JP7317605B2 - Colorant dispersion liquid, dispersant, photosensitive colored resin composition, cured product, color filter, display device - Google Patents

Description

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

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

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

Here, the color filter is generally composed of a transparent substrate, a colored layer formed on the transparent substrate and composed of colored patterns of the 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 blocking portion.

As a method for forming pixels in a color filter, among others, a pigment dispersion method, which has excellent average characteristics in terms of spectral characteristics, durability, pattern shape, accuracy, etc., is most widely used.
2. Description of the Related Art In a color filter having pixels formed using a pigment dispersion method, miniaturization of pigments is being studied in order to achieve high brightness and high contrast. It is believed that by miniaturizing the pigment, the scattering of light transmitted through the color filter by the pigment particles is reduced, thereby achieving high brightness and high contrast.
However, since fine pigment particles tend to agglomerate, there is a problem that dispersibility and dispersion stability are lowered.

It is known that the use of a dispersant is effective as a technique for improving the dispersibility of finely divided pigments. For example, Patent Document 1 discloses that ammonium An A block containing a specific repeating unit having a base and a specific repeating unit having an amino group, a specific repeating unit containing a carboxylic acid ester, and an ethylene oxide group or a propylene oxide group in the alcohol-derived portion of the carboxylic acid ester A radiation-sensitive composition for forming a colored layer is disclosed, which uses a block copolymer having a B block containing a specific repeating unit containing the B block.
Further, Patent Document 2 discloses that a nitrogen-containing monomer, a polymer chain and its A graft copolymer containing, as a copolymerization component, a polymerizable oligomer consisting of a group having an ethylenically unsaturated double bond at its end, and further represented by the following general formula (II) with the amino group possessed by the nitrogen-containing monomer: A negative resist composition for color filters using a graft copolymer formed by forming a salt with an organic phosphoric acid compound is disclosed. Patent Document 2 describes that alkali developability is improved by forming a salt between an amino group of the nitrogen-containing monomer and an organic phosphoric acid compound represented by the following general formula (II).

Japanese Patent No. 5540599 JP 2009-265649 A

However, in recent years, in color filters, there is an increasing demand for a high concentration of colorants in a photosensitive resin composition due to demands for a wide color gamut and thin films. As the coloring material ratio in the photosensitive resin composition increases, the binder component relatively decreases. Among the binder components, the components related to the curability of the coating film, such as polyfunctional monomers and photoinitiators, are reduced. shortage occurs. In addition, since the amount of components related to developability, such as alkali-soluble resins, is reduced, development residues are generated and development time is delayed. Therefore, in order to meet the demand for increasing the concentration of the coloring material in the photosensitive resin composition, a technique is required that simultaneously solves these problems resulting from the shortage of the binder component. Incidentally, water staining refers to this phenomenon in which traces such as water stains are generated after alkali development and rinsing with pure water. Such water stains disappear after post-baking, so there is no problem with the product. occur. Therefore, if the inspection sensitivity of the inspection apparatus is lowered in the visual inspection, the yield of the final color filter product will be lowered, which is a problem.
The present invention has been made in view of the above-mentioned circumstances, and it is possible to produce a photosensitive colored resin composition that simultaneously satisfies suppression of development residue, shortening of development time, suppression of water staining, and excellent solvent resistance. An object of the present invention is to provide a coloring material dispersion and a dispersing agent. Another object of the present invention is to provide a photosensitive colored resin composition that simultaneously satisfies the suppression of development residue generation, shortening of development time, suppression of water staining, and good solvent resistance. Moreover, an object of this invention is to provide the color filter and display apparatus which were formed using the said photosensitive colored resin composition.

A colorant dispersion according to the present invention is a colorant dispersion containing a colorant, a dispersant, and a solvent, wherein the dispersant is a structural unit represented by the following general formula (I) and the following A graft copolymer having a structural unit represented by the general formula (II), and at least part of the nitrogen site of the structural unit represented by the general formula (I) of the graft copolymer and an organic acid It is at least one salt-type graft copolymer in which a salt is formed with at least one selected from the group consisting of a compound and a halogenated hydrocarbon.

（一般式（Ｉ）中、Ｒ^１は水素原子又はメチル基、Ａ^１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。
一般式（ＩＩ）中、Ｒ^１’は水素原子又はメチル基、Ａ^２は直接結合又は２価の連結基、Ｐｏｌｙｍｅｒはポリマー鎖を表し、当該ポリマー鎖の構成単位には下記一般式（ＩＩＩ）で表される構成単位が含まれる。）

(In general formula (I), R ¹ is a hydrogen atom or a methyl group, A ¹ is a divalent linking group, R ² and R ³ are each independently a hydrogen atom, or a hydrocarbon optionally containing a hetero atom. represents a group, and R ² and R ³ may combine with each other to form a ring structure.
In general formula (II), R ^{1 '} is a hydrogen atom or a methyl group, A ² is a direct bond or a divalent linking group, Polymer represents a polymer chain, and the structural unit of the polymer chain has the following general formula (III) Contains a structural unit represented by )

（一般式（ＩＩＩ）中、Ｒ^４は水素原子又はメチル基、Ａ^３は２価の連結基、Ｒ^５はエチレン基又はプロピレン基、Ｒ^６は、水素原子、又は炭化水素基であり、ｍは１９以上８０以下の数を表す。）

(In the general formula (III), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, m represents a number between 19 and 80.)

The dispersant according to the present invention is a graft copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and the A salt-type graft copolymer in which at least part of the nitrogen moieties of the structural units represented by the general formula (I) and at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons form a salt. At least one.

（一般式（Ｉ）中、Ｒ^１は水素原子又はメチル基、Ａ^１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。
一般式（ＩＩ）中、Ｒ^１’は水素原子又はメチル基、Ａ^２は直接結合又は２価の連結基、Ｐｏｌｙｍｅｒはポリマー鎖を表し、当該ポリマー鎖の構成単位には下記一般式（ＩＩＩ）で表される構成単位が含まれる。）

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A ¹ is a divalent linking group, R ² and R ³ are each independently a hydrogen atom, or a hydrocarbon optionally containing a hetero atom. represents a group, and R ² and R ³ may combine with each other to form a ring structure.
In general formula (II), R ^{1 '} is a hydrogen atom or a methyl group, A ² is a direct bond or a divalent linking group, Polymer represents a polymer chain, and the structural unit of the polymer chain has the following general formula (III) Contains a structural unit represented by )

（一般式（ＩＩＩ）中、Ｒ^４は水素原子又はメチル基、Ａ^３は２価の連結基、Ｒ^５はエチレン基又はプロピレン基、Ｒ^６は、水素原子、又は炭化水素基であり、ｍは１９以上８０以下の数を表す。）

(In the general formula (III), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, m represents a number between 19 and 80.)

The photosensitive colored resin composition according to the present invention contains the colorant dispersion liquid according to the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.

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

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

According to the present invention, a coloring material dispersion and a dispersant that can produce a photosensitive colored resin composition that simultaneously satisfies suppression of development residue, shortening of development time, suppression of water staining, and excellent solvent resistance. can be provided. Further, according to the present invention, the present invention can provide a photosensitive colored resin composition that simultaneously satisfies the suppression of development residue generation, shortening of development time, suppression of water staining, and good solvent resistance. . Moreover, according to this invention, the color filter and display apparatus which were formed using the said photosensitive colored resin composition can be provided.

FIG. 1 is a schematic diagram showing an example of the color filter of the present invention. FIG. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. FIG. 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention. FIG. 4 is a diagram schematically showing part of an example of the structure of the graft copolymer used in the present invention.

Hereinafter, the colorant dispersion, dispersant, photosensitive colored resin composition, color filter, and display device according to the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with a wavelength of 5 μm or less and electron beams.
In the present invention, (meth)acryloyl represents acryloyl and methacryloyl, (meth)acryl represents acrylic and methacrylic, and (meth)acrylate represents acrylate and methacrylate.
In this specification, unless otherwise specified, chromaticity coordinates x and y are in the XYZ color system of JIS Z8701:1999 measured using a C light source.
Further, in this specification, the term "to" indicating a numerical range is used to include the numerical values before and after it as lower and upper limits.

I. Colorant dispersion The colorant dispersion according to the present invention is a colorant dispersion containing a colorant, a dispersant, and a solvent,
The dispersant is a graft copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and the general formula ( At least one salt-type graft copolymer in which at least part of the nitrogen moiety of the structural unit represented by I) forms a salt with at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons. is.

（一般式（Ｉ）中、Ｒ^１は水素原子又はメチル基、Ａ^１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。
一般式（ＩＩ）中、Ｒ^１’は水素原子又はメチル基、Ａ^２は直接結合又は２価の連結基、Ｐｏｌｙｍｅｒはポリマー鎖を表し、当該ポリマー鎖の構成単位には下記一般式（ＩＩＩ）で表される構成単位が含まれる。）

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A ¹ is a divalent linking group, R ² and R ³ are each independently a hydrogen atom, or a hydrocarbon optionally containing a hetero atom. represents a group, and R ² and R ³ may combine with each other to form a ring structure.
In general formula (II), R ^{1 '} is a hydrogen atom or a methyl group, A ² is a direct bond or a divalent linking group, Polymer represents a polymer chain, and the structural unit of the polymer chain has the following general formula (III) Contains a structural unit represented by )

（一般式（ＩＩＩ）中、Ｒ^４は水素原子又はメチル基、Ａ^３は２価の連結基、Ｒ^５はエチレン基又はプロピレン基、Ｒ^６は、水素原子、又は炭化水素基であり、ｍは１９以上８０以下の数を表す。）

(In the general formula (III), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, m represents a number between 19 and 80.)

The colorant dispersion according to the present invention uses the specific graft copolymer or salt-type graft copolymer as a dispersant. FIG. 4 is a diagram schematically showing part of an example of the structure of the graft copolymer used in the present invention. In FIG. 4, the graft copolymer 11 contains a main chain portion 12 having a structural unit 21 represented by the general formula (I) and a structural unit 22 represented by the general formula (II). At least part of the nitrogen moiety of the structural unit 21 represented by (I) and at least one species 23 selected from the group consisting of organic acid compounds and halogenated hydrocarbons may form a salt, and the general Structural unit 22 represented by formula (II) includes structural unit 25 represented by general formula (III) including polyethylene oxide chain or polypropylene oxide chain 26 having a specific repeating number in polymer chain 24 . In the specific graft copolymer used in the present invention, the structural units of the polymer chains 24 thus grafted include structural units 25 having polyethylene oxide chains or polypropylene oxide chains having a specific number of repeats. , the grafting polymer chain 24 itself has a branched structure. Therefore, the photosensitive colored resin composition prepared using the colorant dispersion can simultaneously satisfy suppression of development residue generation, shortening of development time, suppression of water staining, and excellent solvent resistance. . Although the action that exhibits such an effect is not yet clarified, it is presumed as follows.

The specific graft copolymer contains a structural unit having a relatively long polyethylene oxide chain or polypropylene oxide chain as a structural unit of the grafted polymer chain, and the grafted polymer chain itself has a branched structure. It is characterized by having It is thought that the oxygen atoms contained in the polyethylene oxide chain or the polypropylene oxide chain form a hydrogen bond with the alkaline developer, thereby facilitating dissolution in the alkaline developer during development. In addition, the oxygen atoms contained in the polyethylene oxide chain or the polypropylene oxide chain interact with OH and CH such as carboxy groups of the alkali-soluble resin contained in the photosensitive resin composition through hydrogen bonding, thereby increasing the alkalinity during development. It is thought that only the soluble resin is dissolved and the colorant and the dispersant are not left as residue. Since the constituent units of the grafted polymer chain contain branched structural units having relatively long polyethylene oxide chains or polypropylene oxide chains, hydrogen bonding with alkali developing solutions and alkali-soluble resins It is thought that the interaction becomes stronger. Since the graft copolymer has a branched structure in which multiple polymer chains are grafted and becomes the solvent affinity part of the dispersant, the specific surface area of the solvent affinity part of the dispersant is larger than that of the block copolymer. Together with the increase in size, the effect of the solvent affinity portion due to the oxygen atoms contained in the polyethylene oxide chain or polypropylene oxide chain becomes remarkable, the effect of suppressing the generation of development residue is improved, and the development time is shortened. It is estimated to be.
On the other hand, it has been found that if the number of repeating units of the polyethylene oxide chain or polypropylene oxide chain is too large, the effect of suppressing the generation of development residue is not improved. This is because when the number of repeating units of the polyethylene oxide chain or polypropylene oxide chain becomes too large, the affinity with the alkaline developer becomes excessively greater than the pigment adsorptive power, and only the graft copolymer dissolves in the alkaline developer. It is presumed that this is because the pigment remains on the substrate.
In addition, since the graft copolymer has a plurality of grafted polymer chains serving as the solvent affinity portion of the dispersant, the specific surface area of the solvent affinity portion of the dispersant increases. It is presumed that penetration and arrival at the colorant can be suppressed. Therefore, it is presumed that the use of the dispersant of the present invention can improve solvent resistance and resistance (NMP resistance) to N-methylpyrrolidone (NMP), which is used as a solvent in the preparation of alignment films for color filters. .
Furthermore, water absorption into the cured film is one of the causes of water stains in the cured film of the photosensitive resin composition. Since the alkali-soluble resin in the cured film has an acidic group such as a carboxyl group, it easily absorbs water. In addition, it is believed that the acidic group forms a metal salt with an alkali metal typically contained in an alkali developer during development, thereby further increasing the water absorbency. Oxygen atoms contained in polyethylene oxide chains or polypropylene oxide chains can be captured by complexing with metals such as alkali metals. As the number of repeating units of the polyethylene oxide chain or polypropylene oxide chain increases, the complex formation constant increases, and the ability to capture metal molecules increases. It is presumed that water absorption can be suppressed. In addition, the oxygen atoms contained in the polyethylene oxide chain or the polypropylene oxide chain interact with an acidic group such as a carboxyl group of the alkali-soluble resin contained in the photosensitive resin composition through hydrogen bonding, thereby increasing the alkalinity of the acidic group. It is presumed that the metal salt formation can be suppressed and water absorption into the cured film can be suppressed. In the graft copolymer, the multiple polymer chains grafted have a branched structure and serve as a metal-capturing portion. Alternatively, it is presumed that the effect of metal capture by the oxygen atoms contained in the polypropylene oxide chain becomes remarkable, the water absorption suppressing effect is improved, and the occurrence of water stains due to water absorption can be suppressed. It is presumed that the action of suppressing water absorption into the cured film can suppress the occurrence of water stains due to water absorption.

