.
The block copolymer (P1) in the dispersant is
(I) a structural unit derived from a hydroxyl group-containing monomer and a structural unit derived from an aromatic group-containing monomer, and
(Ii) The color material dispersion for color filter according to claim 1, comprising at least one structural unit derived from a hydroxyl group and aromatic group-containing monomer.
In the salt type block copolymer, the salt type block copolymer is selected from the group consisting of the general formulas (1) to (3) with respect to 1 mol of the terminal nitrogen moiety contained in the structural unit represented by the general formula (I). The color material dispersion for a color filter according to claim 1, wherein the one or more compounds are contained in an amount of 0.1 to 0.7 mol.
The color material is C.I. I. The color material dispersion for color filter according to claim 1, comprising Pigment Green 59.
A photosensitive colored resin composition for a color filter, comprising the colorant dispersion according to claim 1, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.
The photosensitive colored resin composition for a color filter according to claim 6, wherein the photoinitiator includes an oxime ester photoinitiator.
A color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is obtained by curing the photosensitive colored resin composition for a color filter according to claim 6. A color filter comprising a colored layer formed.
9. A liquid crystal display device comprising: the color filter according to claim 8; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.
An organic light-emitting display device comprising the color filter according to claim 8 and an organic light emitter.