JPWO2018159458A1 - Color material dispersion for color filter, dispersant, photosensitive colored resin composition for color filter, color filter, display device - Google Patents

Abstract

A colorant dispersion containing a colorant, a dispersant, and a solvent, wherein the dispersant comprises an A block containing a structural unit represented by the following general formula (I), and a general formula (B1) A color material dispersion liquid for a color filter, which is a block copolymer containing a structural unit represented by the formula and a B block containing at least one selected from the structural units represented by the following general formula (B2). I do. (The symbols in the general formula (I), the general formula (B1) and the general formula (B2) are as described in the specification.)

Description

  The present invention relates to a colorant dispersion liquid for a color filter, a dispersant, a photosensitive colored resin composition for a color filter, a color filter, and a display device.

  In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile 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 attracted attention as a next-generation image display device. In the performance of these image display devices, there is a strong demand for further improvement in image quality and reduction in power consumption such as improvement in contrast and color reproducibility.

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, light that has passed through a color filter is directly colored into the color of each pixel constituting the color filter, and light of those colors is combined to form a color image. As a light source at that time, an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used in addition to a conventional cold cathode tube. In the organic light emitting display device, a color filter is used for color adjustment and the like.
Under such circumstances, demands for higher brightness, higher contrast, and improved color reproducibility of color filters have been increasing.

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

As a method of forming pixels in a color filter, among others, a pigment dispersion method having an averagely excellent characteristic is most widely adopted from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, and the like.
In a color filter having pixels formed using a pigment dispersion method, miniaturization of a pigment is being studied in order to achieve higher luminance and higher contrast. It is considered that by making the pigment finer, scattering of light passing through the color filter due to the pigment particles is reduced, and higher luminance and higher contrast are achieved.
However, finely divided pigment particles are liable to agglomerate, which causes a problem that the dispersibility and the dispersion stability are reduced.

It is known that the use of a dispersant is effective as a technique for improving the dispersibility of the finely divided pigment. For example, Patent Document 1 satisfies the initial dispersibility of the finely divided pigment dispersant and the dispersion stability over time, and furthermore, demands for high contrast, high brightness, high developability, etc. of the liquid crystal display element. For the purpose of filling, as a pigment dispersant, an A block containing a specific repeating unit having an amino group or an ammonium group, and a specific repeating containing an oxygen-containing saturated heterocyclic group or an alkenyl group in the alcohol-derived portion of the carboxylic acid ester A coloring composition for a color filter using a block copolymer having a B block containing a unit is disclosed.
Further, Patent Document 2 discloses a method for forming a colored layer having excellent chromaticity characteristics and heat resistance, and dispersing a pigment with the aim of providing a colored composition for a color filter having good dispersibility and storage stability. A coloring composition for a color filter using a copolymer containing a specific repeating unit having an amino group and a repeating unit having a crosslinkable functional group as an agent and having an amine value of 80 to 250 mgKOH / g is disclosed. Have been.

  Patent Documents 3 and 4 disclose that a photosensitive colored resin composition having excellent color material dispersion stability and excellent development adhesion and solvent resolubility while suppressing generation of development residues is obtained. The use of a specific dispersant is described for the purpose. As a specific dispersant, Patent Document 3 discloses a specific structural unit having an amide group and having a terminal nitrogen site corresponding to an amino group or a structure in which the nitrogen site forms a salt with a specific compound. Further, a block copolymer having a specific amine value and a specific glass transition temperature is described, and Patent Literature 4 discloses that a terminal nitrogen site corresponding to an amino group or the nitrogen site has a specific compound and a salt. A block copolymer containing an A block containing a specific structural unit having a formed structure and a B block containing a structural unit derived from a carboxy group-containing monomer, and further having a specific acid value and a specific glass transition temperature Is described.

International Publication No. 2012/063435 JP 2013-88695 A JP 2016-122033 A JP-A-2006-122169

However, in recent years, color filters are required to have higher luminance and various resistances. Further, in the color filter, an ITO (Indium Tin Oxide) film serving as a transparent electrode is generally formed on the coloring layer. However, in the conventional color filter, a crack is easily generated in the ITO film formed adjacent to the coloring layer, and there is a problem that the crack generated in the ITO film does not allow a current to flow and a display defect occurs. Was.
The present invention has been made in view of the above circumstances, and provides a colorant dispersion capable of forming a high-brightness colored layer and suppressing cracks in an ITO film formed adjacent to the colored layer. The purpose is to do. Further, the present invention provides a dispersant used in the color material dispersion liquid, which can form a high-intensity colored layer and can suppress cracks in an ITO film formed adjacent to the colored layer. Aim. Another object of the present invention is to provide a photosensitive color resin composition for a color filter which can form a high-brightness colored layer and can suppress cracks in an ITO film formed adjacent to the colored layer. And Another object of the present invention is to provide a color filter formed using the photosensitive colored resin composition for a color filter. Another object of the present invention is to provide a display device having excellent display characteristics by using the color filter.

Colorant dispersion for color filter according to the present invention, a colorant, a dispersant, a colorant dispersion containing a solvent,
The dispersant is selected from an A block including a structural unit represented by the following general formula (I), a structural unit represented by the following general formula (B1), and a structural unit represented by the following general formula (B2). And a B block containing at least one of the above.

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

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

（一般式（Ｂ１）中、Ａ^１は２価の連結基、Ｒ^１１は酸素原子を含んでいても良い２、３若しくは４価の脂肪族炭化水素基又は炭素原子、Ｒ^１０及びＲ^１２はそれぞれ独立に、水素原子又はメチル基を表す。ｎは１、２又は３である。）

(In the general formula (B1), A ¹ is a divalent linking group, R ¹¹ is a divalent, trivalent or tetravalent aliphatic hydrocarbon group or a carbon atom which may contain an oxygen atom, and R ¹⁰ and R ¹² are Each independently represents a hydrogen atom or a methyl group; n is 1, 2 or 3)

（一般式（Ｂ２）中、Ａ^２は２価の連結基、Ａ^３及びＡ^４はそれぞれ独立に、２、３又は４価の連結基、Ｒ^１３は酸素原子及び窒素原子から選ばれる少なくとも一種を含んでいても良い２価の炭化水素基、Ｒ^１４、Ｒ^１６、Ｒ^１８及びＲ^１９はそれぞれ独立に、酸素原子を含んでいても良い２価の脂肪族炭化水素基、Ｒ^１０、Ｒ^１５及びＲ^１７はそれぞれ独立に、水素原子又はメチル基を表す。ｎ^１は０、１、２又は３、ｎ^２は０又は１、ｎ^３は０、１又は２を表し、ｎ^１＋ｎ^２は１、２又は３であり、ｎ^１＋ｎ^２＋ｎ^３は１、２又は３である。ｍ^１は１、２又は３、ｍ^２は０、１又は２を表し、ｍ^１＋ｍ^２は１、２又は３である。）

(In the general formula (B2), A ² is a divalent linking group, A ³ and A ⁴ are each independently a divalent, tri- or tetravalent linking group, and R ¹³ is at least one selected from an oxygen atom and a nitrogen atom. R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ may each independently represent a divalent aliphatic hydrocarbon group optionally containing an oxygen atom, R ¹⁰ , R ^{10 15} and R ¹⁷ each independently represent a hydrogen atom or a methyl group, n ¹ represents 0, 1, ² , or 3, n ² represents 0 or 1, n ³ represents 0, 1, or 2, and n ¹ + n ² Is 1, 2 or 3 and n ¹ + n ² + n ³ is 1, 2 or 3. m ¹ represents 1, 2 or 3, m ² represents 0, 1 or 2, and m ¹ + m ² represents 1 , 2 or 3.)

  The dispersant according to the present invention includes an A block including a structural unit represented by the general formula (I), a structural unit represented by the general formula (B1), and a structure represented by the general formula (B2). And a B block containing at least one type selected from units.

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

  A display device according to the present invention includes the color filter according to the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the coloring material dispersion liquid which can form a high-luminance coloring layer and can suppress the crack of the ITO film formed adjacently on a coloring layer can be provided. Further, according to the present invention, there is provided a dispersant used in the color material dispersion liquid, which can form a high-luminance colored layer and can suppress cracks in an ITO film formed adjacent to the colored layer. be able to. Further, according to the present invention, it is possible to provide a photosensitive colored resin composition for a color filter, which can form a high-brightness colored layer and can suppress cracks in an ITO film formed adjacent to the colored layer. Can be. Further, according to the present invention, a color filter formed using the photosensitive colored resin composition for a color filter can be provided. Further, according to the present invention, a display device having excellent display characteristics can be provided by using the color filter.

FIG. 1 is a schematic diagram illustrating an example of the color filter of the present invention. FIG. 2 is a schematic view showing one example of the liquid crystal display device of the present invention. FIG. 3 is a schematic diagram illustrating an example of the organic light emitting display device of the present invention.

Hereinafter, the color material dispersion for color filters, the dispersant, the photosensitive colored resin composition for color filters, the color filters, and the display device according to the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and non-visible regions, and furthermore, radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryloyl represents each of acryloyl and methacryloyl, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.
In the present specification, unless otherwise specified, the chromaticity coordinates x and y are in the XYZ color system of JIS Z8701: 1999 measured using a C light source.

I. Color material dispersion for color filter The color material dispersion for color filter according to the present invention is a color material dispersion containing a color material, a dispersant, and a solvent,
The dispersant is selected from an A block including a structural unit represented by the following general formula (I), a structural unit represented by the following general formula (B1), and a structural unit represented by the following general formula (B2). And a B block containing at least one of the above.

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

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

（一般式（Ｂ１）中、Ａ^１は２価の連結基、Ｒ^１１は酸素原子を含んでいても良い２、３若しくは４価の脂肪族炭化水素基又は炭素原子、Ｒ^１０及びＲ^１２はそれぞれ独立に水素原子又はメチル基を表す。ｎは１、２又は３である。）

(In the general formula (B1), A ¹ is a divalent linking group, R ¹¹ is a divalent, trivalent or tetravalent aliphatic hydrocarbon group or a carbon atom which may contain an oxygen atom, and R ¹⁰ and R ¹² are Each independently represents a hydrogen atom or a methyl group; n is 1, 2 or 3)

（一般式（Ｂ２）中、Ａ^２は２価の連結基、Ａ^３及びＡ^４はそれぞれ独立に、２、３又は４価の連結基、Ｒ^１３は酸素原子及び窒素原子から選ばれる少なくとも一種を含んでいても良い２価の炭化水素基、Ｒ^１４、Ｒ^１６、Ｒ^１８及びＲ^１９はそれぞれ独立に、酸素原子を含んでいても良い２価の脂肪族炭化水素基、Ｒ^１０、Ｒ^１５及びＲ^１７はそれぞれ独立に、水素原子又はメチル基を表す。ｎ^１は０、１、２又は３、ｎ^２は０又は１、ｎ^３は０、１又は２を表し、ｎ^１＋ｎ^２は１、２又は３であり、ｎ^１＋ｎ^２＋ｎ^３は１、２又は３である。ｍ^１は１、２又は３、ｍ^２は０、１又は２を表し、ｍ^１＋ｍ^２は１、２又は３である。）

(In the general formula (B2), A ² is a divalent linking group, A ³ and A ⁴ are each independently a divalent, tri- or tetravalent linking group, and R ¹³ is at least one selected from an oxygen atom and a nitrogen atom. R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ may each independently represent a divalent aliphatic hydrocarbon group optionally containing an oxygen atom, R ¹⁰ , R ^{10 15} and R ¹⁷ each independently represent a hydrogen atom or a methyl group, n ¹ represents 0, 1, ² , or 3, n ² represents 0 or 1, n ³ represents 0, 1, or 2, and n ¹ + n ² Is 1, 2 or 3 and n ¹ + n ² + n ³ is 1, 2 or 3. m ¹ represents 1, 2 or 3, m ² represents 0, 1 or 2, and m ¹ + m ² represents 1 , 2 or 3.)

Since the colorant dispersion according to the present invention uses a block copolymer containing the specific A block and the specific B block as a dispersant, a color filter prepared using the colorant dispersion is used. The photosensitive colored resin composition for use can form a high-intensity colored layer, and can suppress cracks in an ITO film formed adjacent to the colored layer. The effect of exerting such an effect is not yet elucidated but is presumed as follows.
The specific block copolymer improves the dispersibility and dispersion stability of the coloring material because the A block is easily adsorbed on the coloring material, and the structural unit represented by the general formula (B1) included in the B block. And in at least one selected from the structural units represented by the general formula (B2), it is considered that the (meth) acryloyl group is likely to crosslink with another crosslinkable group when forming the colored layer. With a conventional dispersant, the crosslinking density near the coloring material is insufficient, and swelling due to a solvent is likely to occur. Therefore, after the ITO film is formed adjacent to the colored layer, a solvent such as NMP (N-methyl-2-pyrrolidone) contained in the coating solution applied on the ITO film in the next step forms a film under the ITO film. It is considered that cracks are likely to occur in the ITO film, which is an inorganic substance, by expanding the colored layer located. In contrast, the dispersant used in the present invention has at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) in the B block (meta) ) The acryloyl group cross-links with other cross-linkable groups, and particularly easily cross-links between the molecules of the dispersant adsorbed on the color material. It is considered that the film strength can be improved by reducing the portion where sparseness is reduced. Therefore, in the present invention, the coloring layer can secure the crosslinking density even in the vicinity of the coloring material, and can reduce the portion where the crosslinking density is low, thereby suppressing swelling due to the solvent. It is presumed that the color filter can be easily formed without causing cracks in the ITO film formed adjacent to the coloring layer. In addition, since the coloring material in the coloring layer is covered with a cured film having a high crosslinking density, thermal motion during baking of coloring material molecules is reduced, and deterioration of the coloring material is suppressed. From this, it is estimated that a decrease in the luminance of the colored layer is suppressed, and thus a colored layer with high luminance can be formed.
Further, the (meth) acryloyl group in the side chain of at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) is other than an oxetanyl group or the like. Compared to the crosslinkable groups of the above, the photopolymerizability when combined with a radical polymerization initiator is excellent, so that when forming a colored layer, it can be sufficiently reacted by exposure to increase the crosslink density, and post-baking. At times, it is considered that the effect of suppressing a decrease in luminance is obtained due to a high crosslinking density, and the luminance of the formed colored layer is further improved. Further, compared to other crosslinkable groups such as oxetanyl groups, the (meth) acryloyl group is superior in storage stability under acid or basicity, and therefore, in the presence of an acidic group of a resin or a basic group of a dispersant. It is thought that the viscosity stability is further improved because of its excellent stability.
Further, in the manufacturing process of the color filter, the coloring material may sublimate or precipitate and adhere to the coloring layer, which may cause a foreign matter defect. When the color material sublimates from the color layer of the color filter, not only does the color tone of the color layer change, but also the color tone of the other color layer changes by attaching to another color layer and the like, and the brightness decreases. There is a problem that contamination in the inside occurs. On the other hand, the present invention uses the specific block copolymer as a dispersant, whereby the coloring material being colored is covered with a cured film having a high crosslinking density, thereby sublimating the coloring material. And precipitation can be suppressed.

The coloring material dispersion according to the present invention contains at least a coloring 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 of the present invention.

<Dispersant>
In the present invention, as a dispersant, an A block containing a structural unit represented by the general formula (I), a structural unit represented by the general formula (B1), and a structural unit represented by the general formula (B2) A block copolymer containing a B block containing at least one selected from structural units is used.
The block copolymer has at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) and at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon. A salt may be formed (hereinafter, sometimes referred to as a salt-type block copolymer).
First, the block copolymer will be described.