The coloring material dispersion liquid according to the present invention contains at least a coloring material, a dispersant, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention. be.
Hereinafter, each component of the colorant dispersion according to the present invention will be described in detail, starting with the dispersant of the present invention.

<Dispersant>
In the present invention, as a dispersant, a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), and the graft copolymer A salt-type graft copolymer in which at least part of the nitrogen moiety of the structural unit represented by the general formula (I) and at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons form a salt. At least one of is used.
First, the graft copolymer will be explained.

(Structural Unit Represented by Formula (I))
The structural unit represented by the general formula (I), which constitutes the main chain of the graft copolymer, has basicity and functions as an adsorption site for the coloring material.
In general formula (I), A ¹ is a divalent linking group. As the divalent linking group, for example, a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, -CONH- group, -COO- group, -NHCOO- groups, ether groups (--O--groups), thioether groups (--S--groups), and combinations thereof. In the present invention, the bonding direction of the divalent linking group is arbitrary. That is, when -CONH- is included in the divalent linking group, -CO may be on the carbon atom side of the main chain and -NH may be on the nitrogen atom side of the side chain, on the contrary, -NH is the main chain --CO may be on the nitrogen atom side of the side chain.
Among them, from the viewpoint of dispersibility, A ¹ in the general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and a -CONH- group or a -COO- group. , and an alkylene group having 1 to 10 carbon atoms are more preferable.

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

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. A heteroatom may be included in the ring structure formed by R ² and R ³ . Although the ring structure is not particularly limited, examples thereof include pyrrolidine ring, piperidine ring, morpholine ring and the like.

In the present invention, among others, 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 or a morpholine ring.

Examples of monomers that derive structural units represented by the general formula (I) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, and the like. Examples thereof include alkyl group-substituted amino group-containing (meth)acrylates and alkyl group-substituted amino group-containing (meth)acrylamides 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 in terms of improving dispersibility and dispersion stability.
The structural unit represented by formula (I) may consist of one type, or may contain two or more types of structural units.

(Structural Unit Represented by General Formula (II))
By having a structural unit represented by the general formula (II) having a specific polymer chain, the graft copolymer has good solvent affinity and good dispersibility and dispersion stability of the coloring material. become a thing. In addition, the graft copolymer has steric hindrance and an increase in specific surface area due to the specific polymer chain contained in the structural unit represented by the general formula (II), and particularly the structural unit of the polymer chain has the general formula (III) ), the interaction with alkali-soluble resins, developers and metals becomes good as described above, suppressing the generation of development residues of the photosensitive resin composition and shortening the development time. Shortening, suppressing water staining, and improving solvent resistance.

In the general formula (II), ^A2 is a direct bond or a divalent linking group. The divalent linking group for ^A2 is not particularly limited as long as it can link the carbon atom derived from the ethylenically unsaturated double bond and the polymer chain. Examples of the divalent linking group for A ² include those similar to the divalent linking group for A ¹ .

In the general formula (II), Polymer represents a polymer chain, and the constituent units of the polymer chain include the constituent units represented by the general formula (III).
In the general formula (III), ^R4 is a hydrogen atom or a methyl group, ^A3 is a divalent linking group, ^R5 is an ethylene group or a propylene group, ^R6 is a hydrogen atom or a hydrocarbon group, m represents a number of 19 or more and 80 or less.

Examples of the divalent linking group for A ³ include those similar to the divalent linking group for A ¹ . Among them, from the viewpoint of solubility in organic solvents used for color filters, A ³ in general formula (III) is preferably a divalent linking group containing a -CONH- or -COO- group. , -CONH- group or -COO- group is more preferred.

The aforementioned m represents the number of repeating units of an ethylene oxide chain or a propylene oxide chain, and represents a number of 19 or more.
On the other hand, although the upper limit of m is 80 or less, it is preferably 50 or less from the viewpoint of solubility in organic solvents used for color filters.

Examples of hydrocarbon groups for R ⁶ include alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, aryl groups, and combinations thereof such as aralkyl groups and alkyl-substituted aryl groups.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl and n- nonyl group, n-lauryl group, n-stearyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like. The number of carbon atoms in the alkyl group is preferably 1-12, more preferably 1-6.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, and propenyl groups. Although the position of the double bond of the alkenyl group is not limited, it is preferable that the alkenyl group has a double bond at the terminal from the viewpoint of the reactivity of the resulting polymer. The alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.
Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. The number of carbon atoms in the aryl group is preferably 6-24, more preferably 6-12.
Moreover, the aralkyl group includes a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent. The number of carbon atoms in the aralkyl group is preferably 7-20, more preferably 7-14.
Further, a linear or branched alkyl group having 1 to 30 carbon atoms may be bonded as a substituent to the aromatic ring such as the aryl group or the aralkyl group.

From the standpoint of dispersion stability, the hydrocarbon group for R ⁶ is, among others, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group, and an alkyl group. It is preferably one or more selected from the group consisting of optionally substituted aralkyl groups having 7 to 14 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n It is preferably one or more selected from the group consisting of -nonyl group, n-lauryl group, n-stearyl group, phenyl group optionally substituted with an alkyl group, and benzyl group.

In the polymer chain, the structural unit represented by the general formula (III) may be of one type alone, or may be of a mixture of two or more types.
From the viewpoint of the effect of the present invention, in the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, when the total structural units of the polymer chain are 100% by mass, the general formula The total proportion of the structural units represented by (III) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more. The total proportion of the structural units represented by the general formula (III) may be 100% by mass when the total structural units of the polymer chain are taken as 100% by mass. The content is preferably 75% by mass or less, more preferably 65% by mass or less, and even more preferably 50% by mass or less from the viewpoint of solvent re-solubility.

The structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer further includes the following general formula (IV), which is different from the structural unit represented by the general formula (III). ) is preferably contained from the viewpoint of dispersibility and dispersion stability of the colorant.

（一般式（ＩＶ）中、Ｒ^４’は水素原子又はメチル基、Ａ^４は２価の連結基、Ｒ^７は、水素原子、又はヘテロ原子を含んでもよい炭化水素基である。）

(In general formula (IV), R ^4' is a hydrogen atom or a methyl group, A ⁴ is a divalent linking group, and R ⁷ is a hydrogen atom or a hydrocarbon group which may contain a hetero atom.)

Examples of the divalent linking group for A ⁴ include those similar to the divalent linking group for A ¹ . Among them, from the viewpoint of solubility in organic solvents used for color filters, A ⁴ in general formula (IV) is preferably a divalent linking group containing a -CONH- or -COO- group. , -CONH- group or -COO- group is more preferred.

Examples of hydrocarbon groups in the hydrocarbon group optionally containing a heteroatom in R ⁷ include alkyl groups, alkenyl groups, aryl groups, and combinations thereof such as aralkyl groups and alkyl-substituted aryl groups. Examples of the hydrocarbon group in the hydrocarbon group optionally containing a heteroatom for R ⁷ include the same hydrocarbon groups as the hydrocarbon group for R ⁶ .

Heteroatoms which the hydrocarbon group may contain include, for example, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like. The hydrocarbon group which may contain a heteroatom includes, for example, -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, - S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O- , —O—NH— and other connecting groups.
Further, the hydrocarbon group may have a substituent as long as it does not interfere with the dispersion performance of the graft copolymer. Nitro group, cyano group, epoxy group, isocyanate group, thiol group and the like.

The hydrocarbon group optionally containing a heteroatom in R ⁷ may have a structure in which a polymerizable group such as an alkenyl group is added to the end of the hydrocarbon group via a linking group containing a heteroatom. For example, the structural unit represented by general formula (IV) may have a structure obtained by reacting a structural unit derived from (meth)acrylic acid with glycidyl (meth)acrylate. That is, the structure of -A ⁴ -R ⁷ in general formula (IV) is -COO-CH ₂ CH(OH)CH ₂ -OCO-CR=CH ₂ (wherein R is a hydrogen atom or a methyl group). It may be a structure that can be Further, the structural unit represented by general formula (IV) may have a structure obtained by reacting a structural unit derived from hydroxyalkyl(meth)acrylate with 2-isocyanatoalkyl(meth)acrylate. That is, R ⁷ in the general formula (IV) is -R'-OCONH-R"-OCO-CR=CH ₂ (wherein R' and R" are each independently an alkylene group, R is a hydrogen atom or a methyl group ) may be used.

Examples of monomers that induce structural units represented by general formula (IV) include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) Acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate , dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, (meth) acrylic acid, 2-methacryloyloxyethyl succinate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxyethyl (meth)acrylate, methoxypolyethylene glycol having less than 19 repeating units in the ethylene oxide chain ( Those having structural units derived from meth)acrylate, polyethylene glycol (meth)acrylate, phenoxyethylene glycol (meth)acrylate and the like are preferred. However, it is not limited to these.

In the present invention, it is preferable to use one having excellent solubility in an organic solvent, which will be described later, as ^R7 , and it may be appropriately selected according to the organic solvent used in the colorant dispersion. Specifically, for example, when the organic solvent is an ether-alcohol acetate-based, ether-based, ester-based, or alcohol-based organic solvent generally used as an organic solvent for a colorant dispersion, methyl group, ethyl group, isobutyl group, n-butyl group, 2-ethylhexyl group, benzyl group, cyclohexyl group, dicyclopentanyl group, hydroxyethyl group, phenoxyethyl group, adamantyl group, methoxypolyethylene glycol group, methoxypolypropylene glycol group , polyethylene glycol group and the like are preferred.

In the polymer chain, the structural unit represented by the general formula (IV) may be used singly or in combination of two or more.
From the viewpoint of the dispersibility and dispersion stability of the coloring material, the total proportion of the structural units represented by the general formula (IV) in the polymer chain is It is preferably 25% by mass or more, more preferably 35% by mass or more. On the other hand, from the viewpoint of suppressing the occurrence of water stains due to the introduction of general formula (III), the total proportion of the structural units represented by general formula (IV) in the polymer chain is 100% of the total structural units of the polymer chain. It is preferably 99% by mass or less, more preferably 98% by mass or less.

In the structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, the structural unit represented by the general formula (IV) may further include the following general formula (IIIa) ) is preferably contained from the viewpoint of improving the effect of suppressing development residue.

（一般式（ＩＩＩａ）中、Ｒ^４は水素原子又はメチル基、Ａ^３は２価の連結基、Ｒ^５はエチレン基又はプロピレン基、Ｒ^６は、水素原子、又は炭化水素基であり、ｍ’は１０以下の数を表す。）

(In the general formula (IIIa), R ⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or a hydrocarbon group, m ' represents a number of 10 or less.)

R ⁴ , A ³ , R ⁵ and R ⁶ in general formula (IIIa) may be the same as R ⁴ , A ³ , R ⁵ and R ⁶ in general formula (III).
Although m' in the general formula (IIIa) represents a number of 10 or less, m' is preferably 2 or more, more preferably 3 or more, from the viewpoint of suppressing development residue generation. In terms of solvent resolubility, m' is preferably 9 or less, more preferably 8 or less.

In the polymer chain, the structural unit represented by the general formula (IIIa) may be used singly or in combination of two or more.
From the viewpoint of improving the effect of suppressing development residue, the total proportion of the structural units represented by the general formula (IIIa) in the polymer chain is 20% by mass when the total structural units of the polymer chain are 100% by mass. It is preferable that it is above. On the other hand, from the viewpoint of solvent resolubility, the total proportion of the structural units represented by the general formula (IIIa) in the polymer chain is 80 mass when the total structural units of the polymer chain are 100 mass%. % or less, more preferably 60 mass % or less.
Further, in the polymer chain, the mixing ratio of the structural unit represented by the general formula (III) and the structural unit represented by the general formula (IIIa) is from the viewpoint of improving the effect of suppressing the generation of development residue. When the total of the structural unit represented by the general formula (III) and the structural unit represented by the general formula (IIIa) is 100 parts by mass, the structural unit represented by the general formula (III) is 3 mass parts. It is preferably 6 parts by mass or more, more preferably 6 parts by mass or more, preferably 80 parts by mass or less, and more preferably 60 parts by mass or less.

The structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer includes the structural unit represented by the general formula (III), and the structural unit represented by the general formula (IIIa). Other structural units may be included in addition to the structural units represented by the general formula (IV) in which the structural units are included.
Other structural units include an unsaturated double bond copolymerizable with a monomer that induces a structural unit represented by the general formula (III) or a monomer that induces a structural unit represented by the general formula (IV). A structural unit derived from a monomer having
Examples of monomers from which other structural units are derived include styrene, styrenes such as α-methylstyrene, vinyl ethers such as phenyl vinyl ether, and the like.

In the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, the total proportion of other structural units is 100% of the total structural units of the polymer chain, from the viewpoint of the effect of the present invention. When expressed as % by mass, it is preferably 30% by mass or less, more preferably 10% by mass or less.

