WO2022202208A1

WO2022202208A1 - Color material liquid dispersion, modified color material, curable coloring composition, color filter, and display device

Info

Publication number: WO2022202208A1
Application number: PCT/JP2022/009303
Authority: WO
Inventors: 健朗長井
Original assignee: 株式会社Ｄｎｐファインケミカル
Priority date: 2021-03-24
Filing date: 2022-03-04
Publication date: 2022-09-29
Also published as: JPWO2022202208A1; CN117043280A; TW202307038A

Abstract

This color material liquid dispersion contains: a color material; a dispersant; a nitrogen-containing basic compound having a pKa of at least 11.5; an acidic group-containing compound having a pKa of at most 4.0; and a solvent, wherein the nitrogen-containing basic compound having a pKa of at least 11.5 and the acidic group-containing compound having a pKa of at most 4.0 are each contained in an amount of 0.1-30.0 part by mass with respect to 100 parts by mass of the color material, and the dispersant includes a polymer which has a structural unit represented by general formula (I) and of which an amine value before salt formation is less than 10 mgKOH/g. (In general formula (I), R¹ represents a hydrogen atom or a methyl group, A represents a direct bond or a divalent linking group, and Q is an acidic group.)

Description

Colorant dispersion liquid, modified colorant, colored curable composition, color filter, display device

The present invention relates to a colorant dispersion, a modified colorant, a colored curable composition, a color filter, and a display device.

In recent years, the demand for liquid crystal displays has increased with the development of personal computers, especially portable personal computers. 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, brightness 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 that has passed through the color filter is colored into the color of each pixel that constitutes the color filter, 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, the pigment dispersion method, which has excellent average characteristics in terms of spectral characteristics, durability, pattern shape and accuracy, 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 using a dispersant is an effective way to improve the dispersibility of finely divided pigments. For example, Patent Literature 1 describes a dispersant composition having excellent pigment dispersibility (a) containing an A block containing a structural unit derived from a vinyl monomer having an acidic group and a vinyl monomer having a tertiary amino group. (b) an aromatic dicarboxylic acid imide, an acidic group-containing aromatic compound and a phenolic hydroxyl group-containing aromatic A dispersant composition is disclosed comprising a mixture of at least one aromatic compound selected from the group consisting of group compounds, and (c) a tertiary amine compound.

Further, Patent Document 2 contains a phthalocyanine pigment (A), a resin-type dispersant (B), and a binder resin (C), and the resin-type dispersant is (B1) a basic resin-type dispersant ( b1), a phosphoric acid-based resin-type dispersant (b2), and a carboxylic acid-based resin-type dispersant (b4), or (B2) a phosphorus compound such as phosphonic acid or a sulfonic acid compound A green colored composition comprising either a salt (b3) with a basic resin-type dispersant (b1) or a resin-type dispersant containing a carboxylic acid-based resin-type dispersant (b4). things are disclosed. Patent Document 2 discloses that a green coloring composition having a viscosity suitable for coating and excellent viscosity stability can be obtained by using a plurality of resin-type dispersants having specific structures and performances in combination. It is