{A block}
(Structural unit represented by general formula (I))
The structural unit represented by the general formula (I) contained in the A block has basicity and functions as an adsorption site for a coloring material.
In the general formula (I), A is a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms (-R'-OR "-). : R ′ and R ″ are each independently an alkylene group) and combinations thereof.
Among them, from the viewpoint of dispersibility, A in the general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group.

Examples of the hydrocarbon group in the hydrocarbon group optionally containing a hetero atom in R ² and R ³ include an alkyl group, an aralkyl group, and an aryl group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group, and the like. 1-18 are preferable, and among them, a methyl group or an ethyl group is more preferable.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 14 carbon atoms.
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 from 6 to 24, and more preferably from 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, a silicon atom and the like.
Further, the hydrogen atom in the hydrocarbon group may be substituted by a halogen atom such as an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom and a bromine atom.

That R ² and R ³ are bonded to each other to form a ring structure means that R ² and R ³ form a ring structure via a nitrogen atom. 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, a morpholine ring and the like.

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, or a phenyl group, or R ² and R ³ are bonded to form a pyrrolidine ring, It preferably forms a piperidine ring and a morpholine ring.

Examples of the monomer for deriving the structural unit represented by the general formula (I) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. Examples thereof include (meth) acrylates containing an alkyl group-substituted amino group and (meth) acrylamides containing an alkyl group-substituted amino group such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide. Among them, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used from the viewpoint 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. Above all, from the viewpoint of improving dispersibility and dispersion stability, it is preferable to include 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. Any polymerizable structural unit can be contained. For example, as the structural units other than the structural units represented by the general formula (I) that may be contained in the A block, the “other structural units” listed in the B block described below can be used. Examples include a structural unit represented by the general formula (II) described below.
The content of the structural unit represented by the general formula (I) in the A block in the block copolymer before salt formation is 50 to 100% by mass based on the total mass of all the structural units in the A block. Is preferred, more preferably 80 to 100% by mass, and most preferably 100% by mass. This is because the higher the proportion of the structural unit represented by the general formula (I), the higher the adsorptivity to the coloring material and the better the dispersibility and dispersion stability of the block copolymer. The content ratio of the above structural units is calculated from the mass charged when synthesizing the A block having the structural unit represented by the general formula (I).

Further, in the block copolymer before salt formation, the content of the structural unit represented by the general formula (I) is determined based on the point that the dispersibility and the dispersion stability are improved. Is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total mass of In addition, the content ratio of each structural unit in the block copolymer is calculated from the charged mass at the time of synthesizing the block copolymer before salt formation.
The structural unit represented by the general formula (I) has only to have an affinity for a coloring material, and may be composed of one type or may include two or more types of structural units. Good.

{B block}
The B block does not include the structural unit represented by the general formula (I), and includes at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2). It is a block that includes seeds and may further include other constituent units as long as the effects of the present invention are not impaired. The B block is appropriately selected from monomers having an unsaturated double bond copolymerizable with the monomer for deriving the structural unit represented by the general formula (I), depending on the solvent so as to have a solvophilic property. It is preferable to use a block configured selectively from the viewpoint of dispersibility and dispersion stability. As a guide, it is preferable to introduce a B block so that the solubility of the copolymer at 23 ° C. in the solvent used in combination is 20 (g / 100 g solvent) or more.

(At least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2))
The B block includes at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2).
As A ^{1 in the} general formula (B1), and the divalent linking group in A ² , A ³ and A ⁴ in the general formula (B2), and the trivalent or tetravalent linking group in A ³ and A ⁴ , For example, it represents an aliphatic hydrocarbon group, an aromatic group, a -CONH- group, a -COO- group, or a combination thereof, and has O (oxygen atom), S (sulfur atom), N (nitrogen atom) in the carbon chain. And may have a substituent. The tetravalent linking group may be a carbon atom.
The aliphatic hydrocarbon group for A ¹ , A ² , A ³ and A ⁴ may be linear, branched or cyclic, saturated or unsaturated, may have a substituent, and may have a carbon chain. It may contain hetero atoms such as O, S, and N. For example, a carbon chain may contain an ether group, a thioether group, a carbonyl group, an oxycarbonyl group, an amide group, and the like. Examples of the substituent include a halogen atom, an alkoxy group, and a phenoxy group.
The aromatic group in A ¹ , A ² , A ³ and A ⁴ includes a monocyclic or polycyclic aromatic group, and may have a substituent, and is a heterocyclic ring containing O, S, and N. There may be. Examples of the aromatic group include a group containing a benzene ring and a naphthalene ring, and among them, a group containing a benzene ring is preferable. Examples of the substituent include the same as those described above.
Examples of the combination of the aliphatic hydrocarbon group and the aromatic group in A ¹ , A ² , A ^3, and A ⁴ include a structure in which the aliphatic hydrocarbon group and the aromatic group are directly bonded, and a structure in which the aliphatic hydrocarbon group is directly combined with the aliphatic hydrocarbon group. And a structure in which a group and the aromatic group are linked by a linking group containing a hetero atom such as the ether group.
As the divalent linking group in A ¹ of the general formula (B1) and A ² of the general formula (B2), among others, a divalent group containing a —COO— group and an alkylene group having 1 to 10 carbon atoms. Is preferable, and a divalent linking group which is a combination of a -COO- group and an alkylene group having 1 to 10 carbon atoms is more preferable. As the divalent linking group in A ³ and A ⁴ in the formula (B2), an alkylene group having 1 to 10 carbon atoms is preferable. A ^{1 in the} general formula (B1) and alkylene groups in A ² , A ³ and A ⁴ in the general formula (B2) may be linear, branched or cyclic, Is preferred. Further, the alkylene group may have a substituent, and a carbon atom may include a hetero atom such as O, S, or N.
As the trivalent linking group in A ³ and A ⁴ of the general formula (B2), among others, the remaining atomic group obtained by removing three hydrogen atoms from an aliphatic saturated hydrocarbon having 1 to 10 carbon atoms is preferable, The remaining atomic groups obtained by removing three hydrogen atoms from an aliphatic saturated hydrocarbon having 1 to 5 carbon atoms are more preferable. These aliphatic saturated hydrocarbon groups may have a substituent, and a carbon atom may contain a hetero atom such as O, S, or N.
As the tetravalent linking group for A ³ and A ⁴ in the general formula (B2), among others, the remaining atomic groups or carbon atoms obtained by removing 4 hydrogen atoms from an aliphatic saturated hydrocarbon having 1 to 10 carbon atoms. Is preferable, and the remaining atomic group or carbon atom obtained by removing 4 hydrogen atoms from an aliphatic saturated hydrocarbon having 1 to 5 carbon atoms is more preferable. These aliphatic saturated hydrocarbon groups may have a substituent, and a carbon atom may contain a hetero atom such as O, S, or N.

The divalent hydrocarbon group which may contain at least one selected from the oxygen atom and the nitrogen atom in R ¹³ of the general formula (B2) is any of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. May be, for example, a straight-chain, branched or cyclic alkylene group and alkenylene group which may contain at least one selected from an oxygen atom and a nitrogen atom, an arylene group, and combinations thereof, and in the carbon chain , -CONH- group, -COO- group, ether group and the like.

Examples of the divalent aliphatic hydrocarbon group which may contain an oxygen atom in R ¹¹ of the general formula (B1) and R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ of the general formula (B2) include , A linear, branched or cyclic alkylene group and an alkenylene group, and an ether group or the like may be contained in the carbon chain. Among them, an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom is preferable.
Incidentally, in the above case ^{where R 14,} R ^{16, R 18} or ^{R 19} there are a plurality in the general formula (B2), a plurality of ^{R 14,} a plurality of ^{R 16,} a plurality of ^{R 18} and a plurality of ^{R 19} are each They may be the same or different.
Examples of the trivalent or tetravalent aliphatic hydrocarbon group which may contain an oxygen atom in R ¹¹ of the general formula (B1) include, for example, a linear, branched or cyclic aliphatic saturated hydrocarbon or aliphatic hydrocarbon. The remaining aliphatic hydrocarbon group or carbon atom obtained by removing three or four hydrogen atoms from the group-unsaturated hydrocarbon may be mentioned, and an ether group or the like may be contained in the carbon chain. Among them, the remaining aliphatic saturated hydrocarbon groups or carbon atoms obtained by removing 3 or 4 hydrogen atoms from a linear, branched or cyclic aliphatic saturated hydrocarbon having 1 to 10 carbon atoms which may contain an oxygen atom Atoms are preferred.

As R ¹⁰ and R ¹² of the general formula (B1) and R ¹⁰ , R ¹⁵ and R ¹⁷ of the general formula (B2), among others, the reactivity is high, the film strength is improved, and the brightness and the brightness of the colored layer are improved. A hydrogen atom is preferable from the viewpoint of improving the crack resistance of the ITO film.
In addition, when there are a plurality of R ¹² in the general formula (B1) and when there are a plurality of R ¹⁵ or R ^{17 in the} general formula (B2), a plurality of R ¹² , a plurality of R ¹⁵ and a plurality of R ¹⁵ are provided. R ¹⁷ may be the same or different.

In the general formula (B2), from the viewpoint that the hydroxyl value of the dispersant is likely to be appropriate, the solvent resolubility and the development adhesion, and the luminance and the crack resistance of the ITO film, n ¹ + n ² > n. ³ , and more preferably, m ¹ > m ² .

  The number of (meth) acryloyl groups in the side chain of at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) is not particularly limited. From the viewpoint of improving the crack resistance of the ITO film, the number is preferably two or more. On the other hand, from the viewpoint of dispersion stability, the number is preferably six or less, more preferably three or less. Or one or two.

At least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) is, for example, a monomer that induces the structural unit represented by the general formula (I) Using a monomer having an unsaturated double bond copolymerizable with and a hydroxyl group (hereinafter referred to as “hydroxyl-containing monomer”), a structural unit having a hydroxyl group is introduced, and an isocyanate group and a (meth) acryloyl group are formed. The isocyanate group of the compound (hereinafter, referred to as “isocyanate group-containing (meth) acrylate”) can be introduced by reacting with a hydroxyl group in the structural unit.
In addition, for the structural unit represented by the general formula (B2), for example, a structural unit having a hydroxyl group is introduced using a hydroxyl group-containing monomer, and one of the isocyanate groups of the diisocyanate compound reacts with the hydroxyl group in the structural unit. Then, the other isocyanate group of the diisocyanate compound can be reacted with a hydroxyl group of a compound having a hydroxyl group and a (meth) acryloyl group to introduce the compound.
Here, the hydroxyl group refers to an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.
Since the hydroxyl group and the isocyanate group have high reactivity, the reaction temperature can be lowered to about 70 to 90 ° C., and there is no need to use an amine catalyst, the structure represented by the general formula (B1) by the above method. By introducing at least one selected from a unit and a structural unit represented by the general formula (B2), yellowing due to heating or a catalyst during the reaction can be suppressed, and thus yellowing of the colored layer is also suppressed. As a result, the luminance of the colored layer can be improved. In addition, in the above introduction method, since the hydroxyl value can be easily adjusted, the solvent resolubility and the like can be improved by setting the hydroxyl value to an appropriate value.

The hydroxyl group-containing monomer is not particularly limited as long as it has an unsaturated double bond copolymerizable with the monomer for deriving the structural unit represented by the general formula (I) and at least one hydroxyl group. For example, 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate, cyclohexane dimethanol mono (meth) acrylate, etc. Hydroxyalkyl (meth) acrylates, alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, hydroxyaryloxyalkyl (meth) acrylates such as 2-hydroxy-3-phenoxypropyl (meth) acrylate, hydroxyalkoxya (Meth) acrylate monomers having a hydroxyl group such as alkyl (meth) acrylate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and 1 mol of ε-caprolactone of 2-hydroxyethyl (meth) acrylate N- (hydroxyalkyl) (meth) such as N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide (Meth) acrylamide monomers having a hydroxyl group such as acrylamide; hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, 2- (or 3- or 4-) hydroxybutyl vinyl ether Vinyl ether monomers having a hydroxyl group such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, and hydroxyalkyl allyl ether such as 2- (or 3- or 4-) hydroxybutyl allyl ether Allyl ether-based monomers having a hydroxyl group such as; among them, (meth) acrylate-based monomers having a hydroxyl group are preferable, and from the viewpoint of improving developability, having a primary hydroxyl group. It is more preferable than having 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. In addition, from the viewpoint of improving development adhesion, it is preferable to use a hydroxyl group-containing monomer having a glass transition temperature (Tgi) of 0 ° C or higher, more preferably 10 ° C or higher, of the homopolymer of each monomer. It is preferable to use a hydroxyl group-containing monomer.
As the (meth) acrylate monomer having a hydroxyl group, at least one selected from hydroxyalkyl (meth) acrylate, hydroxyarylalkyl (meth) acrylate, hydroxyalkoxyalkyl (meth) acrylate and hydroxyaryloxyalkyl (meth) acrylate Species are more preferred, and at least one selected from hydroxyalkyl (meth) acrylate and hydroxyaryloxyalkyl (meth) acrylate is even more preferred, and 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 2 Particularly preferred is at least one member selected from the group consisting of -hydroxy-3-phenoxypropyl (meth) acrylate.

As the isocyanate group-containing (meth) acrylate used when introducing the structural unit represented by the general formula (B1), for example, 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) Acrylate, 2-isocyanato-1-methylethyl (meth) acrylate, 2-isocyanato-1,1-dimethylethyl (meth) acrylate, 4-isocyanatocyclohexyl (meth) acrylate, 2- (2- (meth) acrylic acid Examples include isocyanate ethoxy) ethyl, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, and derivatives thereof. Examples of the derivative include a compound having an isocyanate group masked with a blocking agent and at least one (meth) acryloyl group. For example, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate And 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate.
These commercially available products include, for example, Karenz AOI (registered trademark), Karenz MOI (registered trademark), AOI-VM (registered trademark), Karenz MOI-EG (registered trademark), Karenz BEI (registered trademark), Karenz MOI-BP (Registered trademark), Karenz MOI-BM (registered trademark) (all manufactured by Showa Denko KK) and the like.

The isocyanate group-containing (meth) acrylate used when introducing the structural unit represented by the general formula (B2) is, for example, a hydroxyl group-containing (meth) acrylate and a diisocyanate compound having a molar ratio of about 1: 1. Reaction products.
Examples of the hydroxyl group-containing (meth) acrylate in the reaction product include a (meth) acrylate-based monomer having the hydroxyl group, which can be used as the hydroxyl group-containing monomer, and a hydroxyl group-containing polyfunctional (meth) acrylate. Can be. The hydroxyl group-containing polyfunctional (meth) acrylate is a compound having at least one hydroxyl group and two or more (meth) acryloyl groups, and is not particularly limited, but has 1 to 4 hydroxyl groups and has (meth) acryloyl Those having 2 to 5 groups are preferred. Specific examples of the hydroxyl group-containing polyfunctional (meth) acrylate include, for example, trimethylolpropane di (meth) acrylate, pentaerythritol di- or tri (meth) acrylate, dipentaerythritol di, tri, tetra or penta (meth) acrylate. Acrylate and the like.
Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate, m- Or p-xylylene diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, lysine diisocyanate, pyridinediyl isocyanate and the like.