The weight average molecular weight Mw of the polymer chain in the polymer is preferably 2000 or more, more preferably 3000 or more, and even more preferably 4000 or more, from the viewpoint of the dispersibility and dispersion stability of the colorant. , 15000 or less, and even more preferably 12000 or less.
Within the above range, a sufficient steric repulsion effect as a dispersant can be maintained, and the specific surface area of the solvent affinity portion of the dispersant is increased, resulting from the oxygen atoms contained in the polyethylene oxide chain or polypropylene oxide chain. The interaction becomes remarkable, and the effects of improving the effect of suppressing the generation of development residues, shortening the development time, and improving the solvent resistance can be improved.

In addition, as a guideline, the polymer chain in Polymer preferably has a solubility of 20 (g/100 g solvent) or more at 23° C. in the organic solvent used in combination.
The solubility of the polymer chain can be determined based on the solubility of the raw material into which the polymer chain is introduced in the preparation of the graft copolymer. For example, when a polymerizable oligomer (macromonomer) containing a group having an ethylenically unsaturated double bond at the polymer chain and its terminal is used to introduce the polymer chain into the graft copolymer, the polymerizable oligomer is So long as it has solubility. Further, after a copolymer is formed from a monomer containing a group having an ethylenically unsaturated double bond, using a polymer chain containing a reactive group capable of reacting with the reactive group contained in the copolymer, When a polymer chain is introduced, the polymer chain containing the reactive group should have the aforementioned solubility.

(graft copolymer)
In the graft copolymer, the structural unit represented by the general formula (I) is preferably contained in a proportion of 3 to 60% by mass, more preferably 6 to 45% by mass, and 9 to 30% by mass. % is more preferred. If the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity portion with the coloring material in the graft copolymer will be appropriate, and the solubility in the organic solvent will be good. Since the deterioration of the properties can be suppressed, the adsorptivity to the coloring material is improved, and excellent dispersibility and dispersion stability can be obtained.
On the other hand, in the graft copolymer, the structural unit represented by the general formula (II) is preferably contained at a rate of 40 to 97% by mass, more preferably 55 to 94% by mass, and 70 to 70% by mass. 91% by mass is more preferred. If the structural unit represented by the general formula (II) in the graft copolymer is within the above range, the ratio of the solvent-affinity portion in the graft copolymer will be appropriate, resulting in sufficient stericity as a dispersant. In addition to maintaining the repulsion effect, the specific surface area of the solvent affinity part of the dispersant increases, so that the interaction of oxygen atoms contained in the polyethylene oxide chain or polypropylene oxide chain becomes remarkable, and the effect of suppressing the generation of development residue is improved. improvement, shortening of development time, and improvement of solvent resistance can be improved.
The content ratio of the structural unit is calculated from the amount charged when synthesizing the structural unit represented by the general formula (I) and the graft copolymer having the structural unit represented by the general formula (II). be.

The graft copolymer used in the present invention, other than the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II), within a range that does not impair the effects of the present invention. In addition, it may have other structural units. As the other structural unit, an ethylenically unsaturated double bond-containing monomer that can be copolymerized with the ethylenically unsaturated double bond-containing monomer from which the structural unit represented by the general formula (I) is derived is appropriately selected. can be copolymerized to introduce other structural units.
Other structural units copolymerized with the structural units represented by the general formula (I) include, for example, the structural units of the polymer chain of the structural units represented by the general formula (II), the general formula It has a graft chain different from the structural unit represented by the general formula (II), which does not contain the structural unit represented by (III) and contains the structural unit represented by the general formula (IIIa). Structural units, structural units represented by the general formula (IV), and the like are included.

Further, the weight average molecular weight Mw of the graft copolymer is preferably 4000 or more, more preferably 6000 or more, and even more preferably 8000 or more, from the viewpoint of dispersibility and dispersion stability. . On the other hand, it is preferably 50,000 or less, more preferably 30,000 or less, from the viewpoint of solvent resolubility.
In addition, the mass average molecular weight Mw in the present invention is a value measured by GPC (gel permeation chromatography). The measurement was carried out using Tosoh's HLC-8120GPC, the elution solvent was N-methylpyrrolidone added with 0.01 mol/liter of lithium bromide, and the polystyrene standards for the calibration curve were Mw 377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories) and Mw 1090000 (manufactured by Tosoh), and the measurement column was TSK-GEL ALPHA-M × 2 (manufactured by Tosoh). is.

The amine value of the graft copolymer before salt formation is not particularly limited, but from the viewpoint of colorant dispersibility and dispersion stability, the lower limit is preferably 40 mgKOH/g or more, and 50 mgKOH/g or more. is more preferable, and 60 mgKOH/g or more is even more preferable. 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. If it is more than the said lower limit, dispersion stability will be more excellent. Moreover, if it is below the said upper limit, it will be excellent in compatibility with other components, and solvent re-solubility will become favorable.
In the present invention, the amine value of the graft copolymer before salt formation is potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize 1 g of the solid content of the graft copolymer before salt formation. and is a value measured by the method described in JIS K 7237:1995.

The acid value of the graft copolymer before salt formation is preferably 18 mgKOH/g or less, more preferably 12 mgKOH/g or less, from the viewpoint of good development adhesion and solvent resolubility. Further, the acid value of the graft copolymer before salt formation may be less than 1 mgKOH/g from the viewpoint of further improving solvent resolubility and development adhesion and dispersion stability. On the other hand, from the viewpoint of the effect of suppressing development residue, it is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g or more.

The acid value of the graft copolymer before salt formation represents the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid content of the graft copolymer, and is determined according to JIS K 0070:1992. It is a value measured by the method described in .

(Method for producing graft copolymer)
In the present invention, as the method for producing the graft copolymer, a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) is produced. It is not particularly limited as long as it can be done. When producing a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), for example, a monomer represented by the following general formula (Ia) and a polymerizable oligomer (macromonomer) comprising a group having an ethylenically unsaturated double bond at the end of the polymer chain as a copolymerization component, and copolymerizing to produce a graft copolymer. mentioned.
If necessary, other monomers may also be used, and the graft copolymer can be produced using known polymerization means.

（一般式（Ｉａ）中、Ｒ^１、Ａ^１、Ｒ^２及びＲ^３は、一般式（Ｉ）と同様である。）

(In general formula (Ia), R ¹ , A ¹ , R ² and R ³ are the same as in general formula (I).)

Further, when producing a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), the monomer represented by the general formula (Ia) and other monomers containing groups having ethylenically unsaturated double bonds are added to form a copolymer, after which the reactive groups contained in the copolymer and reactive groups that can react Polymer chains may be used to introduce polymer chains. Specifically, for example, after synthesizing a copolymer having a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond forming group, a functional group that reacts with the substituent is added. A polymer chain may be introduced by reacting with a polymer chain contained therein.
For example, a copolymer having a glycidyl group in the side chain is reacted with a polymer chain having a terminal carboxyl group, or a copolymer having an isocyanate group in the side chain is reacted with a polymer chain having a hydroxyl group at the terminal. can introduce polymer chains.
In addition, in the polymerization, additives commonly used in polymerization, such as polymerization initiators, dispersion stabilizers, and chain transfer agents, may be used.

(At least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons)
In the present invention, the dispersant, from the viewpoint of improving the dispersibility of the coloring material, comprises at least part of the nitrogen moiety of the structural unit represented by the general formula (I) of the graft copolymer, an organic acid compound and a halogen It may be a salt-type graft copolymer formed by forming a salt with at least one selected from the group consisting of hydrocarbons.
As the organic acid compound, among others, a compound represented by the following general formula (1) and a compound represented by the following general formula (3) are preferable. ) are preferred. That is, at least one compound selected from the group consisting of the organic acid compound and the halogenated hydrocarbon is preferably one or more compounds selected from the group consisting of the following general formulas (1) to (3). 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 general formula (1), R ^a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, or -O- Represents R ^e , R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or a C 1 to 4 represents a (meth)acryloyl group via an alkylene group.In 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 which may have a substituent, a phenyl group which may have a substituent or a benzyl group, or -O- R ^f represents an optionally substituted linear, branched or ^cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group optionally having a substituent, a substituted may be a phenyl group or a benzyl group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom. , R ^c and R ^d are each independently a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, Alternatively, —O—R ^e , where R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, or a carbon number represents a (meth)acryloyl group via 1 to 4 alkylene groups, provided that at least one of R ^c and R ^d 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), R ^a , R ^b , R ^b′ , R ^b″ , R ^c , R ^d , R ^e , and R ^f have straight or branched chains having 1 to 20 carbon atoms. Alternatively, the cyclic alkyl group may be either linear or branched, and may contain a cyclic structure. Specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n- Examples include undecyl group, dodecyl group, cyclopentyl group, cyclohexyl group, tetradecyl group, octadecyl group, etc. Preferable examples include linear, branched or cyclic alkyl groups having 1 to 15 carbon atoms, and more preferably straight-chain, branched-chain or cyclic alkyl groups having 1 to 15 carbon atoms. 1 to 8 linear, branched or cyclic alkyl groups are included.
In R ^a , R ^c , R ^d and R ^e , the substituents of the phenyl group or benzyl group which may have a substituent include, for example, an alkyl group having 1 to 5 carbon atoms, an acyl group , an acyloxy group, and the like.

In R ^b , R ^b′ , R ^b″ and R ^f , the substituents of the phenyl group or benzyl group which may have a substituent include, for example, an acidic group or an ester group thereof, a carbon atom number of 1 to 5 alkyl group, acyl group, acyloxy group and the like.
Further, in R ^b , R ^b′ , R ^b″ and R ^f , as a substituent of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or a vinyl group, includes an acidic group or an ester group thereof, a phenyl group, an acyl group, an acyloxy group, and the like.
The acidic group in R ^b , R ^b′ , R ^b″ and R ^f means a group that releases protons 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 ), borinic acid group (>BOH) and the like, may be an anion in which a hydrogen atom is dissociated such as a carboxylate group (—COO ⁻ ), and further alkali metal ions and salts such as sodium ions and potassium ions. It may also be an acid salt formed.
Examples of the ester group of the acidic group include carboxylic acid ester (-COOR), sulfonic acid ester (-SO ₃ R), phosphoric acid ester (-P(=O)(OR) ₂ ), (>P(=O )(OR)), boronate ester (-B(OR) ₂ ), borinate 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. In addition, R is a hydrocarbon group and is not particularly limited, but from the viewpoint of dispersibility and dispersion stability, it is preferably an alkyl group having 1 to 5 carbon atoms, and is preferably a methyl group or an ethyl group. more preferred.

From the viewpoint of dispersibility, dispersion stability, alkali developability, and suppression of development residue, the compound of the general formula (2) has a carboxy group, a boronic acid group, a borinic acid group, their anions, and their alkali metal salts. , and one or more functional groups selected from these esters. Among them, it is more preferable to have a functional group selected from a carboxy group, a carboxylate group, a carboxylic acid group, and a carboxylic acid ester. .
When the compound of the general formula (2) has an acidic group and an ester group thereof (hereinafter referred to as an acidic group, etc.), both the acidic group side and the halogen atom side hydrocarbon of the compound are terminal nitrogen A salt can be formed with the site, but it is presumed that the terminal nitrogen site and the hydrocarbon on the halogen atom side form a salt more stably than the case where the terminal nitrogen site and an acidic group or the like form a salt. It is presumed that dispersibility and dispersion stability are improved by adsorption of the coloring material to the stably existing salt-forming sites.

When the compound of general formula (2) has the acidic group or the like, it may have two or more of the acidic group or the like. In the case of having two or more of the acidic groups, etc., the plurality of acidic groups, etc. may be the same or different. The number of the acidic groups, etc. possessed by the compound of general formula (2) is preferably 1 to 3, more preferably 1 to 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 between the skeleton of the coloring material described later is improved, the dispersibility and dispersion stability of the coloring material are excellent, and a coloring composition with excellent contrast is obtained. It is preferable because it is possible to

The molecular weight of one or more compounds selected from the group consisting of the general formulas (1) to (3) is preferably 1000 or less, especially 50 to 800, from the viewpoint of improving the dispersibility of the colorant. is preferred, more preferably 50-400, even more preferably 80-350, most preferably 100-330.

Examples of the compound represented by the general formula (1) include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfuric acid, monoethylsulfuric acid, mono-n-propylsulfuric acid and the like. A hydrate such as p-toluenesulfonic acid monohydrate may also 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 phosphate, dibutyl phosphate, methyl phosphate, dibenzyl phosphate, diphenyl phosphate, phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, and the like. .
Phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, dibutyl phosphate, methyl chloride, methyl bromide, methyl iodide, benzyl chloride, benzyl bromide, vinyl sulfonic acid, and p- One or more selected from the group consisting of toluenesulfonic acid monohydrate is preferable, and among them, from the group consisting of phenylphosphinic acid, phenylphosphonic acid, benzyl chloride, benzyl bromide, and p-toluenesulfonic acid monohydrate. It is preferable to use one or more selected types.
In addition, the compound represented by the general formula (2) having an acidic group and an ester group thereof is also preferably used because the effect of suppressing development residue is improved by combining with the above-mentioned specific graft 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 is also preferred. Used.

In the salt-type graft copolymer, the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is such that the terminal nitrogen moiety of the structural unit represented by general formula (I) and 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 portion of the structural unit represented by the general formula (I). It is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.1 mol or more, and particularly preferably 0.2 mol or more. When it is at least the above lower limit, the effect of improving the dispersibility of the coloring material by salt formation is likely to be obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, even more preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. When it is not more than the above upper limit, it can be excellent in development adhesion and solvent re-solubility.
At least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used singly 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 graft copolymer, at least one selected from the group consisting of the above organic acid compounds and halogenated hydrocarbons is added to a solvent in which the graft copolymer before salt formation is dissolved or dispersed. , stirring, and heating if necessary.
The terminal nitrogen portion of the structural unit represented by the general formula (I) of the graft copolymer and at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon form a salt. It can be confirmed by a known technique such as NMR, for example.