Japanese Patent No. 6605783 JP 2020-169242 A

There is a demand for the formation of a colored layer in which the chromaticity change during heating is suppressed and the brightness is improved. The improvement in luminance is still insufficient, and there is also the problem that foreign matter is likely to occur on the coating film.
Patent Document 1 discloses that (b) at least one aromatic compound selected from the group consisting of an aromatic dicarboxylic acid imide, an acidic group-containing aromatic compound and a phenolic hydroxy group-containing aromatic compound has a pKa of 4. 0 or less acidic group-containing compounds are also exemplified. However, in the examples of Patent Document 1, a strong acid such as an acidic group-containing compound having a pKa of 4.0 or less and a strong base such as a nitrogen-containing basic compound having a pKa of 11.5 or more are used in combination. do not have. When a strong acid, such as an acidic group-containing compound with a pKa of 4.0 or less, and a strong base, such as a nitrogen-containing basic compound with a pKa of 11.5 or more, are used in combination, the salt is difficult to dissolve and precipitates easily. This is probably because there is a problem that foreign substances are likely to be generated in the film. (a) of Patent Document 1: A block containing a structural unit derived from a vinyl monomer having an acidic group, a structural unit derived from a vinyl monomer having a tertiary amino group, and a structure derived from a vinyl monomer having a quaternary ammonium base A block copolymer having a B block containing units is a site in which the B block has affinity with the coloring agent in Patent Document 1, and the A block is a solvent-soluble site, and is substantially a basic dispersant. . The structural units derived from vinyl monomers having acidic groups in the A block are included for the purpose of facilitating alkali development, and are randomly arranged in the A block. A strong base such as a nitrogen-containing basic compound having a pKa of 11.5 or more forms a salt in a structural unit derived from a vinyl monomer having an acidic group randomly arranged in the A block, which is a solvent-soluble site. Also, the solvent-soluble portion becomes difficult to dissolve in the solvent and precipitates, and foreign matter is likely to occur in the coating film. In particular, when a random copolymer having an acidic group, which is often used as a binder resin or an alkali-soluble resin, is used in combination, foreign substances are significantly generated on the coating film.

The present invention has been made in view of the above circumstances, and a coloring material dispersion capable of forming a coating film in which chromaticity change during heating is suppressed, luminance is improved, and foreign matter generation is suppressed, and when heated It is an object of the present invention to provide a coloring material in which the chromaticity change of is suppressed and the luminance is improved. Another object of the present invention is to provide a colored curable composition capable of forming a coating film in which chromaticity change upon heating is suppressed, luminance is improved, and generation of foreign matter is suppressed. Another object of the present invention is to provide a color filter and a display device formed using the colored curable composition.

The coloring material dispersion according to the present invention contains a coloring material, a dispersant, a nitrogen-containing basic compound having a pKa of 11.5 or more, an acidic group-containing compound having a pKa of 4.0 or less, and a solvent. ,
The nitrogen-containing basic compound having a pKa of 11.5 or more and the acidic group-containing compound having a pKa of 4.0 or less are added in an amount of 0.1 parts by mass to 30 parts by mass, respectively, based on 100 parts by mass of the coloring material. Contains 0 parts by mass,
The dispersant contains a polymer having a structural unit represented by the following general formula (I) and having an amine value of less than 10 mgKOH/g before salt formation.

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a direct bond or a divalent linking group, and Q is an acidic group.)

The modified colorant according to the present invention contains a colorant, a nitrogen-containing basic compound with a pKa of 11.5 or more, and an acidic group-containing compound with a pKa of 4.0 or less, and the pKa is 11.5 or more. and the acidic group-containing compound having a pKa of 4.0 or less, each containing 0.1 parts by mass to 30.0 parts by mass with respect to 100 parts by mass of the coloring material. It is a coloring material.

The colored curable composition according to the present invention contains the coloring material dispersion liquid according to the present invention, a polymerizable compound, and an initiator.

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 product of the colored curable composition according to the present invention. is.

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

According to the present invention, the chromaticity change during heating is suppressed, the brightness is improved, the colorant dispersion capable of forming a coating film in which the generation of foreign matter is suppressed, and the chromaticity change during heating is suppressed, and the brightness can provide a coloring material with improved Further, according to the present invention, it is possible to provide a colored curable composition capable of forming a coating film in which chromaticity change upon heating is suppressed, luminance is improved, and generation of foreign matter is suppressed. Moreover, according to this invention, the color filter and display apparatus which were formed using the said colored curable 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.

Hereinafter, the colorant dispersion liquid, the modified colorant, the colored curable composition, the color filter, and the display device according to the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and 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.
Also, 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.
In the present invention, a transmittance of Z % or more in the range of X nm to Y nm means that the transmittance is Z % or more in the entire wavelength range of X nm to Y nm.