  In the isocyanate group-containing (meth) acrylate, the isocyanate group is preferably 0.1 equivalent or more and 0.9 equivalent or less, more preferably 0.15 equivalent or more and 0.1 equivalent or less with respect to 1 equivalent of the hydroxyl group of the hydroxyl group-containing monomer. It is preferable to use the compound so as to have an equivalent weight of 8 equivalents or less, since the hydroxyl value is easily adjusted to an appropriate value, the development adhesion, the solvent resolubility, and the adhesion of the colored resin composition.

  In the isocyanate group-containing (meth) acrylate, the (meth) acryloyl group is preferably 0.1 equivalent or more and 3.0 equivalent or less, more preferably 0.15 equivalent or less with respect to 1 equivalent of the hydroxyl group of the hydroxyl group-containing monomer. It is preferable to use it so as to be not less than 2.5 equivalents in view of luminance and crack resistance of the ITO film.

Further, the structural unit represented by the general formula (B2) may be obtained by reacting a hydroxyl group of a structural unit derived from the hydroxyl group-containing monomer with one isocyanate group of a diisocyanate compound, and further reacting with the other isocyanate group of the diisocyanate compound. In the case of a structural unit introduced by reacting a hydroxyl group-containing (meth) acrylate, the hydroxyl group-containing (meth) acrylate here is reacted with the hydroxyl group-containing (meth) acrylate at a molar ratio of about 1: 1 of the diisocyanate compound. The same ones as described for the product can be used. In this case, one isocyanate group of the diisocyanate compound is preferably 0.1 equivalent or more and 0.9 equivalent or less, more preferably 0.15 equivalent or more and 0.1 equivalent or less with respect to 1 equivalent of the hydroxyl group of the structural unit derived from the hydroxyl group-containing monomer. It is preferable to use a diisocyanate compound so as to have an equivalent weight of 8 equivalents or less, since the hydroxyl value is easily adjusted to an appropriate value, the development adhesion and the solvent resolubility, and the adhesion of the colored resin composition.
Further, the hydroxyl group of the hydroxyl group-containing (meth) acrylate is preferably 0.1 equivalent or more and 0.9 equivalent or less, more preferably 0.15 equivalent or more and 0.8 equivalent with respect to 1 equivalent of the other isocyanate group of the diisocyanate compound. It is preferable to use a hydroxyl group-containing (meth) acrylate as described below.

In the block copolymer, the content of at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) is not particularly limited, but the block copolymer is not particularly limited. Is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 4% by mass or more, and 35% by mass or less, based on the total mass of all the structural units. Is preferably 30% by mass or less, and may be 20% by mass or less.
Since the content ratio of at least one kind selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) is equal to or more than the lower limit, the luminance of the colored layer and the coloring The effect of suppressing cracks in the ITO film formed adjacently on the layer (hereinafter, simply referred to as crack resistance of the ITO film) is improved, and the plate making characteristics can be improved by being equal to or less than the upper limit.
In addition, at least one kind selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) may be composed of one kind or two or more kinds. Units may be included.

In the block copolymer before salt formation, the (meth) acryloyl group equivalent contained in the side chain is preferably in the range of 100 to 6000, and particularly preferably in the range of 250 to 4500. When the (meth) acryloyl group equivalent is at least the above lower limit, the luminance of the colored layer and the crack resistance of the ITO film are further improved. Is improved.
Here, the (meth) acryloyl group equivalent is a weight average molecular weight per 1 mol of the (meth) acryloyl group in the block copolymer before salt formation, and is represented by the following formula (1).

Formula (1) (meth) acryloyl group equivalent (g / mol) = W ′ (g) / M ′ (mol)
(In the formula (1), W ′ represents the mass (g) of the block copolymer before salt formation, and M ′ is contained in the block copolymer W ′ (g) before salt formation. (It represents the number of moles (mol) of acryloyl group.)

  The (meth) acryloyl group equivalent is determined, for example, by the number of (meth) acryloyl groups contained in 1 g of the block copolymer before salt formation in accordance with the test method of element value as described in JIS K 0070: 1992. May be calculated by measuring.

  In addition, in the synthesis of the block copolymer used in the present invention, by appropriately adjusting the charged amount of each structural unit, the content of the structural unit of the block copolymer can be set to a desired content, and the copolymer having the desired performance can be obtained. Can be combined. Among them, at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2), using the hydroxyl group-containing monomer and the isocyanate group-containing (meth) acrylate. When one kind is introduced, in the synthesis of the block copolymer, the charged amount of the hydroxyl group-containing monomer is at least 5% by mass based on the total amount of the monomers, thereby improving the brightness of the colored layer and the crack resistance of the ITO film. It is preferable from the point that it does, and it is more preferable that it is 10 mass% or more. In addition, from the viewpoint of solvent resolubility, the amount of the hydroxyl group-containing monomer to be charged is preferably 50% by mass or less, more preferably 40% by mass or less based on the total amount of the monomers. Further, the charged amount of the isocyanate group-containing (meth) acrylate is 10% by mass with respect to the charged amount of the hydroxyl group-containing monomer from the viewpoint of improving the luminance of the colored layer, the crack resistance of the ITO film, and the adhesion. It is preferably at least 15% by mass, and more preferably at most 120% by mass, from the viewpoint of solvent resolubility, development adhesion, brightness, and crack resistance of the ITO film, and preferably 90% by mass. %, More preferably at most 85% by mass.

(Other units)
The B block may contain other structural units for further improving the solvophilicity.
Examples of the other structural units constituting the B block include a monomer having an unsaturated double bond copolymerizable with a monomer that derives the structural unit represented by the general formula (I), Among them, a structural unit represented by the following general formula (II) is preferable.

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

(In the general formula (II), A ′ is a direct bond or a divalent linking group, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ or a monovalent group represented by — [(CH ₂ ) _y —O] _z —R ^8. R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group. R ⁸ is a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or a carbon atom having 1 to 5 carbon atoms. It is an alkyl group.
The hydrocarbon group may have a substituent.
x 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 the general formula (II), A ′ is a direct bond or a divalent linking group. The direct bond means that A ′ has no atom, that is, C (carbon atom) in the general formula (II) and R ⁵ are bonded without any other atom. Examples of the divalent linking group include those similar to A in the general formula (I). A ′ in the general formula (II) is preferably a direct bond or a divalent linking group containing a —CONH— group or a —COO— group 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. Is shown.
The hydrocarbon group for R ⁵ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group.
The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, -Ethylhexyl, 2-ethoxyethyl, cyclopentyl, cyclohexyl, bornyl, isobornyl, dicyclopentanyl, dicyclopentenyl, adamantyl, lower alkyl-substituted adamantyl, and the like.
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. Although the position of the double bond of the alkenyl group is not limited, it is preferable that the terminal of the alkenyl group has a double bond from the viewpoint of the reactivity of the obtained polymer.
Examples of the substituent of an aliphatic hydrocarbon such as an alkyl group and 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 from 6 to 24, and more preferably from 6 to 12.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent. The aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 14 carbon atoms.
Examples of the substituent for an aromatic ring such as an aryl group or an aralkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, a nitro group, and a halogen atom.
The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

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

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

As the R ^5, among others, preferably be selected to be excellent in compatibility with a solvent to be described later, specifically, for example, the solvent is generally a solvent for a color filter colored resin composition When a 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 and the like are preferable.

Furthermore, the R ⁵ is within a range which does not impair the dispersion performance of the block copolymer, an alkoxy group, a hydroxyl group, an acidic group, an epoxy group, may be those substituted by a substituent such as an isocyanate group, and After the synthesis of the block copolymer, the substituent may be added by reacting with the compound having the substituent.

(Structural unit derived from acidic group-containing monomer)
It is preferable that the B block further contains a structural unit derived from an acidic group-containing monomer, from the viewpoint of improving the solvent affinity of the B block and improving the dispersibility and dispersion stability of the colorant dispersion.
Examples of the acidic group-containing monomer include a monomer having an acidic group and an unsaturated double bond copolymerizable with the monomer for deriving the structural unit represented by the general formula (I).
Examples of the acidic group include a carboxy group, a phosphoric acid group, a sulfo group, a boric acid group, and the like. Among them, a carboxy group is preferable from the viewpoint of developability.
Examples of the carboxy group-containing monomer include (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. An addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate with a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic anhydride; ω-carboxy-polycaprolactone; Mono (meth) acrylates can also be used. Further, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as a precursor of the carboxy group. Among them, (meth) acrylic acid is particularly preferable in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.

When containing a structural unit derived from an acidic group-containing monomer, in the block copolymer before salt formation, the content ratio of the structural unit derived from the acidic group-containing monomer is not particularly limited, but all the structural units of the block copolymer It is preferably from 0.05 to 4.5% by mass, more preferably from 0.07 to 3.7% by mass, based on the total mass.
When the content ratio of the structural unit derived from the acidic group-containing monomer is at least the lower limit value, the effect of suppressing the development residue is excellent, and the deterioration of the development adhesion and the solvent resolubility deteriorate at the lower limit value or less. Can be prevented.
The structural unit derived from the acidic group-containing monomer may be composed of one type, or may include two or more types of structural units.

  The number of structural units constituting the B block is not particularly limited, but is preferably 10 to 300 from the viewpoint that the lipophilic portion and the lipophilic material portion act effectively and improve the dispersibility of the coloring material. Preferably, the number is 10 to 100, more preferably 10 to 70.

  In the B block in the block copolymer, the content of the structural unit represented by the general formula (II) is determined based on the total mass of all the structural units of the B block from the viewpoint of improving the solvophilicity and the dispersibility of the coloring material. On the other hand, the content is preferably 30 to 95% by mass, and more preferably 40 to 90% by mass. The content ratio of the above structural units is calculated from the charged mass when synthesizing the B block.

  Further, in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (II) is determined based on the total mass of all the structural units of the block copolymer from the viewpoint of improving the colorant dispersibility. Is preferably 40 to 95% by mass, more preferably 50 to 90% by mass. In addition, the content ratio of the structural unit is calculated from the charged mass at the time of synthesizing the block copolymer before salt formation.

  In the B block, it is preferable to appropriately select a structural unit so as to function as a lipophilic moiety. The structural unit represented by the general formula (II) may be composed of one type or two types. The above constituent units may be included. Two or more types of structural units included in the B block may be randomly arranged in the block.

  In the present invention, it is preferred that the block unit derived from the hydroxyl group-containing monomer be contained in the B block of the block copolymer before salt formation, from the viewpoint of improving development adhesion. When the structural unit derived from the hydroxyl group-containing monomer is included, it tends to interact with glass, metal, or the like which is usually used as a substrate, so that it is considered that development adhesion is improved. When the structural unit derived from the hydroxyl group-containing monomer is contained in the B block, the developing speed is further improved.

  When a structural unit derived from a hydroxyl group-containing monomer is contained, the content ratio of the structural unit derived from the hydroxyl group-containing monomer in the block copolymer before salt formation is 1 to the total mass of all the structural units of the block copolymer. It is preferably at least 2% by mass, more preferably at least 2% by mass, still more preferably at least 3% by mass, particularly preferably at least 4% by mass. When the ratio is equal to or more than the lower limit, the developing adhesion can be made preferable. Similarly, the content 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. It is preferable that the ratio is equal to or less than the above upper limit since the introduction ratio of other useful monomers can be increased. In addition, the content ratio of the structural unit is calculated from the charged mass at the time of synthesizing the block copolymer before salt formation.

Further, in the present invention, it is preferable that a structural unit derived from an aromatic group-containing monomer be contained in the B block from the viewpoint of improving solvent resolubility. When a structural unit derived from an aromatic group-containing monomer is included, compatibility with a solvent and other components is easily improved, and thus it is considered that 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 copolymerizable with the monomer for deriving the structural unit represented by the general formula (I) can be used. . Examples of such a monomer include acrylates such as benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and phenoxyethyl (meth) acrylate; styrenes such as styrene; and vinyl ethers such as phenyl vinyl ether. And the like.
From the viewpoint of improving development adhesion, it is preferable to use an aromatic group-containing monomer having a glass transition temperature (Tgi) of a homopolymer of each monomer of 0 ° C. or higher, and more preferably 10 ° C. or higher. It is preferable to use an aromatic group-containing monomer.
In particular, it is at least one selected from the group consisting of benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and phenoxyethyl (meth) acrylate because resolubility is easily improved. And more preferably one or more selected from the group consisting of benzyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate.

  When a structural unit derived from an aromatic group-containing monomer is contained, the content ratio of the structural unit derived from an aromatic group-containing monomer in the block copolymer prior to salt formation is preferably from the viewpoint of improving solvent resolubility. It is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and still more preferably 4% by mass or more, based on the total mass of all the structural units of the polymer. Is particularly preferred. When it is at least the above lower limit, the solvent resolubility can be made preferable. Similarly, the content 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. It is preferable that the ratio is equal to or less than the above upper limit since the introduction ratio of other useful monomers can be increased.

  In particular, the B block contains at least one of (i) a structural unit derived from a hydroxyl group-containing monomer and an aromatic group-containing monomer, and (ii) a structural unit derived from a hydroxyl group and an aromatic group-containing monomer. Is preferable from the viewpoint of improving development adhesion and solvent resolubility.

(I) When a structural unit derived from a hydroxyl group-containing monomer and a structural unit derived from an aromatic group-containing monomer are respectively contained, the structural unit derived from the hydroxyl group-containing monomer is added 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. This is because when the ratio is equal to or more than the above lower limit, the developing adhesion can be excellent. Similarly, the structural unit derived from the hydroxyl group-containing monomer is preferably contained in an amount of 15 parts by mass or less, more preferably 7 parts by mass or less, based on 1 part by mass of the structural unit of the aromatic group-containing monomer. This is because when the content is equal to or less than the above upper limit, the solvent resolubility can be excellent. Above all, the value of the glass transition temperature (Tgi) of the homopolymer (Tgi) is 10 per 1 part by mass of the structural unit derived from the aromatic group-containing monomer in which the value of the glass transition temperature (Tgi) of the homopolymer is 10 ° C or more. It is particularly preferable to contain a structural unit derived from a hydroxyl group-containing monomer having a temperature of not less than ° C within the above range. When the content is not less than the above lower limit, the developing adhesion can be further improved, and when the content is not more than the above upper limit, the solvent resolubility can be further excellent.

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

  In addition, from the viewpoint of improving development adhesion, it is preferable that the total of monomers having a glass transition temperature (Tgi) of 10 ° C. or higher of the homopolymer of the monomer be 75% by mass or more in the B block, Further, it is preferably at least 85% by mass.

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

The amine value of the block copolymer before salt formation is not particularly limited, but from the viewpoint of colorant dispersibility and dispersion stability, the lower limit is preferably 40 mgKOH / g or more, and more preferably 50 mgKOH / g or more. Is more preferable, and even more preferably 60 mgKOH / g or more. The upper limit is preferably 140 mgKOH / g or less, more preferably 130 mgKOH / g or less, and even more preferably 120 mgKOH / g or less. When it is at least the lower limit, the dispersion stability is more excellent. Further, when the content is not more than the above upper limit, the compatibility with other components is excellent, and the solvent resolubility becomes good.
In the present invention, the amine value of the block copolymer before salt formation is defined as potassium hydroxide which is equivalent to the amount of hydrochloric acid necessary to neutralize 1 g of the solid content of the block copolymer before salt formation. And the value measured by the method described in JIS K 7237: 1995.