The amine value of the resulting salt-type graft copolymer is smaller than that of the graft copolymer before salt formation by the amount of salt formation. However, since the salt-forming site becomes a colorant adsorption site that is similar to or rather strengthened as the terminal nitrogen site corresponding to the amino group, the salt formation tends to improve colorant dispersibility and colorant dispersion stability. be. Also, similarly to amino groups, too many salt-forming sites adversely affect solvent resolubility. Therefore, in the present invention, the amine value of the graft copolymer before salt formation can be used as an index for improving colorant dispersion stability and solvent re-solubility. The amine value of the resulting salt-type graft copolymer is preferably 0 to 130 mgKOH/g, more preferably 10 to 120 mgKOH/g, even more preferably 20 to 110 mgKOH/g. .
If it is less than the above upper limit, the compatibility with other components will be excellent, and the solvent re-solubility will be good.

Among the salt-type graft copolymers, the amine value of the salt-type graft copolymer salt-formed with the compound represented by the general formula (2) is measured by the method described in JIS K 7237:1995. can be the value In the compound of general formula (2), the terminal nitrogen site of the structural unit represented by general formula (I) and the hydrocarbon on the halogen atom side form a salt. This is because the amine value can be measured without causing any change.
On the other hand, among the salt-type graft copolymers, the amine value of the salt-type graft copolymer salt-formed with the compound represented by the general formula (1) or (3) is It is obtained by the following calculation from the amine value of the graft copolymer. In the compound represented by the general formula (1) or (3), since the terminal nitrogen site and the acidic group of the structural unit represented by the general formula (I) form a salt, such a salt-type graft 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 graft copolymer before salt formation is determined by the method described above. Next, the 13C-NMR spectrum of the salt-type graft copolymer was measured using a nuclear magnetic resonance apparatus. In the site, from the ratio of the integrated value of the carbon atom peak adjacent to the non-salted nitrogen atom and the carbon atom peak adjacent to the salted nitrogen atom, the salt-type graft copolymer, the general formula (I ) of one or more compounds selected from the group consisting of the general formula (1) or (3) with respect to the terminal nitrogen site of the structural unit represented by (the salt-formed terminal nitrogen site ratio). The terminal nitrogen portion of the structural unit represented by general formula (I), which is a salt formed by one or more compounds selected from the group consisting of general formula (1) or (3), has an amine value of 0. (Amine value of the graft copolymer before salt formation measured by the method described in JIS K 7237: 1995) × (Ratio of salt-formed end nitrogen sites calculated from 13C-NMR spectrum ( %)/100) by subtracting the amine value consumed by salt formation from the amine value of the graft copolymer before salt formation.
Amine value of salt-type graft copolymer = {amine value of graft copolymer before salt formation measured by the method described in JIS K 7237: 1995} - {measured by the method described in JIS K 7237: 1995 Amine value of graft copolymer before salt formation}×{ratio of salt-formed end nitrogen sites calculated from 13C-NMR spectrum (%)/100}

Further, in the present invention, the hydroxyl value of the dispersant is preferably 120 mgKOH/g or less, more preferably 60 mgKOH/g or less, and 30 mgKOH/g or less from the viewpoint of solvent resolubility. is even more preferred, preferably 0 mgKOH/g.
On the other hand, the hydroxyl value of the dispersant is preferably 5 mgKOH/g or more, more preferably 15 mgKOH/g or more, from the viewpoint of developability.
In the present invention, the hydroxyl value represents the mass (mg) of KOH required to neutralize the acetic acid bound to the acetylated product obtained from 1 g of the solid content, and is determined by the potentiometric titration method according to JIS K 0070:1992. It means the value obtained by

In the colorant dispersion according to the present invention, at least one of the above-mentioned graft copolymer and salt-type graft copolymer is used as the dispersant, and the content thereof is determined by the type of colorant used and the photosensitivity described later. It is appropriately selected according to the solid content concentration in the colored resin composition.
The content of the dispersant is preferably 3 to 45 parts by mass, more preferably 5 to 35 parts by mass, per 100 parts by mass of the total solid content in the colorant dispersion. When it is at least the above lower limit, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive colored resin composition is excellent. Further, when the content is equal to or less than the above upper limit value, the development residue is good.
Particularly when forming a coating film or a colored layer having a high colorant concentration, the content of the dispersant is 3 to 35 parts by mass, more preferably 3 to 35 parts by mass, with respect to 100 parts by mass of the total solid content in the colorant dispersion. It is preferable to mix in a ratio of 5 to 25 parts by mass.
In the present invention, the solid content refers to all substances other than the solvent described above, 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 develop a desired color when the colored layer of the color filter is formed, and various organic pigments, inorganic pigments, dispersible dyes, and 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 of their high color developability and high heat resistance. Examples of organic pigments include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colorists). .) numbered ones can be mentioned.

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. Derivative pigments of Pigment Yellow 150;
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, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265, 269, 272, 291;
C. I. Pigment Blue 15, 15:3, 15:4, 15:6, 60;
C. I. Pigment Green 7, 36, 58, 59, 62, 63;
C. I. Pigment Brown 23, 25;
C. I. Pigment Black 1, 7.

Specific examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, Prussian blue, oxide Chromium green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like can be mentioned.

For example, when forming a pattern of a light-shielding layer on a substrate of a color filter using the colorant dispersion according to the present invention as a photosensitive colored resin composition described later, a black pigment having high light-shielding properties is blended in the ink. . As a black pigment with high light shielding properties, for example, an inorganic pigment such as carbon black or triiron tetroxide, or an organic pigment such as cyanine black can be used.

Examples of the dispersible dyes include dyes that are made dispersible by adding various substituents to the dye or by 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 counterion. Examples thereof include a salt-forming compound of a basic dye and an acid, and a salt-forming compound of an acid dye and a base, which are soluble in solvents. It also includes a lake pigment obtained by insolubilizing the dye in a solvent using a known lake formation (chlorination) technique.
In the present invention, a coloring material containing at least one selected from dyes and salt-forming compounds of dyes is used in combination with the dispersant of the present invention to improve the dispersibility and dispersion stability of the coloring material. can be done.

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, quinoneimine dyes, methine dyes, and phthalocyanine dyes.
As a guideline, if the amount of dye dissolved in 10 g of the solvent (or mixed solvent) is 10 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

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 effect of suppressing the sublimation or precipitation of the colorant due to the use of the dispersant is high, and it is preferable in that a colored layer with high brightness can be formed. Moreover, it is preferable that the coloring material 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 diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, 255, 264, 272, 291, and diketopyrrolopyrrole pigments represented by the following general formula (i), among which C.I. I. Pigment Red 254, 272, 291, and at least one selected from diketopyrrolopyrrole pigments in which R ²¹ and R ²² in the following general formula (i) are each a 4-bromophenyl group are preferred.

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

Examples of quinophthalone pigments include C.I. I. Pigment Yellow 138 and the like.
Examples of copper phthalocyanine pigments 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, among which C.I. I. Pigment Blue 15:6 is preferred.
Examples of zinc phthalocyanine pigments include C.I. I. Pigment Green 58, 59 and the like.
Examples of quinophthalone dyes include C.I. I. Disperse Yellow 54, 64, 67, 134, 149, 160, C.I. I. Solvent Yellow 114, 157 and the like, among which C.I. I. Disperse Yellow 54 is preferred.

The average primary particle diameter of the coloring material used in the present invention is not particularly limited as long as the coloring layer of the color filter can develop a desired color, 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. Since the average primary particle size of the colorant is within the above range, a display device equipped with a color filter manufactured using the colorant dispersion according to the present invention can have high contrast and high quality. can.

Further, the average dispersed particle size of the colorant in the colorant dispersion varies depending on the type of 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 dispersed particle size of the colorant in the colorant dispersion is the dispersed particle size of the colorant particles dispersed in the dispersion medium containing at least the solvent, and is measured by a laser light scattering particle size distribution meter. is. As for the measurement of the particle size by the laser light scattering particle size distribution meter, the solvent used in the colorant dispersion liquid is appropriately diluted to a concentration that can be measured by the laser light scattering particle size distribution meter (for example, 1000 times etc.), and can be measured at 23° C. by a dynamic light scattering method using a laser light scattering particle size distribution analyzer (for example, Nanotrack particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distribution particle size here is the volume average particle size.

The coloring material used in the present invention can be produced by known methods such as a recrystallization method and a solvent salt milling method. Alternatively, a commercially available coloring material may be used after undergoing fine processing.

The content of the coloring material in the coloring material dispersion liquid according to the present invention is not particularly limited. From the viewpoint of dispersibility and dispersion stability, the content of the coloring material is 5 to 80 parts by weight, more preferably 8 to 70 parts by weight, with respect to 100 parts by weight of the total solid content in the coloring material dispersion. Blending is preferred.
Especially when forming a coating film or a colored layer with a high colorant concentration, the ratio of 30 to 80 parts by mass, more preferably 40 to 75 parts by mass, is based on 100 parts by mass of the total solid content in the colorant dispersion. It is preferable to blend with

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

In the coloring material dispersion liquid according to the present invention, the solvent as described above is usually contained in the range of 55 to 95% by mass, preferably 65 to 90% by weight, based on the total amount of the coloring material dispersion liquid containing the solvent. It is preferably in the range of 70 to 88% by mass, more preferably in the range of 70 to 88% by mass. If the amount of 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 is lowered, and it may be difficult to achieve the target chromaticity coordinates.

<Other ingredients>
As long as the effects of the present invention are not impaired, the colorant dispersion according to the present invention may further contain a dispersion assisting resin and other components, if necessary.
Examples of dispersion-assisting resins include alkali-soluble resins exemplified in the photosensitive colored resin composition described later. The steric hindrance of the alkali-soluble resin may make it difficult for the colorant particles to come into contact with each other, and may have the effect of stabilizing the dispersion and reducing the amount of the dispersant due to the effect of stabilizing the dispersion.
In addition, other components include, for example, a surfactant for improving wettability, a silane coupling agent for improving adhesion, an antifoaming agent, an anti-cratering agent, an antioxidant, an anti-aggregating agent, and an ultraviolet absorber. etc.

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

<Method for Producing Colorant Dispersion>
In the present invention, the method for producing a colorant dispersion is a method in which a colorant dispersion is obtained in which the colorant is dispersed in a solvent by the dispersant of the graft copolymer or the salt-type graft copolymer. There is no particular limitation, if any. Among them, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material, one of the following two production methods is preferable.

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

A second method for producing a colorant dispersion liquid according to the present invention in the case of using a dispersant that is a salt-type graft copolymer comprises a solvent, the graft copolymer, an organic acid compound, etc., and a colorant. and dispersing the coloring material while forming a salt of at least part of the terminal nitrogen portion of the structural unit represented by the general formula (I) and an organic acid compound or the like. It is.

In the case of using a salt-type graft copolymer, according to the first production method, after the salt-type graft copolymer is prepared, the salt-type graft copolymer is used as a dispersant to disperse the coloring material. Therefore, it is preferable from the point of being able to accurately confirm the reaction end point and the reaction rate of the graft copolymer and the organic acid compound before salt formation.
In addition, according to the second production method, the colorant is dispersed while preparing the dispersant for the salt-type graft copolymer. A liquid can be efficiently prepared, and dispersibility can be improved.

In the first manufacturing method and the second manufacturing method, the colorant can be dispersed using a conventionally known disperser.
Specific examples of the disperser include roll mills such as two-roll and three-roll roll mills, ball mills such as ball mills and vibrating ball mills, bead mills such as paint conditioners, continuous disk-type bead mills, and continuous annular-type bead mills. As preferable dispersing conditions for 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, pre-dispersion is performed with 2.0 mm zirconia beads having a relatively large bead diameter, and main dispersion is further performed with 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, after dispersion, it is preferable to filter through a filter of 0.5 to 2 μm.

<Application>
The colorant dispersion and dispersant according to the present invention can produce a photosensitive colored resin composition that simultaneously satisfies the suppression of development residue generation, shortening of development time, suppression of water staining, and excellent solvent resistance. Therefore, it can be preferably used for color filters.

II. Photosensitive colored resin composition The photosensitive colored resin composition according to the present invention is characterized by containing the colorant dispersion liquid according to the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. do.
By using the colorant dispersion according to the present invention, the photosensitive colored resin composition of the present invention simultaneously suppresses the occurrence of development residues, shortens the development time, suppresses the occurrence of water stains, and has excellent solvent resistance. It is possible to meet

The photosensitive colored resin composition of the present invention contains at least a coloring material, a dispersant, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, impairing the effects of the present invention. It may contain other components as long as they are not included. Hereinafter, each component contained in the photosensitive colored resin composition of the present invention will be described, but the dispersant, colorant, and solvent are the same as those described in the colorant dispersion liquid according to the present invention. , the description here is omitted.

<Alkali-soluble resin>
The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected and used from those that act as a binder resin and are soluble in an alkali developer used for pattern formation.
In the present invention, the alkali-soluble resin can be defined as having an acid value of 40 mgKOH/g or more.
A preferable alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group. resins, epoxy (meth)acrylate resins having a carboxyl group, and the like. Among these, particularly preferred are those having a carboxy group in the side chain and 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. Two or more of these acrylic copolymers, acrylic resins such as styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination.