I. Colorant dispersion The colorant dispersion according to the present invention comprises a colorant, a dispersant, a nitrogen-containing basic compound having a pKa of 11.5 or more, an acidic group-containing compound having a pKa of 4.0 or less, and a solvent. and
The nitrogen-containing basic compound having a pKa of 11.5 or more and the acidic group-containing compound having a pKa of 4.0 or less are added in an amount of 0.1 parts by mass to 30 parts by mass, respectively, based on 100 parts by mass of the coloring material. Contains 0 parts by mass,
The dispersant contains a polymer having a structural unit represented by the following general formula (I) and having an amine value of less than 10 mgKOH/g before salt formation.

The coloring material dispersion liquid according to the present invention contains a specific amount of a nitrogen-containing basic compound having a pKa of 11.5 or more and a specific amount of an acidic group-containing compound having a pKa of 4.0 or less relative to the coloring material. And, as a dispersant, an acidic dispersant that is a polymer having a structural unit represented by the general formula (I) and having an amine value before salt formation of less than 10 mgKOH/g is used. It is possible to form a coating film in which change in chromaticity over time is suppressed, luminance is improved, and generation of foreign matter is suppressed.
In the colorant dispersion according to the present invention, a specific amount of a nitrogen-containing basic compound having a pKa of 11.5 or more and a specific amount of a pKa of 4 are interposed between the colorant and the specific acidic dispersant. 0.0 or less acidic group-containing compound intervening, high interaction such as acid-base interaction, π-π interaction, hydrogen bonding, etc., is considered to enhance the colorant adsorptivity of the dispersant. Since the coloring material is likely to be highly coated with a nitrogen-containing basic compound having a pKa of 11.5 or more, an acidic group-containing compound having a pKa of 4.0 or less, and a dispersant, the coloring material It is presumed that the heat resistance of the coloring material is improved, the chromaticity change during heating of the coloring material is easily suppressed, and the brightness is improved. In addition, in the colorant dispersion according to the present invention, even if a nitrogen-containing basic compound having a pKa of 11.5 or more and an acidic group-containing compound having a pKa of 4.0 or less are used in combination, the specific acidic The combination of the dispersant suppresses the generation of foreign matter on the coating film. In combination with the specific acidic dispersant, a nitrogen-containing basic compound having a pKa of 11.5 or more and an acidic group-containing compound having a pKa of 4.0 or less, which becomes a poorly soluble salt, has a pKa of 11.5 or more. Because the nitrogen-containing basic compound portion of the acidic dispersant easily adsorbs to the acidic group, which is the coloring material adsorption site of the specific acidic dispersant, the slightly soluble salt is surrounded by the acidic dispersant as well as the coloring material, and the acidic dispersant Since solvent solubility can be ensured by the solvent-soluble portion of the agent, it is presumed that it is possible to form a coating film in which precipitation is unlikely to occur and the generation of foreign matter is suppressed.
By combining a nitrogen-containing basic compound with a pKa of 11.5 or more and an acidic group-containing compound with a pKa of 4.0 or less, a highly heat-resistant salt is formed, and the pKa is 11.5 or more when heated at a high temperature. and an acidic group-containing compound with a pKa of 4.0 or less are inhibited from decomposing. It is presumed that the chromaticity change during heating of the coloring material is more likely to be suppressed and the luminance is improved compared to the case of combining them.