The weight average molecular weight Mw of the block copolymer is not particularly limited. More preferably, it is more preferably 3,000 to 12,000.
Here, the weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) as a standard polystyrene equivalent value.
In the present invention, the weight average molecular weight Mw of the block copolymer is determined by GPC (gel permeation chromatography) as a standard polystyrene equivalent value. The measurement was performed using HLC-8120GPC manufactured by Tosoh Corporation, the elution solvent was N-methylpyrrolidone to which 0.01 mol / l of lithium bromide was added, and the polystyrene standard for the calibration curve was Mw377400, 210500, 96000, 50400. , 20650, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories) and Mw 1090000 (manufactured by Tosoh Corporation), and the measurement columns were TSK-GEL ALPHA-M × 2 (Tosoh). (Manufactured by Co., Ltd.). In addition, the macromonomer, the salt type block copolymer, and the graft copolymer which are the raw materials of 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 may be, for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, or the like. Above all, 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, production by a living polymerization method is preferable. This is because chain transfer and deactivation hardly 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 cationic 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 on the A block. In the above-described production method, the order of polymerization of the A block and the B block can be reversed. Alternatively, the A block and the B block can be manufactured separately, and then the A block and the B block can be coupled.

{At least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons}
In the present invention, as the block copolymer, the structural unit represented by the general formula (I) is selected from the group consisting of at least a part of a terminal nitrogen site, an organic acid compound, and a halogenated hydrocarbon. A salt type block copolymer in which at least one kind forms a salt is preferable from the viewpoint of improving dispersibility of the coloring material.
As the organic acid compound, a compound represented by the following general formula (1) and a compound represented by the following general formula (3) are preferable, and the halogenated hydrocarbon is preferably a compound represented by the following general formula (2) ) Is preferred. That is, as at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon, one or more compounds selected from the group consisting of the following general formulas (1) to (3) are preferably used. it can.

（一般式（１）において、Ｒ^ａは、炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは−Ｏ−Ｒ^ｅを表し、Ｒ^ｅは、炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１〜４のアルキレン基を介した（メタ）アクリロイル基を表す。一般式（２）において、Ｒ^ｂ、Ｒ^ｂ’、及びＲ^ｂ”はそれぞれ独立に、水素原子、酸性基又はそのエステル基、置換基を有してもよい炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、置換基を有してもよいビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは−Ｏ−Ｒ^ｆを表し、Ｒ^ｆは、置換基を有してもよい炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、置換基を有してもよいビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１〜４のアルキレン基を介した（メタ）アクリロイル基を表し、Ｘは、塩素原子、臭素原子、又はヨウ素原子を表す。一般式（３）において、Ｒ^ｃ及びＲ^ｄはそれぞれ独立に、水素原子、水酸基、炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは−Ｏ−Ｒ^ｅを表し、Ｒ^ｅは、炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１〜４のアルキレン基を介した（メタ）アクリロイル基を表す。但し、Ｒ^ｃ及びＲ^ｄの少なくとも一つは炭素原子を含む。）

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

(One or more compounds selected from the group consisting of the general formulas (1) to (3))
In the general formulas (1) to (3), a linear or branched chain having 1 to 20 carbon atoms in ^Ra , ^Rb , ^{Rb '} , ^{Rb "} , ^Rc , ^Rd , ^Re , and ^Rf . Or, the cyclic alkyl group may be any of a linear or branched chain, and may include a cyclic structure, specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n- Examples include an undecyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a tetradecyl group, an octadecyl group, and the like, preferably a straight-chain, branched or cyclic alkyl group having 1 to 15 carbon atoms, and more preferably a carbon number. 1-8 Examples include a chain, branched or cyclic alkyl group.
^Furthermore, R ^a, R c, in ^{R d,} and ^{R e,} The substituent of the phenyl group or benzyl group which may have a substituent, for example, an alkyl group having 1 to 5 carbon atoms, an acyl group 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, for example, an acidic group or an ester group thereof, and a C 1 to C 1 group. 5 alkyl groups, acyl groups, acyloxy groups and the like.
In R ^b , R ^{b ′} , R ^{b ″} , and R ^f , as a substituent of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or a vinyl group; Is 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 emits a proton in water and exhibits acidity. Specific examples of the acidic group include a carboxy group (—COOH), Sulfo group (—SO ₃ H), phosphono group (—P (＝ O) (OH) ₂ ), phosphinico group (> P (＞ O) (OH)), boronic acid group (—B (OH) ₂ ), A borinic acid group (>BOH); an anion having a hydrogen atom dissociated, such as a carboxylate group (—COO ⁻ ); It may be an acid salt formed.
Further, 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 (ＰO) ) (OR)), boronic ester (-B (OR) ₂ ), borinic acid ester (> BOR) and the like. Among them, the ester group of the acidic group is preferably a carboxylic acid ester (—COOR) from the viewpoint of dispersibility and dispersion stability. R is a hydrocarbon group, and is not particularly limited. From the viewpoint of dispersibility and dispersion stability, R is preferably an alkyl group having 1 to 5 carbon atoms, and is preferably a methyl group or an ethyl group. More preferred.

From the viewpoints of dispersibility, dispersion stability, alkali developability, and suppression of development residue, the compound represented by the general formula (2) includes a carboxy group, a boronic acid group, a borinic acid group, anions thereof, and alkali metal salts thereof And at least one functional group selected from these esters, and more preferably a carboxy group, a carboxylate group, a carboxylate 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 and the like hydrocarbons of the compound and the halogen atom-side hydrocarbon have terminal nitrogen. It is presumed that the terminal nitrogen site and the hydrocarbon at the halogen atom side form a salt more stably than when the terminal nitrogen site and the acidic group or the like form a salt, although salt formation may occur with the site. Then, it is presumed that the dispersibility and the dispersion stability are improved by the adsorption of the coloring material on the salt formation site that is stably present.

  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 it has two or more acidic groups and the like, the plurality of acidic groups and the like may be the same or different. The number of the acidic groups and the like contained in the compound of the general formula (2) is preferably 1 to 3, more preferably 1 or 2, and even 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 has an aromatic ring, the affinity with the skeleton of the coloring material described later is improved, the dispersibility and the dispersion stability of the coloring material are excellent, and a colored composition having excellent contrast is obtained. It is preferable because it can be performed.

  The molecular weight of at least one compound selected from the group consisting of the general formulas (1) to (3) is preferably 1,000 or less, and more preferably 50 to 800, from the viewpoint of improving colorant dispersibility. Is more preferably 50 to 400, still more preferably 80 to 350, and most preferably 100 to 330.

Examples of the compound represented by the general formula (1) include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethyl sulfate, monoethyl sulfate, and mono-n-propyl sulfate. 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 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, and dimethacryloyloxyethyl acid phosphate. .
A group consisting of phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, dibutylphosphoric acid, benzyl chloride, benzyl bromide, vinylsulfonic acid, and p-toluenesulfonic acid monohydrate, from the viewpoint of particularly excellent dispersion stability. And at least one selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, benzyl chloride, benzyl bromide, and p-toluenesulfonic acid monohydrate. preferable.
In addition, the compound represented by the general formula (2) having an acidic group and its ester group is also preferably used from the viewpoint that the effect of suppressing the development residue is improved by combination with the specific block copolymer. One or more selected from the group consisting of α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, and 4-iodophenylbenzoic acid are also suitable. Used.

In the salt-type block copolymer, the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is determined by the content of the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the salt formation. Therefore, the total of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is added to the terminal nitrogen moiety of the structural unit represented by the general formula (I). It is preferably at least 0.01 mol, more preferably at least 0.1 mol, further preferably at least 0.2 mol, particularly preferably at least 0.3 mol. When the ratio is equal to or more than the lower limit, the effect of improving the dispersibility of the coloring material by salt formation is easily obtained. Similarly, it is preferably at most 1 mol, more preferably at most 0.8 mol, further preferably at most 0.7 mol, particularly preferably at most 0.6 mol. When the content is not more than the above upper limit, excellent adhesion to development and resolubility in solvent can be obtained.
In addition, at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used alone or in combination of two or more. When two or more are combined, the total content is preferably within the above range.

As a method for preparing the salt type block copolymer, a solvent in which the block copolymer before salt formation is dissolved or dispersed is added with at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon. , Stirring, and, if necessary, heating.
The terminal nitrogen moiety of the structural unit of the block copolymer represented by the general formula (I) and at least one selected from the group consisting of the organic acid compounds and the halogenated hydrocarbons form a salt. And the ratio can be confirmed by a known method such as NMR.

The amine value of the obtained salt-type block copolymer is smaller than that of the block copolymer before salt formation by an amount corresponding to the formation of the salt. However, since the salt-forming site is similar to or rather an enhanced colorant-adsorbing site at the terminal nitrogen site corresponding to the amino group, the salt-forming tends to improve the colorant dispersibility and the colorant dispersion stability. is there. Further, as in the case of the amino group, if the amount of the salt-forming site is too large, the solvent resolubility is adversely affected. Therefore, in the present invention, the amine value of the block copolymer before salt formation can be used as an index for improving the colorant dispersion stability and the solvent resolubility. The amine value of the obtained salt-type block copolymer is preferably from 0 to 130 mgKOH / g, more preferably from 0 to 120 mgKOH / g.
When the content is equal to or less than 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 in which a salt is formed with the compound represented by the general formula (2) among the salt-type block copolymers is measured by the method described in JIS K 7237: 1995. Value. In the compound of the general formula (2), the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the hydrocarbon on the halogen atom side form a salt. This is because the amine value can be measured without any change.
On the other hand, among the salt-type block copolymers, the amine value of the salt-type block copolymer in which a salt is formed by the compound represented by the general formula (1) or (3) is the above-described amine value before salt formation. It is determined from the amine value of the block copolymer by the following calculation. 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: 1995, the state of salt formation changes, and an accurate value cannot be measured.
First, the amine value of the block copolymer before salt formation is determined by the 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 spectral data, the nitrogen at the terminal of the structural unit represented by the general formula (I) was determined. From the ratio of the integrated value of the carbon atom peak adjacent to the non-salt-formed nitrogen atom to 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 moiety of the structural unit represented by the formula (1). Ratio). The terminal nitrogen moiety of the structural unit represented by the general formula (I) in which one or more compounds selected from the group consisting of the general formulas (1) and (3) form a salt has an amine value of 0 It is assumed that the nitrogen content ratio of the terminal terminal of the salt formed as calculated from the 13C-NMR spectrum ((amine value of the block copolymer before salt formation measured by the method described in JIS K 7237: 1995)) %) Calculated by subtracting the amine value consumed by salt formation from the amine value of the block copolymer before salt formation.
Amine value of salt type block copolymer = {Amine value of block copolymer before salt formation measured by method described in JIS K 7237: 1995}-{measured by method described in JIS K 7237: 1995. Amine value of block copolymer before salt formation} × {Ratio of salt-forming terminal nitrogen sites (%) / 100} calculated from 13 C-NMR spectrum

The acid value of the dispersant used in the present invention is not particularly limited, but is preferably 18 mgKOH / g or less, and more preferably 12 mgKOH / g or less, from the viewpoint of improving development adhesion and solvent resolubility. More preferably, there is. On the other hand, the acid value of the dispersant used in the present invention is preferably 0 mgKOH / g from the viewpoints of further improving solvent resolubility and developing adhesion, and from the viewpoint of substrate adhesion and dispersion stability. It is considered that the smaller the acid value, the less the erosion of the basic developer, and thus the better the adhesion to development. On the other hand, from the viewpoint of the effect of suppressing the development residue, it is preferably at least 1 mgKOH / g, more preferably at least 2 mgKOH / g.
In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 18 mgKOH / g or less, and more preferably 12 mgKOH / g, from the viewpoint of improving development adhesion and solvent resolubility. g or less. In addition, the acid value of the block copolymer before salt formation is preferably 0 mgKOH / g from the viewpoints of further improving solvent resolubility and development adhesion, and substrate adhesion and dispersion stability. On the other hand, from the viewpoint of the effect of suppressing the development residue, it is preferably at least 1 mgKOH / g, more preferably at least 2 mgKOH / g.

As described above, the acid value of the block copolymer before salt formation represents the mass (mg) of potassium hydroxide required to neutralize acidic components contained in 1 g of the solid content of the block copolymer, and is defined by JIS. K 0070: Value measured by the method described in 1992.
Further, the acid value of the salt type block copolymer in which the salt type block copolymer is formed with the compound represented by the general formula (2) is also measured by the method described in JIS K 0070: 1992. Value. In the compound of the general formula (2), the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the hydrocarbon on the halogen atom side form a salt. This is because it can be measured without any change.
On the other hand, when the salt-type block copolymer is a salt-type block copolymer in which a salt is formed by the compound represented by the general formula (1) or (3), the acidic group used for salt formation is used. Is excluded and the acid value is calculated. This is because the acidic group used for salt formation does not function as an acidic group that increases the acid value of the dispersant. Therefore, in the present application, the acid value of the salt-type block copolymer in which a salt is formed by the compound represented by the general formula (1) or (3) is calculated by a value obtained by the following equation. When the acid value of the salt type block copolymer in which a salt is formed by the compound represented by the general formula (1) or (3) is measured by the method described in JIS K 0070: 1992, the state of salt formation is determined. Because it is impossible to measure an accurate value.

Acid value of salt type block copolymer = {total acid value of compound represented by formula (1) or (3) used for salt formation−acid value consumed by salt formation} + block before salt formation Acid value of copolymer Here, the total acid value of the compound represented by formula (1) or (3) used for the salt formation is measured by the method described in JIS K 0070: 1992. be able to. On the other hand, the acid value consumed by salt formation is calculated from the salt formation ratio obtained by NMR.
The acid value consumed by the salt formation is specifically, for example, a 13C-NMR spectrum of the salt-type block copolymer is measured using a nuclear magnetic resonance apparatus, and among the obtained spectrum data, a terminal nitrogen site In 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, Calculate the ratio of the number of nitrogen sites. {Amine value of the block copolymer before salt formation measured by the method described in JIS K 7237: 1995} × {Ratio (%) / 100 of the terminal nitrogen site of salt formation calculated from 13C-NMR spectrum }, The consumed amine value is calculated, and this value is the same as the acid value consumed by salt formation.
However, when the compound represented by the general formula (1) is salt-formed at 1 mol or less with respect to the terminal nitrogen moiety of the structural unit represented by the general formula (I), the compound has one acidic group. When the compound represented by the general formula (3) is salt-formed at 1 mol or less, or the compound represented by the general formula (3) having two acidic groups is salt-formed at 0.5 mol or less. In this case, if the entire amount of the acidic group forms a salt with the terminal nitrogen moiety of the structural unit represented by the general formula (I), the acidic group becomes an acid in the salt-type block copolymer after salt formation. Since it does not affect the 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 unsalt-formed acidic group in the dispersant even after salt formation. Therefore, as in the above formula, the acid value of the non-salt-formed acidic group is added to the acid value of the block copolymer before salt formation to calculate the acid value of the dispersant.

In the present invention, the hydroxyl value of the dispersant is preferably 120 mgKOH / g or less, more preferably 80 mgKOH / g or less, even more preferably 60 mgKOH / g or less. If the hydroxyl value of the dispersant is too high, the solvent resolubility may decrease. On the other hand, the hydroxyl value of the dispersant is preferably 2 mgKOH / g or more, more preferably 5 mgKOH / g or more, from the viewpoint of dispersibility and dispersion stability.
In the present invention, the hydroxyl value indicates the mass (mg) of KOH required to neutralize acetic acid bound to acetylated product obtained from 1 g of solid content, and is determined by potentiometric titration according to JIS K 0070: 1992. Means the value obtained by

In the colorant dispersion according to the present invention, as the dispersant, at least one of the block copolymer and the salt-type block copolymer is used, and the content thereof is determined by the type of the colorant used and the color filter described below. Is appropriately selected according to the solid content concentration in the photosensitive colored 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, based on 100 parts by mass of the total solids in the colorant dispersion. When the value is equal to or more than the above lower limit, the dispersibility and the dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive colored resin composition for a color filter is excellent. Further, when the content is equal to or less than the above upper limit, the developability becomes good.
In particular, when forming a coating film or a colored layer having a high colorant concentration, the content of the dispersant is preferably 3 to 25 parts by mass, more preferably 3 to 25 parts by mass, based on 100 parts by mass of the total solids in the colorant dispersion. It is preferable to mix at a ratio of 5 to 20 parts by mass.
In the present invention, the solid content is all other than the above-mentioned solvent, and includes monomers and the like dissolved in the solvent.