Acrylic resins such as acrylic copolymers having a structural unit having a carboxy group and styrene-acrylic copolymers having a carboxy group are, 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.
Carboxy group-containing ethylenically unsaturated monomers include, for example, (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. be done. Also, addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride and cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylate and the like can also be used. Anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may also be used as precursors of the carboxy group. Among them, (meth)acrylic acid is particularly preferable from the viewpoint 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. The present inventors have found that the presence of a hydrocarbon ring, which is a bulky group, in the alkali-soluble resin suppresses the solvent resistance of the resulting colored layer, particularly swelling of the colored layer. Although the action is not clear, the presence of bulky hydrocarbon rings in the colored layer suppresses the movement of molecules in the colored layer, which increases the strength of the coating film and suppresses swelling due to solvents. presumed to be
Examples of such hydrocarbon rings include cyclic aliphatic hydrocarbon rings which may have substituents, aromatic rings which may have substituents, and combinations thereof, and hydrocarbon rings may have a substituent such as a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group, or the like. Among them, when an alicyclic ring is contained, the heat resistance and adhesion of the colored layer are improved, and the brightness of the obtained colored layer is improved.
Specific examples of hydrocarbon rings include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane. Aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene; cardo structures represented by the following chemical formula (ii); be done.

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

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

(In general formula (iii), ^RM is an optionally substituted hydrocarbon ring.)

When the alkali-soluble resin has a maleimide structure represented by the general formula (iii), it has a nitrogen atom in the hydrocarbon ring, so that it has very good compatibility with the dispersant of the present invention, and an effect of suppressing development residue. improves.
Specific examples of the optionally substituted hydrocarbon ring in R 1 ^M of the general formula (iii) are the same as the specific examples of the hydrocarbon ring described above.

When an aliphatic ring is included as the hydrocarbon ring, the heat resistance and adhesiveness of the colored layer are improved, and the brightness of the obtained colored layer is also preferably improved.
Moreover, when the cardo structure represented by the chemical formula (ii) is contained, the curability of the colored layer is improved, and the solvent resistance (NMP swelling suppression) is improved, which is particularly preferable.

In the alkali-soluble resin used in the present invention, apart from the structural unit having a carboxy group, using an acrylic copolymer having a structural unit having the above hydrocarbon ring makes it easy to adjust the amount of each structural unit, and the above It is preferable from the viewpoint that the amount of structural units having a hydrocarbon ring can be increased to easily improve the functions of the structural units.
The acrylic copolymer having a structural unit having a carboxyl group and the hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer". be able to.
Examples of ethylenically unsaturated monomers having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenoxy Ethyl (meth) acrylate, styrene, etc., and from the point that the cross-sectional shape of the colored layer after development is maintained even in heat treatment, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (Meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate and styrene are preferred.

The alkali-soluble resin used in the present invention also preferably has an ethylenic double bond in its side chain. When it has an ethylenic double bond, the alkali-soluble resin and the above-described dispersant of the present invention can form a crosslinked bond in the step of curing the resin composition during the production of a color filter, and The alkali-soluble resins can form cross-links, or the alkali-soluble resins and the photopolymerizable compound can form cross-links. Therefore, when an alkali-soluble resin having an ethylenic double bond in the side chain and the dispersant of the present invention are used in combination, the film strength of the cured film is further improved by a synergistic effect, so that the brightness of the colored layer and the ITO film Furthermore, the resistance to development is improved, and the heat shrinkage of the cured film is suppressed, resulting in excellent adhesion to the substrate.
A method for introducing an ethylenic double bond into an 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 carboxyl group of the alkali-soluble resin to introduce an ethylenic double bond into the side chain. Alternatively, a structural unit having a hydroxyl group is introduced into a copolymer, a compound having an isocyanate group and an ethylenic double bond is added to the molecule, and an ethylenic double bond is introduced into the side chain. etc.

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

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

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

The amount of the carboxyl group-containing ethylenically unsaturated monomer to be charged is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount of the monomers in order to obtain a good pattern. On the other hand, from the viewpoint of suppressing film roughness on the pattern surface after development, the amount of the carboxyl group-containing ethylenically unsaturated monomer charged is preferably 50% by mass or less, and 40% by mass or less with respect to the total amount of the monomer. It is more preferable to have
When the proportion of the carboxy group-containing ethylenically unsaturated monomer is at least the above lower limit, the coating film obtained has sufficient solubility in an alkaline developer, and the proportion of the carboxy group containing ethylenically unsaturated monomer is at the above upper limit. If it is below, the formed pattern tends not to come off from the substrate and the film roughening on the pattern surface tends not to occur during development with an alkaline developer.

In addition, in acrylic resins such as acrylic copolymers and styrene-acrylic copolymers having structural units having ethylenic double bonds, which are more preferably used as alkali-soluble resins, the epoxy group and the ethylenic double bond 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.

A preferred weight average molecular weight (Mw) of the carboxy group-containing copolymer is in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. If it is less than 1,000, the binder function after curing may be significantly deteriorated, and if it exceeds 50,000, 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 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)acrylate 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.
Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known ones and used. Epoxy (meth)acrylate resins having a carboxyl group may be used alone or in combination of two or more.

From the standpoint of developability (solubility) in an alkaline aqueous solution used as a developer, it is preferable to select and use an alkali-soluble resin having an acid value of 50 mgKOH/g or more. The alkali-soluble resin preferably has an acid value of 60 mgKOH/g or more and 300 mgKOH/g or less from the viewpoint of developability (solubility) in an alkaline aqueous solution used as a developer and adhesion to a substrate. It is preferably 70 mgKOH/g or more and 200 mgKOH/g or less.
The acid value of the alkali-soluble resin can be measured according to JIS K 0070:1992.

The ethylenically unsaturated bond equivalent when the side chain of the alkali-soluble resin has an ethylenically unsaturated group improves the film strength of the cured film, improves the development resistance, and provides the effect of excellent adhesion to the substrate. From the point of view, it is preferably in the range of 100 to 2000, more preferably in the range of 140 to 1500. When the ethylenically unsaturated bond equivalent is 100 or more, the development resistance and adhesion are excellent. Also, if it is 2000 or less, the ratio of other structural units such as structural units having a carboxy group and structural units having a hydrocarbon ring can be relatively increased, so that excellent developability and heat resistance can be obtained. there is
Here, the ethylenically unsaturated bond equivalent is the weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (2).

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

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

Alkali-soluble resin used in the photosensitive colored resin composition may be used alone, may be used in combination of two or more, the content is not particularly limited, photosensitive colored resin The content of the alkali-soluble resin is preferably 5% to 60% by mass, more preferably 10% to 40% by mass, based on the total solid content of the composition. When the content of the alkali-soluble resin is at least the above lower limit, sufficient alkali developability is obtained, and when the content of the alkali-soluble resin is at most the above upper limit, film roughness and pattern chipping during development are prevented. can be suppressed.

<Polyfunctional Monomer>
The polyfunctional monomer used in the photosensitive colored resin composition is not particularly limited as long as it can be polymerized by the photoinitiator described later, and usually a compound having two or more ethylenically unsaturated double bonds. Polyfunctional (meth)acrylates having two or more acryloyl groups or methacryloyl groups are particularly preferred.
Such a polyfunctional (meth)acrylate may be appropriately selected from among conventionally known ones and used. Specific examples include 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. Further, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present invention, the polyfunctional monomer has three polymerizable double bonds (trifunctional) or more. is preferred, and poly (meth) acrylates of trihydric or higher polyhydric alcohols and dicarboxylic acid-modified products thereof are preferred. 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)acrylate Succinic acid-modified products, dipentaerythritol hexa(meth)acrylate and the like are preferred.
The content of the polyfunctional monomer used in the photosensitive colored resin composition is not particularly limited, but the polyfunctional monomer is preferably 5 to 60% by mass with respect to the total solid content of the photosensitive colored resin composition, and further It is preferably within the range of 10 to 40% by mass. If the content of the polyfunctional monomer is less than the above lower limit, sufficient photocuring may not proceed, and the exposed portion may be eluted during development. may decrease.

<Photoinitiator>
The photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited, and can be used alone or in combination of two or more of conventionally known various initiators.
Examples of photoinitiators include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone, and the like. be able to. Specific examples of photoinitiators include aromatic ketones such as benzophenone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, and ethylbenzoin. benzoin, biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole and the like halomethyloxadiazole compounds, halomethyl-S-triazine compounds 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]-2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl )-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, p-dimethylaminobenzoate isoamyl acid, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenylsulfide, 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, combining an α-aminoacetophenone initiator such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one with a thioxanthone initiator such as diethylthioxanthone can improve sensitivity. It is preferable from the viewpoint of adjustment, suppressing water staining, and improving development resistance.
When using an α-aminoacetophenone-based initiator and a thioxanthone-based initiator, the total content thereof is preferably 5% by mass to 15% by mass based on the total solid content of the colored resin composition. If the amount of initiator is 15% by mass or less, sublimation during the production process is reduced, which is preferable. When the amount of the initiator is 5% by mass or more, resistance to development such as water staining is improved.

In the present invention, the photoinitiator preferably contains an oxime ester photoinitiator, among others, because it can improve sensitivity. In addition, by using an oxime ester-based photoinitiator, in-plane variations in line width can be easily suppressed when a fine line pattern is formed. Furthermore, the use of an oxime ester-based photoinitiator tends to improve the residual film rate and enhance the effect of suppressing the occurrence of water stains. The term "water stain" means that when a component that enhances alkali developability is used, after alkali development and rinsing with pure water, water stain marks are produced. Such water stains disappear after post-baking, so there is no problem with the product. occur. Therefore, if the inspection sensitivity of the inspection apparatus is lowered in the visual inspection, the yield of the final color filter product will be lowered, which is a problem.
As the oxime ester photoinitiator, from the viewpoint of reducing contamination of the photosensitive colored resin composition and contamination of the device due to decomposition products, among them, those having an aromatic ring are preferable, and those having a condensed ring containing an aromatic ring is more preferred, and it is even more preferred to have a condensed ring containing a benzene ring and a hetero ring.
Oxime ester photoinitiators include 1,2-octadione-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-A-2010-527339, JP-A-2010-527338, It can be appropriately selected from oxime ester photoinitiators described in JP-A-2013-041153 and the like. Commercially available products include Irgacure OXE-01, Adeka Arcules 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 (manufactured by Changzhou Yuan Yuan Electronic New Materials Co., Ltd.) may be used. In particular, it is preferable to use an oxime ester photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton from the viewpoint of brightness. Further, it is preferable to use an oxime ester photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.
The combined use of two or more oxime ester-based photoinitiators is preferable because the luminance and film retention rate are likely to be improved, and the effect of suppressing the occurrence of water stains is high. In particular, the combined use of two types of oxime ester photoinitiators having a diphenylsulfide skeleton, or the combined use of an oxime ester photoinitiator having a diphenylsulfide skeleton and an oxime ester photoinitiator having a fluorene skeleton provides high brightness and heat resistance. It is preferable because of its high efficiency. Further, it is preferable to use an oxime ester photoinitiator having a carbazole skeleton and an oxime ester photoinitiator having a fluorene skeleton or an oxime ester photoinitiator having diphenyl sulfide in combination in terms of excellent sensitivity and brightness.

Moreover, it is preferable to use the oxime ester photoinitiator in combination with a photoinitiator having a tertiary amine structure from the viewpoint of suppressing water staining and improving sensitivity. A photoinitiator having a tertiary amine structure has a tertiary amine structure, which is an oxygen quencher, in its molecule, so that radicals generated from the initiator are less likely to be deactivated by oxygen, and sensitivity can be improved. be. Commercially available photoinitiators having a tertiary amine structure include, for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (eg Irgacure 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (eg Irgacure 369, manufactured by BASF), 4,4′-bis(diethylamino)benzophenone (eg Hycure ABP, Kawaguchi Pharmaceutical Co., Ltd.) and the like.
In addition, it is preferable to combine an oxime ester photoinitiator with a thioxanthone initiator from the viewpoint of adjusting sensitivity, suppressing water staining, and improving development resistance. Combining an initiator is preferable in that the brightness and film remaining rate are improved, the sensitivity is easily adjusted, the effect of suppressing the occurrence of water stains is high, and the development resistance is improved.

The content of the photoinitiator used in the photosensitive colored resin composition of the present invention is usually about 0.01 parts by mass to 100 parts by mass, preferably 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the polyfunctional monomer. part by mass. When the content is at least the above lower limit, photocuring proceeds sufficiently to suppress the elution of the exposed portion during development. You can suppress the decline.
In addition, as the photoinitiator used in the photosensitive colored resin composition of the present invention, the total content of two or more oxime ester photoinitiators is 0.00% relative to the total solid content of the photosensitive colored resin composition. The range of 1% by mass to 12.0% by mass, more preferably 1.0% by mass to 8.0% by mass, is preferable from the viewpoint of sufficiently exhibiting the effect of combined use of these photoinitiators.

The total content of the binder component used in the photosensitive colored resin composition of the present invention is preferably 35% by mass to 97% by mass with respect to the total solid content of the photosensitive colored resin composition, and 40% by mass to It is more preferable to mix at a rate of 96% by mass. If it is at least the above lower limit, a colored layer having excellent hardness and adhesion to the substrate can be obtained. Moreover, if it is below the said upper limit, it will be excellent in developability, and generation|occurrence|production of the fine wrinkle by heat shrinkage will also be suppressed. Especially when forming a colored layer with a high colorant concentration, the total content of these binder components is preferably 20 to 90% by mass, based on the total solid content of the photosensitive colored resin composition, and 25 to It is more preferable to mix at a rate of 80% by mass.

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

Hindered phenol-based antioxidants include, for example, 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-hydroxybenzylphosphone and diethyl acid (trade name: Irgamod 195, manufactured by BASF). Among them, 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. .

When the photosensitive colored resin composition of the present invention contains the oxime ester photoinitiator and an antioxidant in combination, the synergistic effect improves the brightness, the film retention rate is improved, and the fine line pattern is improved. It is preferable in terms of improving the linearity when forming and improving the ability to form a fine line pattern as designed for the mask line width.