<Color material>
In the present invention, the coloring material is not particularly limited as long as it can form a desired color when a colored layer of a color filter is formed, and various organic pigments, inorganic pigments, dispersible dyes, dyes Salt-forming compounds and the like can be used alone or in combination of two or more. Among them, organic pigments are preferably used because they have high coloring properties and high heat resistance. As the organic pigment, for example, a compound classified as a Pigment in a color index (CI; published by The Society of Dyers and Colorists), specifically, the following color index (CI) .) Can be listed.

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 pigments;
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, 06,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265,272;
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 1,7.

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

  For example, when a colorant dispersion according to the present invention is formed on a color filter substrate as a photosensitive color resin composition for a color filter to form a pattern of a light-shielding layer, a black pigment having a high light-shielding property is contained in the ink. Is blended. As the black pigment having high light-shielding properties, for example, inorganic pigments such as carbon black and iron tetroxide, or organic pigments such as cyanine black can be used.

Examples of the dispersible dye include dyes which can be dispersed by imparting various substituents to the dye or using the dye in combination with a solvent having low solubility.
The salt-forming compound of the dye refers to a compound in which the dye forms a salt with a counter ion. Lake pigments obtained by insolubilizing the above dye in a solvent using a known lake formation (chlorination) technique are also included.
In the present invention, the dispersibility and dispersion stability of the coloring material are improved by using a coloring material containing at least one selected from a dye and a salt-forming compound of the dye in combination with the dispersant of the present invention. Can be.

The 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, quinone imine dyes, methine dyes, and phthalocyanine dyes.
As a guide, if the amount of dye dissolved in 10 g of a solvent (or mixed solvent) is 10 mg or less, it can be determined that the dye is dispersible in the solvent (or mixed solvent).

  Among them, the coloring material is at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, quinophthalone dyes, coumarin dyes, cyanine dyes, and salt-forming compounds of these dyes. When it is contained, the use of the dispersing agent is preferable because the effect of suppressing sublimation or precipitation of the coloring material is high, and a high-luminance colored layer can be formed. In addition, it is preferable that the colorant contains at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, and quinophthalone dyes.

Examples of the diketopyrrolopyrrole pigment include C.I. I. Pigment Red 254, 255, 264, 272 and a diketopyrrolopyrrole pigment represented by the following general formula (i). I. Pigment Red 254, 272, and at least one selected from diketopyrrolopyrrole pigments in which R ²¹ and R ²² are each a 4-bromophenyl group in the following general formula (i).

（一般式（ｉ）中、Ｒ^２１及びＲ^２２は、それぞれ独立に、４−クロロフェニル基、又は４−ブロモフェニル基である。）

(In the general formula (i), R ²¹ and R ²² are each independently a 4-chlorophenyl group or a 4-bromophenyl group.)

Examples of the quinophthalone pigment include C.I. I. Pigment Yellow 138 and the like.
Examples of the copper phthalocyanine pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, C.I. I. Pigment Green 7, 36 and the like. I. Pigment Blue 15: 6 is preferred.
Examples of the zinc phthalocyanine pigment include C.I. I. Pigment Green 58, 59 and the like.
Examples of the quinophthalone dye include C.I. I. Disperse Yellow 54, 64, 67, 134, 149, 160, C.I. I. Solvent Yellow 114, 157 and the like. I. Disperse Yellow 54 is preferred.

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

Further, the average dispersed particle size of the colorant in the colorant dispersion varies depending on the type of the colorant used, but is preferably in the range of 10 to 100 nm, more preferably in the range of 15 to 60 nm. preferable.
The average dispersion particle size of the colorant in the colorant dispersion is the dispersion particle size of the colorant particles dispersed in a dispersion medium containing at least a solvent, which is measured by a laser light scattering particle size distribution meter. It is. The measurement of the particle size by the laser light scattering particle size distribution analyzer is performed by appropriately diluting the colorant dispersion with a solvent used for the colorant dispersion to a concentration that can be measured by the laser light scattering particle size distribution analyzer (for example, 1000 times). And the like, and can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrac 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 coloring material used in the present invention can be produced by a known method such as a recrystallization method and a solvent salt milling method. Further, a commercially available coloring material may be used after being refined.

In the colorant dispersion according to the present invention, the content of the colorant is not particularly limited. From the viewpoint of dispersibility and dispersion stability, the content of the coloring material is from 5 to 80 parts by mass, more preferably from 8 to 70 parts by mass, based on 100 parts by mass of the total solids in the coloring material dispersion. It is preferable to mix them.
In particular, when forming a coating film or a colored layer having a high coloring material concentration, a proportion of 30 to 80 parts by mass, more preferably 40 to 75 parts by mass, based on 100 parts by mass of the total solids in the coloring material dispersion. It is preferable to mix them.

<Solvent>
The solvent used in the present invention is not particularly limited as long as it is an organic solvent which does not react with each component in the colorant dispersion and can dissolve or disperse these components. The solvents can be used alone or in combination of two or more.
Specific examples of the solvent include, for example, alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxy ethoxy ethanol and ethoxy ethoxy ethanol; 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 and 2-heptanone Glycol acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate and 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, diethyl Glycol ether solvents such as glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; γ-butyrolactone Lactone-based solvents; cyclic ether-based solvents such as tetrahydrofuran; unsaturated hydrocarbon-based solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon-based solvents such as N-heptane, N-hexane, and N-octane; 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 in view of the 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, And it is preferable that it is at least one selected from the group consisting of 3-methoxybutyl acetate from the viewpoint of solubility of other components and suitability for application.

  The colorant dispersion according to the present invention preferably contains the solvent as described above in a range of usually 55 to 95% by mass with respect to the total amount of the colorant dispersion containing the solvent. It is preferably within the range of 70% by mass, more preferably within the range of 70 to 88% by mass. If the amount of the solvent is too small, the viscosity increases and the dispersibility tends to decrease. On the other hand, if the amount of the solvent is too large, the concentration of the coloring material may decrease, and it may be difficult to achieve the target chromaticity coordinates.

<Other ingredients>
The colorant dispersion according to the present invention may further contain a dispersion assisting resin and other components, if necessary, as long as the effects of the present invention are not impaired.
Examples of the dispersion assisting resin include, for example, an alkali-soluble resin exemplified by a photosensitive colored resin composition for a color filter described below. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant particles to come into contact with each other, stabilizing the dispersion, and reducing the dispersant due to the effect of stabilizing the dispersion in some cases.
Other components include, for example, a surfactant for improving wettability, a silane coupling agent for improving adhesion, an antifoaming agent, an anti-cissing agent, an antioxidant, an anti-agglomerating agent, and an ultraviolet absorber. And the like.

  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 below. That is, the colorant dispersion is (prepared by the mass of the colorant component in the composition) / (the colorant component in the composition), which is preliminarily prepared in the stage before preparing the photosensitive colored resin composition for a color filter described below. The colorant dispersion has a high ratio (mass of solid content other than the above). Specifically, the ratio of (mass of coloring material component in composition) / (mass of solid content other than coloring material component in composition) is usually 1.0 or more. By mixing the colorant dispersion and the components described below, a photosensitive colored resin composition for a color filter having excellent dispersibility can be prepared.

<Production method of colorant dispersion>
In the present invention, the method for producing a colorant dispersion is a method in which the colorant is obtained by using a dispersant for the block copolymer or the salt-type block copolymer to obtain a colorant dispersion in a solvent. There is no particular limitation if it exists. Among them, it is preferable to use one of the following two production methods from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

  That is, the first production method of the colorant dispersion according to the present invention, a step of preparing a dispersant of the block copolymer or salt type block copolymer, in a solvent, in the presence of the dispersant, And a step of dispersing the coloring material.

  Further, the second method for producing a colorant dispersion according to the present invention when a dispersant that is a salt type block copolymer is used, comprises a solvent, the block copolymer, an organic acid compound and the like, and a colorant. And dispersing the colorant while salt-forming at least a part of the terminal nitrogen site of the structural unit represented by the general formula (I) with an organic acid compound or the like. Things.

In the case of using a salt-type block copolymer, according to the first production method, after preparing the salt-type block copolymer, the colorant is dispersed using the salt-type block copolymer as a dispersant. Therefore, it is preferable because the reaction end point and the reaction rate of the block copolymer and the organic acid compound before the salt formation can be accurately confirmed.
Further, according to the second production method, since the colorant is dispersed while the dispersant for the salt-type block copolymer is being prepared, the salt-type block copolymer does not self-aggregate, and the colorant is dispersed. The liquid can be efficiently prepared, and the dispersibility can be improved.

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

  Specifically, preliminary dispersion is performed using 2.0 mm zirconia beads having a relatively large bead diameter, and further main dispersion is performed using 0.1 mm zirconia beads having a relatively small bead diameter. After dispersion, it is preferable to filter through a 0.5-2 μm filter.

II. Photosensitive Coloring Resin Composition for Color Filter The photosensitive coloring resin composition for color filter according to the present invention comprises the colorant dispersion according to the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. It is characterized by containing.
The photosensitive colored resin composition for a color filter of the present invention can form a high-brightness colored layer by using the colorant dispersion according to the present invention, and is formed of an ITO formed adjacent to the colored layer. Cracks in the film can be suppressed.

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

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

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

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. It has been found that the presence of a hydrocarbon ring, which is a bulky group, in the alkali-soluble resin suppresses the solvent resistance of the obtained colored layer, in particular, the swelling of the colored layer. Although the function is unclear, the presence of a bulky hydrocarbon ring in the coloring layer suppresses the movement of molecules in the coloring layer, resulting in an increase in the strength of the coating film and suppression of swelling due to the solvent. It is estimated that
Examples of such a hydrocarbon ring include a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and a combination thereof. May have a substituent such as a carbonyl group, a carboxy group, an oxycarbonyl group, and an amide group. Above all, when an aliphatic ring is contained, the heat resistance and adhesion of the colored layer are improved, and the luminance of the obtained colored layer is improved.
Specific examples of the hydrocarbon ring include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), and adamantane. Ring; aromatic ring such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; linear polycyclic ring such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene; and cardo structure represented by the following chemical formula (ii). Can be

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

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

(In the general formula (iii), R ^M is an optionally substituted hydrocarbon ring.)

When the alkali-soluble resin has a maleimide structure represented by the above general formula (iii), since it has a nitrogen atom in the hydrocarbon ring, the compatibility with the dispersant of the present invention is very good, and the effect of suppressing the development residue is improved. Is improved.
In R ^M in the general formula (iii), Examples of the optionally substituted hydrocarbon ring, those similar to the specific example of the hydrocarbon ring.

It is preferable to use an aliphatic ring as the hydrocarbon ring, since the heat resistance and the adhesion of the colored layer are improved and the luminance of the obtained colored layer is improved.
In addition, when a cardo structure represented by the chemical formula (ii) is included, it is particularly preferable since the curability of the colored layer is improved and the solvent resistance (NMP swelling suppression) is improved.

In the alkali-soluble resin used in the present invention, apart from the structural unit having a carboxy group, it is easy to adjust the amount of each structural unit by using an acrylic copolymer having the structural unit having a hydrocarbon ring, This is preferable because the function of the structural unit can be easily improved by increasing the amount of the structural unit having a hydrocarbon ring.
The acrylic copolymer having a structural unit having a carboxy group and the hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the “other copolymerizable monomer” described above. be able to.
Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and phenoxy Ethyl (meth) acrylate, styrene and the like. Cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and styrene are preferred, and styrene is particularly preferred.
Further, from the viewpoint of the effect of suppressing the development residue, the ethylenically unsaturated monomer having a hydrocarbon ring is preferably a monomer having a maleimide structure and styrene, and particularly preferably styrene.

The alkali-soluble resin used in the present invention preferably has an ethylenic double bond in a side chain. When having an ethylenic double bond, in the curing step of the resin composition during the production of a color filter, the alkali-soluble resin and the dispersant of the present invention described above can form a cross-linking, The alkali-soluble resins, or the alkali-soluble resin and the photopolymerizable compound can form a cross-linking bond. Therefore, when the alkali-soluble resin having an ethylenic double bond in the side chain is used in combination with the dispersant of the present invention, the film strength of the cured film is further improved by a synergistic effect, and the luminance of the colored layer and the ITO film are improved. Of the cured film can be further improved, the development resistance can be further improved, and the heat shrinkage of the cured film can be suppressed and the adhesion to the substrate can be improved.
The method for introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method in which a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, is added to the carboxy group of the alkali-soluble resin to introduce an ethylenic double bond into the side chain. Or a method in which a structural unit having a hydroxyl group is introduced into a copolymer, and a compound having an isocyanate group and an ethylenic double bond in a molecule is added to introduce a ethylenic double bond into a side chain. And the like.

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

  The alkali-soluble resin used in the present invention may be an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxy group and a structural unit having a hydrocarbon ring. Preferably, an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxy group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenic double bond. More preferably, there is.

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

The charged amount of the carboxy group-containing ethylenically unsaturated monomer is preferably 5% by mass or more, more preferably 10% by mass or more based on the total amount of the monomers, from the viewpoint of obtaining a good pattern. On the other hand, the amount of the carboxy group-containing ethylenically unsaturated monomer to be added is preferably 50% by mass or less, more preferably 40% by mass or less, based on the total amount of the monomers, from the viewpoint of suppressing film roughness on the pattern surface after development. More preferably, there is.
When the ratio of the carboxy group-containing ethylenically unsaturated monomer is not less than the above lower limit, the solubility of the obtained coating film in an alkali developing solution is sufficient, and the ratio of the carboxy group-containing ethylenically unsaturated monomer is not more than the above upper limit. If it is less than the above, there is a tendency that the formed pattern is less likely to fall off from the substrate and the film surface of the pattern is less likely to be roughened at the time of development with an alkali developing solution.

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

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

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

The alkali-soluble resin is preferably selected from those having an acid value of 50 mgKOH / g or more from the viewpoint of developability (solubility) with respect to an aqueous alkali solution used for a developer. The alkali-soluble resin preferably has an acid value of 70 mgKOH / g or more and 300 mgKOH / g or less from the viewpoint of developability (solubility) with respect to an aqueous alkali solution used for a developer and adhesion to a substrate. It is preferably from 70 mgKOH / g to 280 mgKOH / g.
The acid value of the alkali-soluble resin can be measured according to JIS K 0070: 1992.

In the case where the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated bond equivalent has an effect that the film strength of the cured film is improved, the development resistance is improved, and the adhesion to the substrate is excellent. From the viewpoint, it is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. When the equivalent of the ethylenically unsaturated bond is 100 or more, development resistance and adhesion are excellent. Further, when the molecular weight is 2000 or less, the ratio of the structural unit having a carboxy group or another structural unit such as a structural unit having a hydrocarbon ring can be relatively increased, so that the developing unit is excellent in heat resistance and heat resistance. I have.
Further, from the viewpoint of excellent synergistic effect when combined with the dispersant and further improvement of the luminance and the ITO crack resistance of the colored layer, the dispersant is included in the side chain in the block copolymer before salt formation ( It is preferable that the (meth) acryloyl group equivalent is within the above-mentioned preferred range, and that the ethylenically unsaturated bond equivalent of the alkali-soluble resin is within the aforementioned preferred range.
Here, the ethylenically unsaturated bond equivalent is a weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (2).