The amount of the antioxidant compounded is preferably 0.1 part by mass to 10.0 parts by mass of the antioxidant with respect to 100 parts by mass of the total solid content in the colored resin composition, and 0.5 parts by mass. parts to 5.0 parts by mass is more preferable. If it is at least the above lower limit value, it is excellent in heat resistance and light resistance. On the other hand, if it is the above upper limit or less, the colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

When an antioxidant is used in combination with the oxime ester photoinitiator, the antioxidant content is 1 part by mass with respect to 100 parts by mass of the total amount of the oxime ester photoinitiator. It is preferably up to 250 parts by mass, more preferably 3 parts by mass to 80 parts by mass, even more preferably 5 parts by mass to 45 parts by mass. Within the above range, the effect of the above combination is excellent.

<Optional Addition Ingredients>
If necessary, the photosensitive colored resin composition of the present invention may contain various additives in addition to the antioxidant.
Examples of additives include polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.
Specific examples of surfactants and plasticizers include those described in JP-A-2013-029832.

Examples of silane coupling agents include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403 , KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicone Co., Ltd.) and the like. Among them, KBM-502, KBM-503, KBE-502, KBE-503 and KBM-5103 having a methacrylic group or an acrylic group are preferable from the viewpoint of adhesion to SiN substrates.

The content of the silane coupling agent is preferably 0.05 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the total solid content in the photosensitive colored resin composition. , 0.1 parts by mass or more and 5.0 parts by mass or less. If it is more than the said lower limit and below the said upper limit, it is excellent in board|substrate adhesiveness.

<Ratio of each component in the photosensitive colored resin composition>
The total content of the colorant 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. If it is at least the above lower limit, the colored layer will have sufficient color density when the photosensitive colored resin composition is applied to a predetermined film thickness (usually 1.0 to 5.0 μm). Moreover, if it is below the said upper limit, while being excellent in storage stability, the coloring layer which has sufficient hardness and adhesiveness with a board|substrate can be obtained. Especially when forming a colored layer with a high colorant concentration, the content of the colorant is 15 to 75% by mass, more preferably 25 to 70% by mass, based on the total solid content of the photosensitive colored resin composition. It is preferable to mix in a ratio of
Further, the content of the dispersant is not particularly limited as long as it can uniformly disperse the coloring material. It can be used at a rate of 40% by mass. Furthermore, it is preferably blended in a proportion of 2 to 30% by mass, particularly preferably 3 to 25% by mass, based on the total solid content of the photosensitive colored resin composition. When it is at least the above lower limit, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive colored resin composition is excellent. Moreover, if it is below the said upper limit, developability will become favorable. Especially when forming a colored layer with a high colorant concentration, the content of the dispersant is 2 to 25% by mass, more preferably 3 to 20% by mass, based on the total solid content of the photosensitive colored resin composition. It is preferable to mix in a ratio of In addition, in the case of a salt-type graft copolymer, the mass of the dispersant is the total mass of the graft copolymer and the organic acid compound before salt formation.
In addition, the content of the solvent may be appropriately set within a range that allows the colored layer to be formed with high accuracy. It is usually preferably in the range of 55 to 95% by mass, more preferably in the range of 65 to 88% by mass, based on the total amount of the photosensitive colored resin composition containing the solvent. When the content of the solvent is within the above range, excellent applicability can be obtained.

<Method for producing a photosensitive colored resin composition>
The method for producing the photosensitive colored resin composition of the present invention is not particularly limited, for example, the colorant dispersion according to the present invention, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and if necessary It can be obtained by adding other components and mixing using a known mixing means.

<Application>
The photosensitive colored resin composition according to the present invention can simultaneously satisfy the suppression of development residue generation, shortening of development time, suppression of water stain generation, and excellent solvent resistance. It can be suitably used for

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

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

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

The colored layer can be formed, for example, by the following method.
First, the photosensitive colored resin composition of the present invention described above is applied onto a substrate described later 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, or a die coating method. to form a wet coating. Among them, the spin coating method and the die coating method can be preferably used.
Next, after drying the wet coating film using a hot plate, oven, etc., it is exposed through a mask of a predetermined pattern to photopolymerize the alkali-soluble resin and the polyfunctional monomer, etc. to cure. It is used as a coating film. Light sources used for exposure include, for example, ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, electron beams, and the like. The amount of exposure is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to accelerate the polymerization reaction after exposure, heat treatment may be performed. The heating conditions are appropriately selected according to the mixing ratio of each component in the photosensitive colored resin composition to be used, the thickness of the coating film, and the like.

Next, a coating film is formed in a desired pattern by developing with a developer to dissolve and remove 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. Moreover, a general method can be adopted as the developing method.
After the development processing, the developing solution is usually washed and the cured coating film of the photosensitive colored resin composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after development processing. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.

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

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

<Substrate>
As the substrate, a transparent substrate, a silicon substrate, and a transparent substrate or a silicon substrate on which an aluminum, silver, silver/copper/palladium alloy thin film or the like is formed are used. Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on these substrates.
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and transparent substrates used in general color filters can be used. Specifically, transparent rigid materials without flexibility such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials such as transparent resin films, optical resin plates, and flexible glass. material.
Although the thickness of the transparent substrate is not particularly limited, a thickness of about 100 μm to 1 mm, for example, can be used depending on the application of the color filter of the present invention.
The color filter of the present invention may be formed with, for example, an overcoat layer, a transparent electrode layer, an alignment film, columnar spacers, etc., in addition to the above substrate, light shielding portion and colored 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, such as liquid crystal display devices and organic light-emitting display devices.

[Liquid crystal display device]
Examples of the liquid crystal display device of the present invention include 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 diagram showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, a 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.
The liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and may have a known configuration as a liquid crystal display device generally using color filters.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include the TN method, IPS method, OCB method, and MVA method. Any of these methods can be suitably used in the present invention.
Also, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.
Further, as the liquid crystal forming the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method. After the liquid crystal layer is formed by the above method, the liquid crystal cell is gradually cooled to normal temperature, thereby aligning the sealed liquid crystal.

[Organic Light Emitting Display Device]
Examples of the organic light-emitting display device of the present invention include an organic light-emitting display device having the above-described color filter according to the present invention and an organic light-emitting material.
The organic light-emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram 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 has a color filter 10 and an organic light-emitting body 80. As shown in FIG. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80 .

As a method of stacking the organic light emitter 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. method, and a method of bonding the organic light emitter 80 formed on another substrate onto the inorganic oxide film 60, and the like. As for 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 structures in the organic light emitter 80, known structures can be appropriately used. The organic light-emitting display device 100 manufactured in this way can be applied to, for example, a passive drive type organic EL display and an active drive type organic EL display.
Note that the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may have a known configuration as an organic light-emitting display device generally using color filters.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the invention.
The amine value of the block copolymer before salt formation and the amine value of the salt-type block copolymer were determined according to the measurement method described in the specification of the present invention.
The weight average molecular weight (Mw) of the block copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method described in the specification of the present invention.

(Synthesis Example 1: Production of macromonomer A)
A reactor equipped with a cooling pipe, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 70.0 parts by mass of propylene glycol methyl ether acetate (PGMEA), and the temperature was raised to 90 while stirring under a nitrogen stream. It was warmed to °C. A monomer having a PEG chain that induces a structural unit represented by general formula (III) (manufactured by Evonik, trade name: VISIOMER MPEG 1005 MA W, R ⁴ in general formula (III) is CH ₃ , A ³ is COO , R ⁵ is an ethylene group, R ⁶ is CH ₃ , m = 22) 1.0 parts by mass, methyl methacrylate (MMA) 99.0 parts by mass, mercaptoethanol 4.0 parts by mass, PGMEA 30 parts by mass, α, α A mixed solution of 1.0 part by mass of '-azobisisobutyronitrile (AIBN) was added dropwise over 1.5 hours, and the reaction was further continued for 3 hours. Next, the nitrogen gas flow was stopped, the reaction solution was cooled to 80° C., and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko K.K.), 0.125 g of dioctyltin dilaurate, and 0.25 g of p-methoxyphenol were added. 125 parts by mass and 30 parts by mass of PGMEA were added and stirred for 3 hours to obtain a 50% solution of macromonomer A. The obtained macromonomer A was confirmed by GPC (gel permeation chromatography) under the conditions of N-methylpyrrolidone, 0.01 mol/L lithium bromide addition/polystyrene standard, and found to have a weight average molecular weight (Mw). 4500, and the molecular weight distribution (Mw/Mn) was 1.6.

(Synthesis Examples 2 to 10: Production of macromonomers B to K)
In the production of macromonomer A of Synthesis Example 1, instead of using 1.0 parts by mass of a monomer that induces a structural unit represented by general formula (III) and 99.0 parts by mass of MMA as monomers, as shown in Table 1 Macromonomers B to K were produced in the same manner as in Synthesis Example 1, except that at least one of the types and mass ratios of the monomers was changed. Table 1 shows the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained macromonomer.

(Comparative Synthesis Examples 1 to 3: Production of macromonomers L to N)
In the production of macromonomer A of Synthesis Example 1, instead of using 1.0 parts by mass of a monomer that induces a structural unit represented by general formula (III) and 99.0 parts by mass of MMA as a monomer, as shown in Table 1 Macromonomers L to N were produced in the same manner as in Synthesis Example 1, except that at least one of the types and mass ratios of the monomers was changed. Table 1 shows the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the obtained macromonomer.

Abbreviations in the table are as follows.
Monomer having a PEG chain (m = 30); manufactured by NOF Corporation, trade name: Blenmer PSE-1300, R ⁴ in general formula (III) is CH ₃ , A ³ is COO, R ⁵ is an ethylene group, R ⁶ is _C18H37 , m ₌ 30
Monomer having a PEG chain (m = 45); manufactured by Evonik, trade name: VISIOMER MPEG 2005 MA W, R ⁴ in general formula (III) is CH ₃ , A ³ is COO, R ⁵ is an ethylene group, R ⁶ is _CH3 , m=45
Monomer with PEG chain (m = 90); manufactured by NOF, trade name: Blenmer PME-4000, number of repetitions of PEG chain m = 90
Monomer with PEG chain (m=17); manufactured by Evonik, trade name: VISIOMER MPEG 750 MA W, repeating number of PEG chain m=17
Monomer with PEG chain (m = 9); manufactured by NOF, trade name: Blenmer PME-400, number of repetitions of PEG chain m = 9
Monomer having a PEG chain (m = 3); manufactured by Tokyo Kasei Kogyo, trade name: triethylene glycol monoethyl ether methacrylate, repeating number of PEG chain m = 3
BMA; n-butyl methacrylate 2-EHMA; 2-ethylhexyl methacrylate BzMA; benzyl methacrylate

(Production Example 1: Production of graft copolymer A)
A reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer and a digital thermometer was charged with 63.1 parts by mass of PGMEA and heated to 85° C. while stirring under a nitrogen stream. 141 parts by mass of the macromonomer A solution of Synthesis Example 1 (effective solid content: 70.5 parts by mass), 29.5 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMMA), 1.24 parts by mass of n-dodecyl mercaptan, A mixed solution of 49.4 parts by mass of PGMEA and 1.0 parts by mass of AIBN was added dropwise over 1.5 hours, and after heating and stirring for 3 hours, a mixed solution of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA was added over 10 minutes. A 35.0% by mass solution of graft copolymer A was obtained by adding dropwise and aging at the same temperature for 1 hour. The obtained graft copolymer A had a weight average molecular weight (Mw) of 10,000 as a result of GPC measurement. The amine value was 105 mgKOH/g.

(Production Examples 2 to 9: Production of graft copolymers B to K)
In Production Example 1, instead of using 70.5 parts by mass of macromonomer A effective solid content and 29.5 parts by mass of DMMA, the type of macromonomer and the mass ratio of macromonomer to DMMA were changed as shown in Table 2. Graft copolymers B to K were produced in the same manner as in Production Example 1, except that Table 2 shows the weight average molecular weight (Mw) and the amine value before modification of the obtained graft copolymers B to K.

(Comparative Production Examples 1 to 4: Production of graft copolymers L to O)
In Production Example 1, instead of using 70.5 parts by mass of macromonomer A effective solid content and 29.5 parts by mass of DMMA, the type of macromonomer and the mass ratio of macromonomer to DMMA were changed as shown in Table 2. Graft copolymers L to O were produced in the same manner as in Production Example 1, except that Table 2 shows the weight average molecular weight (Mw) and the amine value before modification of the obtained graft copolymers L to O.
In addition, in the production of the graft copolymer O of Comparative Production Example 4, instead of the macromonomer A, a monomer having a PEG chain (m=90) was used. The monomer having the PEG chain (m=90) is manufactured by NOF Corporation, trade name: Blenmer PME-4000, and the number of repetitions of the PEG chain is m=90.

(Production Example 3′: Production of salt-type graft copolymer C)
To 4.22 parts by mass of the graft copolymer C solution, 0.15 parts by mass of phenylphosphonic acid (manufactured by Nissan Chemical Industries, Ltd., "PPA"), which is a salt-forming component (DMMA unit of graft copolymer C 0.5 equivalent) was added and stirred at room temperature for 1 hour to prepare a salt-type graft copolymer C solution. The resulting salt-type graft copolymer C solution was adjusted with PGMEA so as to have a solid content of 35%.

(Production Examples 6', 7', 8', 9', 10' and 11', Comparative Production Examples 2' and 3': Salt type graft copolymers F, G, H, I, J, K, M, and production of N)
In Production Example 3′, the graft copolymer F, G, H, I, J, K, M, or N solution was used instead of the graft copolymer C solution, and the type and amount of the salt-forming agent (graft copolymer Salt-type graft copolymers F, G, H, I, J, K, M, and N solutions were prepared respectively. Table 2 shows the post-salting amine values of the salt-type graft copolymers.