Formula (2) Ethylenically unsaturated bond equivalent (g / mol) = W (g) / M (mol)
(In the formula (2), W represents the mass (g) of the alkali-soluble resin, and M represents the mole number (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).)

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

  The alkali-soluble resin used in the photosensitive color resin composition for a color filter may be used singly or in combination of two or more, and the content thereof is not particularly limited. The alkali-soluble resin is preferably in the range of 5% by mass to 60% by mass, more preferably 10% by mass to 40% by mass, based on the total solid content of the photosensitive colored resin composition for filters. When the content of the alkali-soluble resin is equal to or more than the lower limit, sufficient alkali developability is obtained, and when the content of the alkali-soluble resin is equal to or less than the upper limit, film roughness and chipping of a pattern during development are reduced. Can be suppressed.

<Polyfunctional monomer>
The polyfunctional monomer used in the photosensitive color resin composition for a color filter is not particularly limited as long as it can be polymerized by a photoinitiator described below, and usually has two or more ethylenically unsaturated double bonds. And a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups.
Such a polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples include, for example, those described in JP-A-2013-029832.

One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination. When the photosensitive color resin composition for a color filter of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three polymerizable double bonds (trifunctional). Those having the above are preferable, and poly (meth) acrylates of trihydric or higher polyhydric alcohols and modified products of dicarboxylic acids thereof are preferable. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, succinic acid-modified pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) ) Succinic acid modified acrylate, dipen Hexa (meth) acrylate are preferable.
The content of the polyfunctional monomer used in the photosensitive color resin composition for a color filter is not particularly limited, but the content of the polyfunctional monomer is preferably 5 to the total solid content of the photosensitive color resin composition for a color filter. ６０60% by mass, more preferably 10-40% by mass. If the content of the polyfunctional monomer is less than the lower limit, the photocuring does not proceed sufficiently, and the exposed portion may be eluted during development. May decrease.

<Photo initiator>
The photoinitiator used in the colored resin composition for a color filter of the present invention is not particularly limited, and one or a combination of two or more of conventionally known initiators can be used.
Examples of the photoinitiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthones, and the like. be able to. Specific examples of the photoinitiator include benzophenone, aromatic ketones such as 4,4′-bisdiethylaminobenzophenone and 4-methoxy-4′-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, and ethyl benzoin. Biimidazoles such as benzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole and the like Halomethyloxadiazole compound, halomethyl-S-triazine-based compound such as 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1 , 2-Diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl]- Morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenylketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethyl Thioxanthon, 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1 [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone , Α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1 -Propanone and the like.
Among them, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1- Butanone, 4,4'-bis (diethylamino) benzophenone and diethylthioxanthone are preferably used. Furthermore, it is sensitive to combine an α-aminoacetophenone-based initiator such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one with a thioxanthone-based initiator such as diethylthioxanthone. It is preferable from the viewpoint that the adjustment and the water stain are suppressed and the development resistance is improved.
When the α-aminoacetophenone-based initiator and the thioxanthone-based initiator are used, the total content thereof is preferably from 5% by mass to 15% by mass based on the total solid content of the colored resin composition. When the amount of the initiator is 15% by mass or less, the amount of sublimates during the production process is reduced, which is preferable. When the amount of the initiator is 5% by mass or more, development resistance such as water stain is improved.

In the present invention, the photoinitiator preferably contains an oxime ester-based photoinitiator from the viewpoint of improving sensitivity. In addition, by using an oxime ester-based photoinitiator, when a fine line pattern is formed, variation in in-plane line width is easily suppressed. Further, by using an oxime ester-based photoinitiator, the residual film ratio tends to be improved, and the effect of suppressing the occurrence of water stain tends to be increased. In addition, the term “water stain” means that when a component that enhances alkali developability is used, traces of water stain appear after rinsing with pure water after alkali development. Such a water stain disappears after post-baking, so there is no problem as a product.However, in the appearance inspection of the patterning surface after development, it is detected as unevenness abnormality, and there is a problem that a normal product and an abnormal product cannot be distinguished. Occurs. Therefore, if the inspection sensitivity of the inspection device is reduced in the appearance inspection, the yield of the final color filter product is reduced, which is a problem.
As the oxime ester-based photoinitiator, from the viewpoint of reducing contamination of the colored resin composition for a color filter and a device due to a decomposition product, among others, those having an aromatic ring are preferable and having a condensed ring containing an aromatic ring. And more preferably a fused ring containing a benzene ring and a hetero ring.
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-A-2000-80068, JP-A-2001-233842, JP-T-2010-527339, JP-T-2010-527338, It can be appropriately selected from oxime ester-based photoinitiators described in JP-A-2013-041153 and the like. Commercially available products include Irgacure OXE-01, ADEKA ARKULS NCI-930 having a diphenyl sulfide skeleton, TR-PBG-345, TR-PBG-304 having a carbazole skeleton, TR-PBG-365 having a fluorene skeleton, and diphenyl sulfide skeleton TR-PBG-3057 having the above (all manufactured by Changzhou Strong Electronics New Materials Co., Ltd.) may be used. It is particularly preferable to use an oxime ester-based photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton from the viewpoint of luminance. It is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.
The use of two or more oxime ester-based photoinitiators is preferable in that the luminance and the residual film ratio are easily improved and the effect of suppressing the occurrence of water stain is high. In particular, the combined use of two types of oxime ester-based photoinitiators having a diphenyl sulfide skeleton, or the combined use of an oxime ester-based photoinitiator having a diphenyl sulfide skeleton and an oxime ester-based photoinitiator having a fluorene skeleton are high in luminance and heat resistance. It is preferable from the viewpoint of high performance. It is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton and an oxime ester-based photoinitiator having a fluorene skeleton or an oxime ester-based photoinitiator having diphenylsulfide in terms of excellent sensitivity and luminance.

It is preferable to use a photoinitiator having a tertiary amine structure in combination with the oxime ester photoinitiator from the viewpoint of suppressing water stain and improving sensitivity. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure which is an oxygen quencher in the molecule, the radical generated from the initiator is hardly deactivated by oxygen, and the sensitivity can be improved. is there. Commercial products of the photoinitiator having the tertiary amine structure include, for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (for example, Irgacure 369, manufactured by BASF), 4,4′-bis (diethylamino) benzophenone (for example, High Cure ABP, Kawaguchi Pharmaceutical Co., Ltd.).
Further, it is preferable to combine a thioxanthone initiator with an oxime ester photoinitiator from the viewpoint of sensitivity adjustment, suppressing water stain, and improving development resistance. The combination of an initiator is preferred in that the luminance and the residual film ratio are improved, the sensitivity is easily adjusted, the effect of suppressing the occurrence of water stain is high, and the development resistance is improved.

The content of the photoinitiator used in the colored resin composition for a color filter of the present invention is usually about 0.01 part by mass to 100 parts by mass, preferably 5 parts by mass, based on 100 parts by mass of the polyfunctional monomer. 60 parts by mass. If this content is at least the lower limit, photocuring will proceed sufficiently to prevent the exposed portion from being eluted during development, while if it is at most the above upper limit, the yellowing of the resulting colored layer will be weakened and the brightness will be reduced. Reduction can be suppressed.
Further, as the photoinitiator used in the colored resin composition for a color filter of the present invention, the total content of two or more oxime ester-based photoinitiators is based on the total solid content of the colored resin composition for a color filter. It is preferable that it is in the range of 0.1% by mass to 12.0% by mass, more preferably in the range of 1.0% by mass to 8.0% by mass, from the viewpoint of sufficiently exhibiting the combined effect of these photoinitiators. .

  The total content of the binder components used in the colored resin composition for color filters of the present invention is preferably 35% by mass to 97% by mass, and preferably 40% by mass, based on the total solid content of the colored resin composition for color filters. % To 96% by mass. If it is at least the above lower limit, a colored layer excellent in hardness and adhesion to a substrate can be obtained. When the content is equal to or less than the upper limit, the developability is excellent, and the generation of minute wrinkles due to heat shrinkage is suppressed.

<Antioxidant>
The photosensitive colored resin composition for a color filter of the present invention preferably further contains an antioxidant from the viewpoint of improving heat resistance, suppressing fading of the coloring material, and improving luminance. The antioxidant may be appropriately selected from conventionally known ones. Specific examples of the antioxidant include, for example, a hindered phenol antioxidant, an amine antioxidant, a phosphorus antioxidant, a sulfur antioxidant, a hydrazine antioxidant, and the like. From the viewpoint, it is preferable to use a hindered phenol-based antioxidant. It may be a latent antioxidant as described in WO 2014/021023.

  Examples of the hindered phenolic antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF). 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris (4-hydroxy-3 , 5-di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, Sumitomo Chemical), 6,6'-thiobis (2-tert-butyl-4-methylphenol) Trade name: Irganox 1081, manufactured by BASF), 3,5-di -tert- butyl-4-hydroxybenzyl phosphonic acid diethyl (trade name: Irugamodo 195, manufactured by BASF), and the like. Above all, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. .

  The photosensitive color resin composition for a color filter of the present invention, when containing the oxime ester-based photoinitiator and an antioxidant in combination, the point that the luminance is improved by a synergistic effect, the point that the residual film ratio is improved, When forming a fine line pattern, it is preferable in that the linearity is further improved and the ability to form a fine line pattern as designed by the mask line width is improved.

  The compounding amount of the antioxidant is preferably 0.1 parts by mass to 10.0 parts by mass with respect to 100 parts by mass of the total solids in the colored resin composition, and is preferably 0.5 part by mass. Parts by mass to 5.0 parts by mass. If it is not less than the above lower limit, heat resistance and light resistance are excellent. On the other hand, when the content is equal to or less than the above upper limit, the colored resin composition of the present invention can be a highly sensitive photosensitive resin composition.

  When the antioxidant is used in combination with the oxime ester photoinitiator, the amount of the antioxidant is 1 part by mass based on 100 parts by mass of the total amount of the oxime ester photoinitiator. The amount is preferably from 250 to 250 parts by mass, more preferably from 3 to 80 parts by mass, and still more preferably from 5 to 45 parts by mass. Within the above range, the effect of the above combination is excellent.

<Optional components>
The photosensitive colored resin composition for a color filter of the present invention may contain various additives in addition to the antioxidant, if necessary.
Examples of the additives include 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.
Specific examples of the surfactant and the plasticizer include, for example, those described in JP-A-2013-029832.

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

  The content of the silane coupling agent is preferably 0.05 parts by mass or more and 10.0 parts by mass or less based on 100 parts by mass of the total solids in the photosensitive colored resin composition. And more preferably 0.1 part by mass or more and 5.0 parts by mass or less. If it is not less than the lower limit and not more than the upper limit, the substrate has excellent adhesion.

<Blend ratio of each component in photosensitive colored resin composition for color filter>
The total content of the coloring material is preferably 3 to 65% by mass, more preferably 4 to 60% by mass, based on the total solid content of the photosensitive colored resin composition for a color filter. If it is at least the above lower limit, the colored layer when the photosensitive colored resin composition for a color filter is applied to a predetermined film thickness (usually 1.0 to 5.0 μm) will have a sufficient color density. When the content is equal to or less than the upper limit, a colored layer having excellent storage stability, sufficient hardness and adhesion to a substrate can be obtained. In particular, when a coloring layer having a high coloring material concentration is formed, the content of the coloring material is from 15 to 65% by mass, more preferably from 25 to 65% by mass, based on the total solid content of the photosensitive coloring resin composition for a color filter. It is preferable to mix at a ratio of 60% by mass.
The content of the dispersant is not particularly limited as long as the colorant can be uniformly dispersed, for example, with respect to the total solid content of the photosensitive color resin composition for color filters. At a rate of 1 to 40% by mass. Furthermore, it is preferable to mix at a ratio of 2 to 30% by mass, particularly preferably at a ratio of 3 to 25% by mass, based on the total solid content of the photosensitive colored resin composition for a color filter. When the value is equal to or more than the above lower limit, the dispersibility and the dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive colored resin composition for a color filter is excellent. Further, when the content is equal to or less than the above upper limit, the developability becomes good. In particular, when a colored layer having a high color material concentration is formed, the content of the dispersant is preferably 2 to 25% by mass, more preferably 3 to 25% by mass, based on the total solid content of the photosensitive colored resin composition for a color filter. It is preferable to mix at a ratio of 20% by mass. In the case of a salt type block copolymer, the mass of the dispersant is the total mass of the block copolymer and the organic acid compound before salt formation.
Further, the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. Usually, it is preferably within a range of 55 to 95% by mass, and more preferably within a range of 65 to 88% by mass, based on the total amount of the photosensitive colored resin composition for a color filter containing the solvent. preferable. When the content of the solvent is within the above range, excellent coating properties can be obtained.

<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, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, Can be obtained by adding other components according to the above and mixing using a known mixing means.

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

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

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

The coloring layer can be formed, for example, by the following method.
First, the above-described photosensitive color resin composition for a color filter of the present invention is applied to a substrate described below using a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, and a die coating method. Apply on top to form a wet coating. Among them, a spin coating method and a die coating method can be preferably used.
Next, the wet coating film is dried using a hot plate or an oven, and then exposed to light through a mask having a predetermined pattern, and cured by a photopolymerization reaction of an alkali-soluble resin and a polyfunctional monomer. Make a coating. Examples of the light source used for the 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.
Further, heat treatment may be performed after the exposure in order to accelerate the polymerization reaction. The heating conditions are appropriately selected according to the mixing ratio of each component in the photosensitive color resin composition for a color filter to be used, the thickness of a coating film, and the like.

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

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

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

<Substrate>
As the substrate, a transparent substrate described later, a silicon substrate, or a substrate obtained by forming aluminum, silver, a silver / copper / palladium alloy thin film on a transparent substrate or a silicon substrate, or the like is used. On these substrates, another color filter layer, a resin layer, a transistor such as a TFT, a circuit, or the like may be formed.
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, a transparent rigid material having no flexibility such as quartz glass, non-alkali glass, and synthetic quartz plate, or a transparent flexible material having flexibility such as a transparent resin film, an optical resin plate, and flexible glass. Materials.
The thickness of the transparent substrate is not particularly limited, but a thickness of, for example, about 100 μm to 1 mm can be used depending on the use of the color filter of the present invention.
In addition, the color filter of the present invention may be one in which, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, and the like are formed in addition to the substrate, the light-shielding portion, and the coloring layer.

IV. Display Device A display device according to the present invention includes the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, and examples thereof include a liquid crystal display device and an organic light emitting display device.

[Liquid crystal display]
The liquid crystal display device of the present invention includes, for example, a liquid crystal display device having the above-described color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. .
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing one 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.
It should be noted that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but may have a generally known configuration 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 adopted. Examples of such a driving 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 suitably used.
The counter substrate can be appropriately selected and used depending on the driving method of the liquid crystal display device of the present invention and the like.
Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and a mixture thereof can be used according to the driving method of the liquid crystal display device of the present invention and the like.

  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. After forming the liquid crystal layer by the above method, the sealed liquid crystal can be oriented by gradually cooling the liquid crystal cell to room temperature.

[Organic light emitting display]
The organic light emitting display device of the present invention includes, for example, an organic light emitting display device having the above-described color filter according to the present invention and an organic luminous body.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view showing 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 emitting body 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic luminous body 80.

As a method of laminating the organic light emitting body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter. And a method of bonding the organic light emitting body 80 formed on another substrate to 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 components of the organic light emitting body 80, known structures can be used as appropriate. The organic light-emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display and an active drive type organic EL display.
The configuration of the organic light emitting display of the present invention is not limited to the configuration shown in FIG. 3, but may be a configuration generally known as an organic light emitting display using a color filter.

Hereinafter, the present invention will be specifically described with reference to examples. The description is not intended to limit the invention.
The acid value of the block copolymer before salt formation and the acid value of the salt type block copolymer salt-formed by the compound represented by the general formula (2) are described in JIS K 0070: 1992. Was determined by a method according to
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 formula (2) are described in JIS K 7237: 1995. Was determined by a method according to
The hydroxyl value of the block copolymer before and after salt formation was determined by a method according to JIS K 0070: 1992.
The weight average molecular weight (Mw) of the block copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the above-described measurement method of the present invention.

(Example 1: Synthesis of salt type block copolymer A-1)
250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round-bottom, four-neck separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and nitrogen was sufficiently replaced. Was. After cooling the reaction flask to −60 ° C., 4.9 parts by mass of butyllithium (15% by mass in hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 12.1 parts by mass of 2-ethylhexyl methacrylate (EHMA), 12.9 parts by mass of n-butyl methacrylate (BMA), 12.9 parts by mass of methacrylic acid 9.0 parts by mass of benzyl (BzMA), 16.6 parts by mass of methyl methacrylate (MMA), and 17.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA) were added dropwise over 60 minutes using an addition funnel. After 30 minutes, 25.3 parts by mass of dimethylaminoethyl methacrylate (DMMA), a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum-dried, and diluted with PGMEA to obtain a solution having a solid content of 30% by mass. 32.5 parts by mass of water was added, the temperature was raised to 100 ° C., and the reaction was carried out 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 A-1 ″ PGMEA solution was reprecipitated in hexane, filtered and purified by vacuum drying. The purified block copolymer A-1 ″ was dissolved again in 400 parts by mass of PGMEA, and A (2-isocyanatoethyl methacrylate, trade name: Karenz MOI, manufactured by Showa Denko) 5.3 parts by mass, and dibutyl tin (trade name: Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) 0.008 parts by mass. After raising the temperature to 80 ° C. and reacting for 2 hours, the A block containing the structural unit represented by the general formula (I), the structural unit represented by the general formula (B1) and the monomer derived from the carboxy group-containing monomer A block copolymer A-1 ′ solution (solid content: 20% by mass) having a B block containing a structural unit was obtained.

In a 100 mL round bottom flask, 50 parts by mass of the obtained block copolymer A-1 ′ solution is placed, and 1.27 masses of phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry), which is a compound represented by the general formula (3), is added. Parts (PPA was added in an amount of 0.5 mol per 1 mol of DMMA unit of the block copolymer A-1 ′), and the mixture was stirred at a reaction temperature of 30 ° C. for 20 hours to obtain a salt-type block copolymer having a solid content of 20% by mass. An acid value of the salt-type block copolymer A-1 after salt formation was the same as that of the block copolymer A-1 'before salt formation, but an amine value after salt formation was obtained. Specifically, it was calculated as follows.
1 g of a solution obtained by mixing 9 parts by mass of the salt-type block copolymer A-1 (solid after reprecipitation) and 91 parts by mass of chloroform-D1NMR was put into an NMR sample tube, 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 carried out at room temperature and under the conditions of 10,000 integrations. In the obtained spectral data, at the terminal nitrogen site (amino group), 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 was calculated. From the ratio, the ratio of the number of amino groups formed into salts to the total number of amino groups was calculated, and was not different from the theoretical salt formation ratio (all phenylphosphonic acids contained a nitrogen moiety at the terminal of DMMA in the block copolymer A-1 ′ at DMMA). And salt formation).

(Examples 2 to 14: Synthesis of salt type block copolymers A-2 to A-14)
In Example 1, the salt block copolymer A of Example 1 was changed except that the material of the A block was changed to the content shown in Table 1 and the material of the B block was changed to the type and content shown in Table 1. In the same manner as -1, salt-type block copolymer A-2 to A-14 solutions were obtained. Note that 1-ethoxyethyl methacrylate (EEMA) was used in an equimolar amount to MAA in Table 1.
Further, in Table 1, the amount of the organic acid compound or the halogenated hydrocarbon used as the salt-forming compound is determined by the mole of the compound relative to 1 mole of the nitrogen moiety (DMMA) of the structural unit represented by the general formula (I). Expressed as a number.
In Example 2, the purified block copolymer A-1 ″ was dissolved again in 400 parts by mass of PGMEA, and isocyanate B (2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate, 12.0 parts by mass of Karenz MOI-BM (manufactured by Showa Denko) and 0.01 parts by mass of dibutyltin dilaurate were added, and the mixture was heated at 130 ° C. for 2 hours. A block copolymer A-2 ′ solution (solid content: 20% by mass) having a block and a B block including a structural unit represented by the general formula (B1) and a structural unit derived from a carboxy group-containing monomer was obtained. .

(Comparative Examples 1-2: Synthesis of Comparative Salt Type Block Copolymers AC-1 and AC-2)
In Example 1, except that the material of the A block was changed to the content shown in Table 1 and the material of the B block was changed to the type and content shown in Table 1, the salt type block copolymer A of Example 1 was used. In the same manner as in Solution No.-1, solutions of comparative salt type block copolymers AC-1 to AC-2 were obtained. In Comparative Example 1, a solution of the comparative salt-type block copolymer AC-1 was obtained without reacting the purified comparative block copolymer AC-1 ″ with the isocyanate compound. Ethyl oxetane-3-yl) methyl acrylate was added together with a B block monomer such as EEMA to obtain a comparative block copolymer AC-2 ″, and the purified comparative block copolymer AC-2 ″ was converted to an isocyanate compound. Without reacting the same, a solution of a comparative salt type block copolymer AC-2 was obtained.

  Before salt formation in the salt type block copolymers A-1 to A-14 obtained in Examples 1 to 14 and the comparative salt type block copolymers AC-1 to AC-2 obtained in Comparative Examples 1 and 2. Table 1 shows the acid value, amine value, hydroxyl value after salt formation, and weight average molecular weight (Mw) before salt formation. The amine value of the salt-type block copolymer after formation of the salt was calculated by subtracting the amine value of the DMMA unit from the amine value before formation of the salt.

(Example 15: Synthesis of block copolymer A-15)
A block copolymer A-15 solution was obtained in the same manner as in Example 1 except that no salt was formed.

(Example 16: Synthesis of block copolymer A-16)
A block copolymer A-16 solution was obtained in the same manner as in Example 3, except that no salt was formed.

(Example 17: Synthesis of block copolymer A-17)
A block copolymer A-17 solution was obtained in the same manner as in Example 5, except that no salt was formed.

(Example 18: Synthesis of salt type block copolymer A-18)
A 500 ml four-neck separable flask was dried under reduced pressure, and then replaced with Ar (argon). While flowing Ar, 100 parts by mass of dehydrated THF, 2.0 parts by mass of methyltrimethylsilyldimethylketene acetal, 0.15 ml of a 1 M solution of tetrabutylammonium-3-chlorobenzoate (TBACB) in acetonitrile, and 0.2 parts by mass of mesitylene were added. Using a dropping funnel, 12.1 parts by mass of 2-ethylhexyl methacrylate (EHMA), 12.9 parts by mass of n-butyl methacrylate (BMA), 9.0 parts by mass of benzyl methacrylate (BzMA), methacrylic acid 17.7 parts by mass of methyl (MMA) and 17.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA) were added dropwise over 45 minutes. Since the reaction generates heat as the reaction proceeds, the temperature was kept below 40 ° C. by cooling with ice. One hour later, 25.3 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 15 minutes. After reacting for 1 hour, the reaction was stopped by adding 5 parts by mass of methanol. The solvent was removed under reduced pressure to obtain a block copolymer A-18 ″. The block copolymer A-18 ″ was dissolved in 400 parts by mass of PGMEA, and isocyanate A (2-isocyanatoethyl methacrylate, trade name: Karenz MOI, 5.3 parts by mass of Showa Denko) and 0.008 parts by mass of dibutyltin (trade name: Neostan U-100, manufactured by Nitto Kasei Co., Ltd.) were added, and the mixture was heated to 80 ° C. and reacted for 2 hours. A block copolymer A having an A block containing a constituent unit represented by the general formula (I) and a B block containing a constituent unit represented by the general formula (B1) and a constituent unit derived from a carboxy group-containing monomer. A -18 'solution (solid content 20% by mass) was obtained.
In the same manner as in Example 1, except that a block copolymer A-18 'solution was used instead of the block copolymer A-1' solution, a salt-type block having a solid content of 20% by mass was used. A copolymer A-18 solution was obtained.

  Table 1 shows the acid value, amine value, hydroxyl value, and weight average molecular weight (Mw) of the block copolymers A-15 to A-17 and the salt type block copolymers A-18 obtained in Examples 15 to 18. Shown in

Here, each symbol in the table is as follows.
DMMA: dimethylaminoethyl methacrylate MAA: methacrylic acid EHMA: 2-ethylhexyl methacrylate BMA: n-butyl methacrylate BzMA: benzyl methacrylate MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate HPhPA: 2-hydroxy-3 -Phenoxypropyl acrylate (trade name: M-600A, manufactured by Kyoeisha Chemical Co., Ltd.)
4HBA: 4-hydroxybutyl acrylate Isocyanate A: 2-isocyanatoethyl methacrylate (trade name; Karenz MOI, manufactured by Showa Denko)
Isocyanate B: 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate (trade name: Karenz MOI-BM, manufactured by Showa Denko)
Isocyanate C: 1,1- (bisacryloyloxymethyl) ethyl isocyanate (trade name; Karenz BEI, manufactured by Showa Denko)
Isocyanate D: 2-methacryloyloxyethoxyethyl isocyanate (trade name: Karenz MOI-EG, manufactured by Showa Denko)
Isocyanate E: 2-isocyanatoethyl acrylate (trade name: Karenz AOI-VM, manufactured by Showa Denko)

(Synthesis Example 1: Synthesis of alkali-soluble resin A solution)
After 300 parts by mass of PGMEA was charged into a polymerization tank and heated to 100 ° C. in a nitrogen atmosphere, 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 dropped over 1.5 hours. Thereafter, the reaction was continued while maintaining the temperature at 100 ° C., and two hours after the completion of the dropwise addition of the mixture for forming a main chain, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization.
Next, while blowing in air, add 20 parts by weight of glycidyl methacrylate (GMA) as an epoxy group-containing compound, raise the temperature to 110 ° C., add 0.8 parts by weight of triethylamine, and add 15 parts at 110 ° C. for 15 hours. The addition reaction was performed to obtain an alkali-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH / g, solid content 40% by mass).
In addition, the measuring method of the said weight average molecular weight measured the weight average molecular weight by Shodex GPC System-21H (Shodex GPC System-21H) using polystyrene as a standard substance and THF as an eluent. The acid value was measured according to JIS K 0070: 1992.

(Example 21)
(1) Production of Coloring Material Dispersion G1 14.8 parts by mass of the salt-type block copolymer A-1 solution (solid content 20% by mass) of Example 1 as a dispersing agent, and C.I. I. Pigment Green 58 (PG58), 10.4 parts by mass, C.I. I. 2.6 parts by mass of CI Pigment Yellow 138 (PY138), 14.6 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 1, 57.6 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm. Into a mayonnaise bottle, shake for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for pre-crushing, and then take out zirconia beads having a particle size of 2.0 mm, and 200 parts by mass of zirconia beads having a particle size of 0.1 mm. Was added, and the mixture was dispersed in a paint shaker for 4 hours to obtain a colorant dispersion G1.

(2) Production of photosensitive colored resin composition G1 for color filter 43.8 parts by mass of colorant dispersion G1 obtained in (1) above and alkali-soluble resin A solution obtained in Synthesis Example 1 in 6. 3 parts by mass, 5.9 parts by mass of a polyfunctional monomer (trade name: Aronix M-403, manufactured by Toagosei Co., Ltd.), and an oxime ester-based initiator (ADEKA Corporation, "ADEKA ARKULS NCI- 930 "), 0.99 parts by mass of an oxime ester-based initiator (" TR-PBG-3057 ", manufactured by Changzhou Strong Electronic Materials Co., Ltd.), 0.69 parts by mass of diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.," DETX "). -S "), 0.11 part by mass of a hindered phenol-based antioxidant (IRGANOX1010, manufactured by BASF) as an antioxidant, 3-methacryloxypropyltrimethoxy. 0.4 parts by mass of silane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.04 parts by mass of Megafac F-559 (manufactured by DIC), and 41.4 parts by mass of PGMEA as a solvent were added. Thereafter, the mixture was mixed until it became uniform to obtain a photosensitive colored resin composition G1 for a color filter.

(3) Formation of Colored Layer The colored resin composition G1 obtained in (2) above was placed on a glass substrate (“NA35”, manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After application using a spin coater, the coating is dried at 80 ° C. for 3 minutes using a hot plate, irradiated with 60 mJ / cm ² ultraviolet rays using an ultra-high pressure mercury lamp, and further post-baked in a 230 ° C. clean oven for 30 minutes. Thus, the thickness was adjusted so that the film thickness after curing was 2.5 μm, and the colored layer G1 was formed.

(Examples 22 to 38, Comparative Examples 11 to 12)
(1) Production of Colorant Dispersions G2 to G18 and Comparative Colorant Dispersions GC1 to GC2 In (1) of Example 21, instead of the salt-type block copolymer A-1 solution, as shown in Table 2, The solution of the salt type block copolymers A-2 to A-14 of Examples 2 to 14, the block copolymers A-15 to A-17 of Examples 15 to 18, and the salt type block copolymer A-18 And the comparative salt type block copolymers AC-1 to AC-2 solutions of Comparative Examples 1 and 2 were used so that the solid content was the same parts by mass as the salt type block copolymer A-1. Color material dispersions G2 to G18 and comparative color material dispersions GC1 to GC2 were obtained in the same manner as in Example 21 (1) except that the amount of PGMEA was adjusted to be parts by mass.

(2) Production of photosensitive colored resin compositions G2 to G18 for color filters and photosensitive colored resin compositions GC1 to GC2 for comparative color filters In (2) of Example 21, instead of the colorant dispersion G1, Except for using the color material dispersions G2 to G18 and the comparative color material dispersions GC1 to GC2, in the same manner as in (2) of Example 21, the photosensitive colored resin compositions G2 to G18 for color filters were compared. Photosensitive colored resin compositions GC1 and GC2 for color filters were obtained.
(3) Formation of Colored Layer In Example 21 (3), except that the above-mentioned colored resin compositions G2 to G18 and GC1 to GC2 were used instead of the colored resin composition G1, respectively. ), Colored layers G2 to G18 and GC1 to GC2 were obtained.

(Example 41)
(1) Production of Coloring Material Dispersion R1 In Example 21 (1), C.I. I. Pigment Green 58 (PG58), 10.4 parts by mass, C.I. I. Pigment Yellow 138 (PY138) was replaced with 2.6 parts by mass of diketopyrrolopyrrole pigment (Irgaphor RED S 3621CF, manufactured by BASF) represented by the following chemical formula (R1) in an amount of 13 parts by mass. A colorant dispersion R1 was obtained in the same manner as in (1) of No. 21.