(Comparative Production Example 5: Production of Block Copolymer P)
250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round-bottomed 4-necked separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the mixture was sufficiently purged with nitrogen. rice field. After cooling the reaction flask to −60° C., 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. . A monomer having a PEG chain (manufactured by Evonik, trade name: VISIOMER MPEG 1005 MA W, R ⁴ in general formula (III) is CH ₃ , A ³ is COO, R ⁵ is an ethylene group, R ⁶ is CH ₃ , m = 22) 23.0 parts by mass, MMA 30.0 parts by mass, and BMA 22.0 parts by mass, using an addition funnel for 60 minutes dripped. After 30 minutes, 25.0 parts by mass of DMMA, which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. The obtained block copolymer THF solution was reprecipitated in hexane, filtered, purified by vacuum drying, and diluted with PGMEA so that the solid content was 35% by mass to obtain a block copolymer P solution. When the block copolymer P thus obtained was confirmed by GPC, the weight average molecular weight Mw was 15,800. Moreover, the amine value was 89 mgKOH/g.
Table 1 shows the monomer composition, weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the block copolymer P. Table 2 shows the amine value of the block copolymer P.

(Comparative Production Example 6: Production of salt-type block copolymer Q)
250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round-bottomed 4-necked separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the mixture was sufficiently purged with nitrogen. rice field. After cooling the reaction flask to −60° C., 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. A monomer having a PEG chain (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: triethylene glycol monoethyl ether methacrylate, general formula (IIIa) in R ⁴ is CH ₃ , A ³ is COO, R ⁵ is an ethylene group, R ⁶ is CH ₃ , m=3) 8.3 parts by mass, MMA 18.8 parts by mass, BMA 20.1 parts by mass, 2-EHMA 14.1 11.8 parts by mass of BzMA was added dropwise over 60 minutes using an addition funnel. After 30 minutes, 26.9 parts by mass of DMMA, which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. The resulting block copolymer THF solution was reprecipitated in hexane, filtered and vacuum dried for purification. When the block copolymer thus obtained was confirmed by GPC, the weight average molecular weight Mw was 4,900. Moreover, the amine value was 81 mgKOH/g. Next, 8.0 parts by mass of the resulting block copolymer was diluted with 10.0 parts by mass of PGMEA, and 1.2 parts by mass of benzyl chloride (0.83 equivalents relative to the DMMA unit of the block copolymer) was added. A salt-type block copolymer Q solution was prepared by stirring at °C for 4 hours. The resulting salt-type block copolymer Q solution was adjusted with PGMEA so as to have a solid content of 35%.
Table 1 shows the monomer composition, weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of block copolymer Q. Table 2 shows the amine value of block copolymer Q before salt formation and the amine value of salt-type block copolymer Q after salt formation.

(Preparation Example 1: Preparation of alkali-soluble resin A)
A polymerization tank was charged with 300 parts by mass of PGMEA, heated to 100° C. under a nitrogen atmosphere, and then 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA) and perbutyl. 6 parts by mass of O (manufactured by NOF Corporation) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. After that, the reaction was continued while maintaining the temperature at 100° C., and 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization two hours after the completion of the dropping of the mixture for forming the main chain.
Next, while blowing in air, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, and the temperature was raised to 110°C. Then, 0.8 parts by mass of triethylamine was added and the mixture was heated to 110°C for 15 hours. Addition reaction was carried out to obtain an alkali-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH/g, solid content 40% by mass).
The weight average molecular weight was measured by Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent. Moreover, the method for measuring the acid value was based on JIS K 0070.

(Example 1)
(1) Production of Colorant Dispersion G-1
9.29 parts by mass of the graft copolymer A of Synthesis Example 1 as a dispersant, and C.I. I. Pigment Green 58 (PG58) 9.10 parts by mass, C.I. I. 3.90 parts by weight of Pigment Yellow 138 (PY138), 14.63 parts by weight of the alkali-soluble resin A solution obtained in Preparation Example 1, 63.09 parts by weight of PGMEA, 100 parts by weight of zirconia beads with a particle size of 2.0 mm is placed in a mayonnaise bottle, shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for preliminary crushing, then zirconia beads with a particle size of 2.0 mm are taken out, and 200 parts by mass of zirconia beads with a particle size of 0.1 mm was added, and dispersion was similarly carried out for 4 hours using a paint shaker as main pulverization to obtain a coloring material dispersion liquid G-1.

(2) Production of photosensitive colored resin composition G-1 9.77 parts by mass of the colorant dispersion G-1 obtained in (1) above, and 0 of the alkali-soluble resin A solution obtained in Preparation Example 1 .28 parts by mass, 0.99 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane- 0.05 parts by mass of 1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Co., Ltd.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 ( Photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) 0.05 parts by mass, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)] (photoinitiator : Trade name Irgacure OXE01, manufactured by BASF Japan Co., Ltd.) 0.02 parts by mass, fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation) 0.07 parts by mass, PGMEA 8 73 parts by mass was added to obtain a photosensitive colored resin composition G-1.

(Examples 2 to 11)
(1) Production of Colorant Dispersions G-2 to G-11 In (1) of Example 1, (salt-type) graft copolymer B was used instead of graft copolymer A as shown in Table 3. , C, D, E, F, G, H, I, J, and K were used, respectively.
(2) Production of photosensitive colored resin compositions G-2 to G-11 In (2) of Example 1, instead of the colorant dispersion G-1, the colorant dispersions G-2 to G- Photosensitive colored resin compositions G-2 to G-11 were obtained in the same manner as in Example 1 (2) except that No. 11 was used.

(Comparative Examples 1 to 6)
(1) Production of Comparative Colorant Dispersions G-1 to G-6 In (1) of Example 1, instead of graft copolymer A, a (salt-type) graft copolymer was used as shown in Table 3. Comparative colorant dispersions G-1 to G-6 were obtained in the same manner as in Example 1 except that L, M, N, and O and block copolymers P and Q were used, respectively.
(2) Production of comparative photosensitive colored resin compositions G-1 to G-6 In (2) of Example 1, instead of the colorant dispersion G-1, the comparative colorant dispersion G-1 Comparative photosensitive colored resin compositions G-1 to G-6 were obtained in the same manner as in Example 1 (2) except that ~G-6 was used.

(Example 12)
(1) Production of Colorant Dispersion G-12
In (1) of Example 1, C.I. I. Pigment Green 58 (PG58) 9.10 parts by mass, C.I. I. Pigment Yellow 138 (PY138) instead of using 3.90 parts by mass of C.I. I. Pigment Green 59 (PG59), 9.10 parts by mass, C.I. I. A colorant dispersion G-12 was produced in the same manner as in Example 1, except that 3.90 parts by mass of Pigment Yellow 150 (PY150) was used.
(2) Production of photosensitive colored resin composition G-12 In (2) of Example 1, instead of the colorant dispersion G-1, the colorant dispersion G-12 was used, except for the examples A photosensitive colored resin composition G-12 was obtained in the same manner as in 1 (2).

(Examples 13-22)
(1) Production of Colorant Dispersions G-13 to G-22 In (1) of Example 12, (salt-type) graft copolymer B was used instead of graft copolymer A as shown in Table 4. , C, D, E, F, G, H, I, J, and K were used, respectively, in the same manner as in Example 1 to prepare colorant dispersions G-13 to G-22.
(2) Production of photosensitive colored resin compositions G-13 to G-22 In (2) of Example 1, instead of the colorant dispersion G-1, the colorant dispersions G-13 to G- Photosensitive colored resin compositions G-13 to G-22 were obtained in the same manner as in Example 1 (2) except that No. 22 was used.

(Comparative Examples 7-12)
(1) Production of Comparative Colorant Dispersions G-7 to G-12 In (1) of Example 12, instead of graft copolymer A, a (salt-type) graft copolymer was used as shown in Table 4. Comparative colorant dispersions G-7 to G-12 were obtained in the same manner as in Example 1 except that L, M, N, and O and block copolymers P and Q were used, respectively.
(2) Production of comparative photosensitive colored resin compositions G-7 to G-12 In (2) of Example 1, instead of the colorant dispersion G-1, the comparative colorant dispersion G-7 Comparative photosensitive colored resin compositions G-7 to G-12 were obtained in the same manner as in Example 1 (2) except that ~G-12 was used.

(Example 23)
(1) Production of Colorant Dispersion R-1
In (1) of Example 1, C.I. I. Pigment Green 58 (PG58) 9.10 parts by mass, C.I. I. Pigment Yellow 138 (PY138) instead of using 3.90 parts by mass of C.I. I. Pigment Red 177 (PR177), 3.90 parts by mass, C.I. I. A colorant dispersion R-1 was produced in the same manner as in Example 1, except that 9.10 parts by mass of Pigment Red 291 (PR291) was used.
(2) Production of photosensitive colored resin composition R-1 In (2) of Example 1, instead of the colorant dispersion G-1, except that the colorant dispersion R-1 was used A photosensitive colored resin composition R-1 was obtained in the same manner as in 1 (2).

(Examples 24-33)
(1) Production of Colorant Dispersions R-2 to R-11 In (1) of Example 23, instead of graft copolymer A, (salt-type) graft copolymer B was used as shown in Table 5. , C, D, E, F, G, H, I, J, and K were used, respectively.
(2) Production of photosensitive colored resin compositions R-2 to R-11 In (2) of Example 1, instead of the colorant dispersion G-1, the colorant dispersions R-2 to R- Photosensitive colored resin compositions R-2 to R-11 were obtained in the same manner as in Example 1 (2) except that No. 11 was used.

(Comparative Examples 13-18)
(1) Production of Comparative Colorant Dispersions R-1 to R-6 In (1) of Example 23, instead of graft copolymer A, as shown in Table 5, a (salt type) graft copolymer Comparative colorant dispersions R-1 to R-6 were obtained in the same manner as in Example 23, except that L, M, N, and O and block copolymers P and Q were used, respectively.
(2) Production of comparative photosensitive colored resin compositions R-1 to R-6 In (2) of Example 1, instead of the colorant dispersion G-1, the comparative colorant dispersion R-1 Comparative photosensitive colored resin compositions R-1 to R-6 were obtained in the same manner as in Example 1 (2) except that ~R-6 was used.

(Example 34)
(1) Production of Colorant Dispersion B-1
In (1) of Example 1, C.I. I. Pigment Green 58 (PG58) 9.10 parts by mass, C.I. I. Pigment Yellow 138 (PY138) instead of using 3.90 parts by mass of C.I. I. Pigment Blue 15:6 (PB15:6), 11.70 parts by mass, C.I. I. A colorant dispersion B-1 was produced in the same manner as in Example 1, except that 1.30 parts by mass of Pigment Violet 23 (PV23) was used.
(2) Production of photosensitive colored resin composition B-1 6.78 parts by mass of the colorant dispersion B-1 obtained in (1) above, 1 part of the alkali-soluble resin A solution obtained in Preparation Example 1 .28 parts by mass, 1.20 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane- 0.08 parts by mass of 1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Co., Ltd.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 ( Photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) 0.08 parts by mass, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)] (photoinitiator : 0.04 parts by mass of Irgacure OXE01 (trade name, manufactured by BASF Japan Co., Ltd.), 0.07 parts by mass of fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 10 parts by mass of PGMEA 48 parts by mass was added to obtain a photosensitive colored resin composition B-1.

(Examples 35-44)
(1) Production of Colorant Dispersions B-2 to B-11 In (1) of Example 34, (salt-type) graft copolymer B was used instead of graft copolymer A as shown in Table 6. , C, D, E, F, G, H, I, J, and K were used, respectively.
(2) Production of photosensitive colored resin compositions B-2 to B-11 In (2) of Example 34, instead of the colorant dispersion B-1, the colorant dispersions B-2 to B- Photosensitive colored resin compositions B-2 to B-11 were obtained in the same manner as in Example 34 (2) except that No. 11 was used.

(Comparative Examples 19-24)
(1) Production of Comparative Colorant Dispersions B-1 to B-6 In (1) of Example 34, instead of the graft copolymer A, as shown in Table 6, a (salt type) graft copolymer Comparative colorant dispersions B-1 to B-6 were obtained in the same manner as in Example 34, except that L, M, N, and O and block copolymers P and Q were used, respectively.
(2) Production of comparative photosensitive colored resin compositions B-1 to B-6 In (2) of Example 34, instead of the colorant dispersion B-1, respectively, the comparative colorant dispersion B-1 Comparative photosensitive colored resin compositions B-1 to B-6 were obtained in the same manner as in Example 34 (2) except that B-6 was used.

[Evaluation method]
<Water stain evaluation>
The photosensitive colored resin compositions obtained in Examples and Comparative Examples were each coated on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35", 100 mm x 100 mm with a thickness of 0.7 mm) using a spin coater. After coating with a film thickness that forms a colored layer with a thickness of 2.0 μm after post-baking, it is dried at 60 ° C. for 3 minutes using a hot plate, and 30 mJ / cm using an ultra-high pressure mercury lamp without a photomask. A colored layer was formed on the glass substrate by irradiating the entire surface with the ultraviolet rays of ^{No. 2} . Then, the substrate was subjected to shower development for 60 seconds using 0.05 wt% potassium (KOH) as a developer, and then washed with pure water for development. Water staining was evaluated by measuring the contact angle of pure water as in .
The contact angle of pure water is measured by dropping a droplet of 1.0 μL of pure water on the surface of the colored layer immediately after removing the water by centrifugation, and measuring the static contact angle 10 seconds after the droplet is deposited according to the θ/2 method. Measured. The contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd. was used as the measurement device.
(Evaluation criteria)
A: contact angle 70 degrees or more B: contact angle 50 degrees or more and less than 70 degrees C: contact angle 30 degrees or more and less than 50 degrees D: contact angle less than 30 degrees If the water stain evaluation criteria is A or B, it can be used practically. However, if the evaluation result is A, the effect is more excellent.