(2) Production of Photosensitive Colored Resin Composition R1 for Color Filter The procedure was the same as in (2) of Example 21, except that the coloring material dispersion R1 obtained above was used instead of the coloring material dispersion G1. In the same manner as in Example 21, (2), a photosensitive colored resin composition R1 for a color filter was obtained.
(3) Formation of Colored Layer Coloring was performed in the same manner as in (3) of Example 21 except that the colored resin composition R1 was used instead of the colored resin composition G1 in (3) of Example 21. Layer R1 was obtained.

(Example 42)
(1) Production of Coloring Material Dispersion B1 In Example 21 (1), C.I. I. Pigment Green 58 (PG58), 10.4 parts by mass, C.I. I. Pigment Yellow 138 (PY138) instead of 2.6 parts by mass. I. Pigment Blue 15: 6 (PB15: 6) Except for using 13 parts by mass, a colorant dispersion B1 was obtained in the same manner as (1) of Example 21.

(2) Production of Photosensitive Colored Resin Composition B1 for Color Filter The procedure was the same as Example 21 (2), except that the colorant dispersion B1 obtained above was used in place of the colorant dispersion G1. In the same manner as in Example 21, (2), a photosensitive colored resin composition B1 for a color filter was obtained.
(3) Formation of Colored Layer Coloring was performed in the same manner as in (3) of Example 21, except that in (3) of Example 21, the colored resin composition B1 was used instead of the colored resin composition G1. Layer B1 was obtained.

(Example 43)
(1) Production of Coloring Material Dispersion Y1 In Example 21 (1), C.I. I. Pigment Green 58 (PG58), 10.4 parts by mass, C.I. I. Pigment Yellow 138 (PY138) instead of 2.6 parts by mass. I. A colorant dispersion liquid Y1 was obtained in the same manner as in (1) of Example 21 except that 13 parts by mass of Disperse Yellow 54 (trade name: KP Plast Yellow HR, manufactured by Kiwa Chemical Co., Ltd.) was used.

(2) Production of Photosensitive Colored Resin Composition Y1 for Color Filter The procedure was the same as in (2) of Example 21, except that the colorant dispersion liquid Y1 obtained above was used instead of the colorant dispersion liquid G1. In the same manner as in Example 21, (2), a photosensitive colored resin composition Y1 for a color filter was obtained.
(3) Formation of Colored Layer Coloring was performed in the same manner as in (3) of Example 21, except that in (3) of Example 21, the colored resin composition Y1 was used instead of the colored resin composition G1. The layer Y1 was obtained.

[Evaluation method]
<Evaluation of viscosity stability of colorant dispersion>
The viscosity of the colorant dispersions obtained in Examples and Comparative Examples was measured immediately after preparation and after storage for 30 days at 25 ° C., and the viscosity change rate was calculated from the viscosity before and after storage to evaluate the viscosity stability. did. Viscosity was measured at 25.0 ± 0.5 ° C. using a vibration viscometer for viscosity measurement. The results are shown in Tables 2 and 3.
(Viscosity stability evaluation criteria)
AA: Change in viscosity before and after storage is less than 10% A: Change in viscosity before and after storage is 10% or more and less than 15% B: Change in viscosity before and after storage is 15% or more and less than 25% C: Before and after storage Change rate of viscosity is 25% or more and less than 40% D: Change rate of viscosity before and after storage is 40% or more provided that the color material is 13% by mass with respect to the total mass of the color material dispersion including the solvent. Is the value of
Even if the evaluation result is C, the coloring material dispersion liquid can be used practically. However, if the evaluation result is B, the coloring material dispersion liquid is better, and if the evaluation result is A, the coloring material dispersion liquid has poor dispersion stability. Are better.

<Evaluation of ITO crack resistance>
The photosensitive colored resin composition for a color filter obtained in each of the examples and the comparative examples was spin-coated 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. Was applied so that the film thickness after post-baking was about 2.5 μm. Thereafter, heating and drying were performed on a hot plate at 80 ° C. for 3 minutes. Ultraviolet light of 40 mJ / cm ² was irradiated using an ultra-high pressure mercury lamp without a photomask, and post-baked in a clean oven at 230 ° C. for 30 minutes to obtain a cured film (colored film).
On the obtained cured film, ITO having a thickness of 120 nm was formed using a sputtering device (manufactured by ULVAC: CS-200). After immersing this film in N-methylpyrrolidone at 25 ° C. for 120 minutes, the substrate was visually inspected for cracks in the ITO film.
(Evaluation criteria for ITO crack resistance)
AA: No cracks generated A: Five or less cracks generated B: Cracks occurred on the entire surface C: Cracks occurred on the entire surface and ITO was partially removed If the above evaluation criteria were AA or A Although it can be used practically, the effect is more excellent if the evaluation result is AA.

<Development adhesion evaluation>
The photosensitive colored resin composition for a color filter obtained in each of Examples and Comparative Examples was spin-coated 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 with 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 subjected to shower development for 60 seconds using a 0.05% by mass aqueous solution of potassium hydroxide as an alkaline developer. The developed substrate was observed with an optical microscope, and the presence or absence of a colored layer with respect to the mask opening line width was observed. The results are shown in Tables 2 and 3.
(Development adhesion evaluation criteria)
AA: A colored layer was observed in a portion having a mask opening line width of less than 10 μm A: A colored layer was observed in a portion having a mask opening line width of 10 μm or more and less than 20 μm B: A portion of a mask opening line width of 20 μm or more and less than 50 μm C: The colored layer was observed at a portion of the mask opening line width of 50 μm or more and less than 80 μm. D: The colored layer was not observed at the portion of the mask opening line width of 80 μm or less. Although the photosensitive colored resin composition for a color filter can be used practically, if the evaluation result is A, the photosensitive colored resin composition for a color filter is more suitable for higher definition. The photosensitive colored resin composition for filters is more suitable for higher definition.

<Development residue evaluation>
The photosensitive colored resin composition for a color filter obtained in each of Examples and Comparative Examples was spin-coated 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 with 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 coloring layer was formed was shower-developed for 120 seconds using a 0.05% by mass aqueous solution of potassium hydroxide as an alkali developing solution. After visually observing an unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer, the glass substrate was sufficiently wiped off with a lens cleaner (trade name: Toraysee MK Clean Cloth, manufactured by Toray Industries Inc.) containing ethanol. The degree of coloring of the lens cleaner was visually observed. The results are shown in Tables 2 and 3.
(Development residue evaluation criteria)
A: No development residue was visually observed, and no coloration was observed on the lens cleaner. B: No development residue was visually observed, and slight coloring of the lens cleaner was observed. C: Development residue was slightly observed, visually. The coloring of the lens cleaner was slightly confirmed. D: The development residue was slightly confirmed visually, and the coloring of the lens cleaner was confirmed. E: The development residue was confirmed visually, and the coloring of the lens cleaner was confirmed. When the development residue evaluation criterion is A, B or C, it is evaluated that the generation of the development residue is sufficiently suppressed, and it can be used without practical problems.

<Evaluation of solvent resolubility>
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 each of Examples and Comparative Examples, and was 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 30 minutes. Next, the glass substrate to which the dried coating film was attached was immersed in PGMEA for 15 seconds. At this time, the re-dissolved state of the dried coating film was visually determined and evaluated. The results are shown in Tables 2 and 3.
(Evaluation criteria for solvent resolubility)
AA: The dried coating film was completely dissolved. A: A flake of the dried coating film was formed in the solvent, and the flake was eventually dissolved. B: A flake of the dried coating film was formed in the solvent, and the solution was colored. C: In the solvent D: A thin film of the dried film was not formed and the solution was not colored. D: A thin film of the dried film was not generated in the solvent and the solution was not colored. It is evaluated as having good re-solubility, and can be used without practical problems.

<Evaluation of colorant sublimability>
The photosensitive coloring composition for a color filter obtained in each of Examples and Comparative Examples is applied onto a glass substrate having a thickness of 0.7 mm using a spin coater, and dried by heating on a hot plate at 80 ° C. for 3 minutes. As a result, a colored layer having a thickness of 2.5 μm was formed. This colored layer was irradiated with 40 mJ / cm ² ultraviolet rays using a super-high pressure mercury lamp through a photomask on which an 80 μm line & space stripe pattern was drawn. Thereafter, the glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass aqueous solution of potassium hydroxide as an alkali developer, and then washed with ultrapure water for another 60 seconds.
A glass substrate was placed on the 0.7 mm upper surface of the glass substrate on which the obtained colored pattern was formed, and heated on a 230 ° C. hot plate for 30 minutes. The sublimability of the coloring material was evaluated by visually checking the presence or absence of a sublimate on the glass substrate on the upper surface.
(Coloring material sublimation evaluation criteria)
A: No coloring and no precipitate on the upper glass substrate due to sublimate B: Coloring by the sublimate on the upper glass substrate, but no precipitate C: Sublimate on the upper glass substrate There was coloring, and precipitates were also confirmed

<Evaluation of substrate adhesion>
The photosensitive colored resin composition for a color filter obtained in each of Examples and Comparative Examples is applied to a 0.7 mm-thick glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater. did. Then, after heating and drying on a hot plate at 80 ° C. for 3 minutes, ultraviolet rays of 60 mJ / cm ² were irradiated using an ultra-high pressure mercury lamp. Thereafter, post-baking was performed in a clean oven at 230 ° C. for 30 minutes to obtain a colored film having a thickness of 2.5 μm.
After making a cut in a grid pattern with a cutter knife in the obtained colored film, a mending tape was stuck thereon and quickly peeled off in the vertical direction. The state of the colored film was visually observed and evaluated based on the following evaluation criteria. The results are shown in Tables 2 and 3.
(Substrate adhesion evaluation criteria)
AA: No peeling can be confirmed at all A: Peeling can be slightly confirmed along the cut of the base line B: Peeling is also confirmed inside the portion surrounded by the cut If the evaluation result is AA or A, the substrate is It is excellent in adhesiveness to aluminum and is evaluated as a practical range.

<Optical performance evaluation>
The photosensitive colored resin composition for a color filter obtained in each of Examples and Comparative Examples was spin-coated 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, it was dried at 80 ° C. for 3 minutes using a hot plate to form a colored layer. The colored layer was irradiated with ultraviolet rays of 60 mJ / cm ² using an ultrahigh pressure mercury lamp.
Next, the colored substrate was post-baked in a clean oven at 230 ° C. for 30 minutes, and the chromaticity (x, y) and luminance (Y) of the obtained colored substrate were measured using an Olympus microspectrophotometer OSP-SP200. It was measured. The results are shown in Tables 2 and 3. The light source used was a C light source.

[Summary of results]
From the results of Tables 2 and 3, the A block containing the structural unit represented by the general formula (I) as a dispersant, and the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) Using the photosensitive colored resin composition for a color filter of Examples 21 to 38 and Examples 41 to 43 using a block copolymer containing a B block containing at least one selected from structural units represented by The formed colored layer has high luminance, excellent crack resistance of the ITO film, excellent development adhesion and solvent resolubility, suppresses sublimation and precipitation of the coloring material in the colored layer, and improves substrate adhesion. Was also excellent.
On the other hand, a salt block copolymer in which the B block does not contain at least one selected from the structural units represented by the general formula (B1) and the structural units represented by the general formula (B2) is used as a dispersant. In Comparative Examples 11 and 12, the luminance was low, the crack resistance of the ITO film was poor, the development adhesion and the solvent resolubility were also poor, and sublimation or precipitation of the coloring material in the colored layer was confirmed. Was.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Counter substrate 30 Liquid crystal layer 40 Liquid crystal display 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 luminous body 100 Organic luminous display

Claims (11)

A colorant, a dispersant, and a colorant dispersion containing a solvent,
The dispersant is selected from an A block including a structural unit represented by the following general formula (I), a structural unit represented by the following general formula (B1), and a structural unit represented by the following general formula (B2). A color material dispersion for a color filter, which is a block copolymer containing at least one B block containing at least one of the above.

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

(In the general formula (B1), A ¹ is a divalent linking group, R ¹¹ is a divalent, trivalent or tetravalent aliphatic hydrocarbon group or a carbon atom which may contain an oxygen atom, and R ¹⁰ and R ¹² are Each independently represents a hydrogen atom or a methyl group; n is 1, 2 or 3)

(In the general formula (B2), A ² is a divalent linking group, A ³ and A ⁴ are each independently a divalent, tri- or tetravalent linking group, and R ¹³ is at least one selected from an oxygen atom and a nitrogen atom. R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ may each independently represent a divalent aliphatic hydrocarbon group optionally containing an oxygen atom, R ¹⁰ , R ^{10 15} and R ¹⁷ each independently represent a hydrogen atom or a methyl group, n ¹ represents 0, 1, ² , or 3, n ² represents 0 or 1, n ³ represents 0, 1, or 2, and n ¹ + n ² Is 1, 2 or 3 and n ¹ + n ² + n ³ is 1, 2 or 3. m ¹ represents 1, 2 or 3, m ² represents 0, 1 or 2, and m ¹ + m ² represents 1 , 2 or 3.)   The color material dispersion for color filters according to claim 1, wherein the dispersant has an acid value of 1 mgKOH / g to 18 mgKOH / g.   The dispersant comprises a salt in which at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) and at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon form a salt. The colorant dispersion for a color filter according to claim 1, comprising the formed salt-type block copolymer.   The colorant dispersion for a color filter according to any one of claims 1 to 3, wherein the dispersant has a hydroxyl value of 120 mgKOH / g or less.   The coloring material contains at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, quinophthalone dyes, coumarin dyes, cyanine dyes, and salt-forming compounds of these dyes. The colorant dispersion for color filters according to any one of claims 1 to 4. A block containing a structural unit represented by the following general formula (I) and at least one selected from a structural unit represented by the following general formula (B1) and a structural unit represented by the following general formula (B2) A dispersant, which is a block copolymer containing

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

(In the general formula (B1), A ¹ is a divalent linking group, R ¹¹ is a divalent, trivalent or tetravalent aliphatic hydrocarbon group or a carbon atom which may contain an oxygen atom, and R ¹⁰ and R ¹² are Each independently represents a hydrogen atom or a methyl group; n is 1, 2 or 3)

(In the general formula (B2), A ² is a divalent linking group, A ³ and A ⁴ are each independently a divalent, tri- or tetravalent linking group, and R ¹³ is at least one selected from an oxygen atom and a nitrogen atom. R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ may each independently represent a divalent aliphatic hydrocarbon group optionally containing an oxygen atom, R ¹⁰ , R ^{10 15} and R ¹⁷ each independently represent a hydrogen atom or a methyl group, n ¹ represents 0, 1, ² , or 3, n ² represents 0 or 1, n ³ represents 0, 1, or 2, and n ¹ + n ² Is 1, 2 or 3 and n ¹ + n ² + n ³ is 1, 2 or 3. m ¹ represents 1, 2 or 3, m ² represents 0, 1 or 2, and m ¹ + m ² represents 1 , 2 or 3.)   A photosensitive colored resin composition for a color filter, comprising the colorant dispersion according to any one of claims 1 to 5, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.   The photosensitive colored resin composition for a color filter according to claim 7, wherein the photoinitiator comprises an oxime ester.   9. The photosensitive colored resin composition for a color filter according to claim 7, wherein the photoinitiator contains at least two kinds of oxime esters and further contains an antioxidant.   A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the photosensitive colored resin for a color filter according to any one of claims 7 to 9. A color filter, which is a cured product of the composition.   A display device comprising the color filter according to claim 10.

Images