<Development residue evaluation>
The photosensitive colored resin compositions obtained in Examples and Comparative Examples are each coated on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") and post-baked using a spin coater to a thickness of 2.0 μm. and then dried at 80° C. for 3 minutes using a hot plate to form a colored layer on the glass substrate. The glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and then washed with pure water for development treatment. After visually observing the formation portion of the colored layer after development, it is thoroughly wiped with a lens cleaner (manufactured by Toray Industries, Inc., trade name Toraysee MK Clean Cloth) impregnated with ethanol, and the degree of coloring of the lens cleaner is visually observed. Observed.
(Development residue evaluation criteria)
A: No development residue was visually observed, and the lens cleaner was not colored at all. B: No development residue was visually observed, and the lens cleaner was slightly colored. C: A slight development residue was visually confirmed. D: Development residue was visually observed and coloration of the lens cleaner was confirmed. If the evaluation criteria for development residue is A or B, generation of development residue is sufficiently suppressed. It is evaluated that there is no problem in practical use.

<Development time evaluation>
The photosensitive colored resin compositions obtained in Examples and Comparative Examples are each coated on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") and post-baked using a spin coater to a thickness of 2.0 μm. After coating with a film thickness that forms a colored layer, the colored layer was formed on the glass substrate by drying at 80° C. for 3 minutes using a hot plate. This colored layer was irradiated with ultraviolet rays of 60 mJ/cm ² using an ultra-high pressure mercury lamp through a photomask. After that, the glass substrate on which the colored layer is formed is subjected to shower development using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, so that the colored layer is completely dissolved, and the portion where the colored layer is formed is exposed. The time until the glass surface appeared was measured as development time.

<NMP resistance evaluation>
The photosensitive colored resin compositions obtained in Examples and Comparative Examples are each coated on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") and post-baked using a spin coater to a thickness of 2.0 μm. After coating with a film thickness that forms a colored layer, the colored layer was formed on the glass substrate by drying at 80° C. for 3 minutes using a hot plate. This colored layer was irradiated with ultraviolet rays of 60 mJ/cm 2 using an ultra-high pressure mercury lamp.
Next, the colored substrate was post-baked in a clean oven at 230° C. for 30 minutes to prepare a colored substrate. After measuring the film thickness of the obtained colored substrate, it was immersed in NMP for 30 minutes, air-dried, and the film thickness was measured again. For the film thickness measurement, a stylus type step film thickness meter "P-15 Tencor" (manufactured by Instruments) was used.
(NMP resistance evaluation criteria)
A: The rate of change in film thickness before and after immersion in NMP is less than 2% B: The rate of change in film thickness before and after immersion in NMP is 2% or more and less than 5% C: The rate of change in film thickness before and after immersion in NMP is 5% or more and 8% Less than D: Change rate of film thickness before and after NMP immersion is 8% or more

<Evaluation of Dispersibility Stability of Colorant Dispersion>
The viscosity of each of the colorant dispersions obtained in Examples and Comparative Examples was measured immediately after preparation and after storage at 25° C. for 30 days, and the viscosity change rate was calculated from the viscosity before and after storage to evaluate the viscosity stability. bottom. Viscosity was measured at 25.0±0.5° C. using a vibrating viscometer.
(Dispersion stability evaluation criteria)
A: Viscosity change rate before and after storage is less than 20% B: Viscosity change rate before and after storage is 20% or more and less than 40% C: Viscosity change rate before and after storage is 40% or more and less than 60% D: Before and after storage Viscosity change rate of 60% or more However, this is a value when the colorant is 13% by mass with respect to the total mass of the colorant dispersion including the solvent.
If the evaluation result is B, the colorant dispersion is good, and if the evaluation result is A, the colorant dispersion is excellent in dispersion stability.

<Optical Performance Evaluation, Contrast Evaluation>
The photosensitive colored resin compositions for color filters obtained in Examples and Comparative Examples were each spun onto a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") having a thickness of 0.7 mm and a size of 100 mm x 100 mm. After coating using a coater, a colored layer was formed by drying at 80° C. for 3 minutes using a hot plate. This colored layer was irradiated with ultraviolet rays of 60 mJ/cm ² using an ultra-high pressure mercury lamp.
Next, the colored substrate is post-baked in a clean oven at 230° C. for 30 minutes, and the contrast, chromaticity (x, y), and luminance (Y) of the obtained colored substrate are measured using a contrast measurement device CT-1B manufactured by Tsubosaka Electric Co., Ltd. was measured using an Olympus microscopic spectrometer OSP-SP200.
(Contrast evaluation criteria)
A: Green more than 7000, Red more than 5000, Blue more than 6000 B: Green more than 5600 and less than 7000, Red more than 4000 and less than 5000, Blue more than 4800 and less than 6000 C: Green more than 4200 and less than 5600, Red more than 3000 D: Green is less than 4200, Red is less than 3000, and Blue is less than 3600. However, Green in Examples 1 to 22 and Comparative Examples 1 to 12 with C light source is y=0. 570, Examples 23 to 33 and Comparative Examples 13 to 18 for Red, x=0.650, and Examples 34 to 44 and Comparative Examples 19 to 24, Blue for y=0.107.

[Summary of results]
By comparing Examples and Comparative Examples, Examples 1 to 44 using the graft copolymer or salt-type graft copolymer specified in the present invention suppressed the generation of development residue, shortened the development time, and generated water stains. It has been found that a photosensitive colored resin composition is obtained which satisfies both suppression and excellent solvent resistance.
On the other hand, Comparative Examples 1, 7, 13, and 19 using the graft copolymer L having too long branched chains in which the number of repeating units of the ethylene oxide chain is 90 in the graft chain (polymer chain) of the graft copolymer. The comparative photosensitive colored resin composition of No. 1 was insufficient in the effect of suppressing the generation of development residues, and further deteriorated in dispersion stability and contrast.
Comparative photosensitivity of Comparative Examples 2, 8, 14 and 20 using the graft copolymer M having a relatively short branched chain in which the number of repeating units of the ethylene oxide chain is 17 in the graft chain (polymer chain) of the graft copolymer. The colorant resin composition was insufficient in the effect of suppressing the occurrence of water stains.
Comparative Examples 3, 9, 9, 10, 11, 12, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 14, 16, 18, 19, 20, 20, 20, 20, 20, 20, 21, 20, 20, 20, 21, 20, 20, 20, 20, 20, 20, 20, 20, 20, 20, 20, 20, 20, 20, respectively, respectively, were used as disclosed in Patent Document 2 of the prior art. The comparative photosensitive colored resin compositions of Nos. 15 and 21 tended to cause water stains and development residues.
Comparative photosensitive colored resins of Comparative Examples 4, 10, 16, and 22 using a graft copolymer O as a polymer chain having a repeating unit number of 90 in the ethylene oxide chain as the graft chain (polymer chain) of the graft copolymer The composition was insufficient in the effect of suppressing the occurrence of water stains and the effect of suppressing the occurrence of development residues, and further deteriorated dispersion stability and contrast.
Comparative photosensitive colored resin compositions of Comparative Examples 5, 11, 17, and 23 using block copolymer P having a polymer chain having 22 repeating units of an ethylene oxide chain as a constituent unit of the block copolymer, The effect of suppressing the occurrence of water stains was insufficient, and the effect of solvent resistance could not be obtained.
A block copolymer Q containing a triethylene glycol ethyl ether methacrylate-derived structural unit having 3 repeating units in an ethylene oxide chain as a structural unit of the block copolymer as disclosed in Patent Document 1 of the prior art. The comparative photosensitive colored resin compositions of Comparative Examples 6, 12, 18, and 24 used are insufficient in the effect of suppressing the occurrence of water stains and the effect of suppressing the occurrence of development residues, and the effect of solvent resistance is not obtained. It was something.

REFERENCE SIGNS LIST 1 substrate 2 light shielding part 3 colored layer 10 color filter 20 counter substrate 30 liquid crystal layer 40 liquid crystal display device 50 organic protective layer 60 inorganic oxide film 71 transparent anode 72 hole injection layer 73 hole transport layer 74 light emitting layer 75 electron injection layer 76 Cathode 80 Organic Light Emitting Body 100 Organic Light Emitting Display

Claims (10)

A coloring material dispersion containing a coloring material, a dispersant, and a solvent,
The dispersant has a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II) , and the structural units represented by the general formula (I) are all structural A graft copolymer containing 3 to 60% by mass of the unit and containing 40 to 97% by mass of the structural unit represented by the general formula (II), and the A salt formed by forming a salt between at least part of the nitrogen sites of the structural units represented by the general formula (I) of the graft copolymer and at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons. A colorant dispersion containing at least one type graft copolymer.

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A ¹ is a -CONH- group or -COO- group and a divalent linking group containing an alkylene group having 1 to 10 carbon atoms , R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms or a phenyl group, or R ² and ^{R 3 are} bonded together to ^form pyrrolidine It forms a ring, piperidine ring, or morpholine ring .
In general formula (II), R ^{1 '} is a hydrogen atom or a methyl group, A ² is a direct bond or a divalent linking group, Polymer represents a polymer chain, and the structural unit of the polymer chain has the following general formula (III) Contains a structural unit represented by )

(In the general formula (III), R ⁴ is a hydrogen atom or a methyl group, A ³ is a -CONH- group or a -COO- group , R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or carbon number an alkyl group of 1 to 18 carbon atoms, an alkenyl group of carbon atoms of 2 to 18, an aryl group of carbon atoms of 6 to 12, or a combination thereof, and m represents a number of 19 or more and 80 or less.) The structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer includes the structural unit represented by the general formula (III) and the structural unit represented by the general formula (III). and a structural unit represented by the following general formula (IV) different from the structural unit represented by the general formula (III) when the total structural units of the polymer chain are 100% by mass. 2. The colorant dispersion according to claim 1, wherein the total proportion of units is 1% by mass or more and 75% by mass or less.

(In the general formula (IV), R ^4' is a hydrogen atom or a methyl group, A ⁴ is a -CONH- group or a -COO- group , R ⁷ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, carbon alkenyl groups of 2 to 18 carbon atoms, aryl groups of 6 to 12 carbon atoms, or hydrocarbon groups that are combinations thereof, and the hydrocarbon groups are halogen atoms, hydroxyl groups, carboxy groups, alkoxy groups, nitro groups, cyano group, an epoxy group, an isocyanate group, and a thiol group, and in the carbon chain of the hydrocarbon group, -CO-, -COO-, -OCO -, -O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH -COO-, -NH-CO-NH-, -NH-O-, or -O-NH- linking groups may be included.) 1 or 2, wherein the structural units of the polymer chain in the structural units represented by the general formula (II) of the graft copolymer further include structural units represented by the following general formula (IIIa): 2. The colorant dispersion liquid according to 2 above.

(In the general formula (IIIa), R ⁴ is a hydrogen atom or a methyl group, A ³ is a -CONH- group or a -COO- group , R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or carbon number an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 2 to 18 carbon atoms, an aryl group of 6 to 12 carbon atoms, or a combination thereof, and m' represents a number of 10 or less.) It has a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and the structural units represented by the general formula (I) are 3 to 60 in all structural units % by mass, and the structural unit represented by the general formula (II) is contained in a proportion of 40 to 97% by mass in all structural units, and the graft copolymer A salt-type graft copolymer in which at least part of the nitrogen moiety of the structural unit represented by the general formula (I) and at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons form a salt. A dispersant that is at least one of

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A ¹ is a -CONH- group or -COO- group and a divalent linking group containing an alkylene group having 1 to 10 carbon atoms , R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms or a phenyl group, or R ² and ^{R 3 are} bonded together to ^form pyrrolidine It forms a ring, piperidine ring, or morpholine ring .
In general formula (II), R ^{1 '} is a hydrogen atom or a methyl group, A ² is a direct bond or a divalent linking group, Polymer represents a polymer chain, and the structural unit of the polymer chain has the following general formula (III) Contains a structural unit represented by )

(In the general formula (III), R ⁴ is a hydrogen atom or a methyl group, A ³ is a -CONH- group or a -COO- group , R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or carbon number an alkyl group of 1 to 18 carbon atoms, an alkenyl group of carbon atoms of 2 to 18, an aryl group of carbon atoms of 6 to 12, or a combination thereof, and m represents a number of 19 or more and 80 or less.) The structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer includes the structural unit represented by the general formula (III) and the structural unit represented by the general formula (III). and a structural unit represented by the following general formula (IV) different from the structural unit represented by the general formula (III) when the total structural units of the polymer chain are 100% by mass. 5. The dispersant according to claim 4, wherein the total proportion of units is 1% by mass or more and 75% by mass or less.

(In the general formula (IV), R ^4' is a hydrogen atom or a methyl group, A ⁴ is a -CONH- group or a -COO- group , R ⁷ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, carbon alkenyl groups of 2 to 18 carbon atoms, aryl groups of 6 to 12 carbon atoms, or hydrocarbon groups that are combinations thereof, and the hydrocarbon groups are halogen atoms, hydroxyl groups, carboxy groups, alkoxy groups, nitro groups, cyano group, an epoxy group, an isocyanate group, and a thiol group, and in the carbon chain of the hydrocarbon group, -CO-, -COO-, -OCO -, -O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH -COO-, -NH-CO-NH-, -NH-O-, or -O-NH- linking groups may be included.) 4. or 5. The dispersant according to 5.

(In the general formula (IIIa), R ⁴ is a hydrogen atom or a methyl group, A ³ is a -CONH- group or a -COO- group , R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom or carbon number an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 2 to 18 carbon atoms, an aryl group of 6 to 12 carbon atoms, or a combination thereof, and m' represents a number of 10 or less.) A photosensitive colored resin composition comprising the dispersant according to any one of claims 4 to 6, a coloring material, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. A cured product of the photosensitive colored resin composition according to claim 7 . A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to claim 8. A display device comprising the color filter according to claim 9 .

Images