The colorant dispersion liquid according to the present invention contains at least a colorant, a dispersant containing the specific polymer, a nitrogen-containing basic compound having a pKa of 11.5 or more, and an acidic group having a pKa of 4.0 or less. It contains a compound and a solvent, and may contain other components as long as the effects of the present invention are not impaired.
The coloring material dispersion according to the present invention comprises a coloring material, a dispersant containing the above-mentioned specific polymer, a nitrogen-containing basic compound having a pKa of 11.5 or more, and an acidic group-containing compound having a pKa of 4.0 or less. and a solvent, and examples of the preparation method include the following aspects.
i) a dispersant containing a coloring material, a specific polymer having a structural unit represented by the general formula (I), a nitrogen-containing basic compound having a pKa of 11.5 or more, and a pKa of 4.0 or less and a solvent are mixed to disperse the coloring material.
ii) a dispersing agent containing a salt-type polymer obtained by salt-forming a specific polymer having a structural unit represented by the general formula (I) with a nitrogen-containing basic compound having a pKa of at least 11.5 or more; , an acidic group-containing compound having a pKa of 4.0 or less, a colorant, and a solvent are mixed to disperse the colorant.
iii) a salt-type polymer obtained by forming a salt in advance with a nitrogen-containing basic compound having at least a pKa of at least 11.5 on a specific polymer having a structural unit represented by the general formula (I), and a basic dispersion; A dispersing agent containing a salt-type polymer obtained by forming a salt in advance with an acidic group-containing compound having a pKa of 4.0 or less, a coloring material, and a solvent are mixed to disperse the coloring material.
iv) a modified coloring material obtained by modifying the coloring material in advance with a nitrogen-containing basic compound having a pKa of 11.5 or more and an acidic group-containing compound having a pKa of 4.0 or less; A dispersing agent containing a specific polymer having a structural unit with a solvent is mixed with a solvent to disperse the coloring material.
Hereinafter, for each component of the colorant dispersion according to the present invention, a nitrogen-containing basic compound having a pKa of 11.5 or more, an acidic group-containing compound having a pKa of 4.0 or less, a colorant, a modified colorant, Description will be made in the order of dispersant, solvent, and other components.

<Nitrogen-containing basic compound having pKa of 11.5 or more>
The nitrogen-containing basic compound having a pKa of 11.5 or higher is one or more selected from the group consisting of a tertiary amino group-containing basic compound and a basic heterocyclic compound, and has a pKa of 11.5 or higher. compounds shown.
As the nitrogen-containing basic compound used in the present invention, a compound having a pKa of 11.5 or more is selected from the viewpoint of dispersibility, dispersion stability, and suppression of colorant chromaticity change. The pKa of the nitrogen-containing basic compound is preferably 12.0 or more, and more preferably 12.5 or more, from the viewpoint of further suppressing chromaticity change upon heating and further improving luminance. On the other hand, the upper limit of the acid dissociation constant is not particularly limited as long as the effects of the present invention are not impaired, but 30 or less can be mentioned.
In the present invention, pKa is the value of the first-stage acid dissociation constant in water at 25°C.
As a method for measuring the acid dissociation constant in the present invention, the neutralization titration method described in Maruzen Co., Ltd., Kagaku Binran, Basic Edition, Revised 4th Edition can be used.

Among the nitrogen-containing basic compounds having a pKa of 11.5 or more, the tertiary amino group-containing basic compound contains a tertiary amino group, and if it is a basic compound, it further has another functional group. may Other functional groups include, for example, hydroxyl group, (meth)acryloyloxy group, (meth)acrylamide group, amide group, ether group and the like.
Examples of the tertiary amino group-containing basic compound include 1,8-bis(dimethylamino)naphthalene (pKa: 12.1).
Examples of basic heterocyclic compounds include 1,8-diazabicyclo[5.4.0]undecene-7 (pKa: 12.5), 1,5-diazabicyclo[4.3.0]nonene- 5 (pKa: 12.7), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (pKa: 14.7), and 7-methyl-1,5,7- and triazabicyclo[4.4.0]dec-5-ene (pKa: 14.4).
In terms of dispersion stability, brightness, contrast, and solvent re-solubility, 1,8-diazabicyclo[5.4.0]undecene-7 (pKa: 12.5), 1,5-diazabicyclo[4. 3.0]nonene-5 (pKa: 12.7), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (pKa: 14.7), and 7-methyl-1 , 5,7-triazabicyclo[4.4.0]dec-5-ene (pKa: 14.4).

A nitrogen-containing basic compound having a pKa of 11.5 or more preferably has a molecular weight of 800 or less, more preferably 650 or less, and 500 or less from the viewpoint of dispersibility, dispersion stability, and coloring power. is even more preferable, and 350 or less is even more preferable. On the other hand, the nitrogen-containing basic compound having a pKa of 11.5 or more preferably has a molecular weight of 60 or more from the viewpoint of heat resistance.

The nitrogen-containing basic compound having a pKa of 11.5 or more used in the present invention has a transmittance of 90% or more in the wavelength range of 400 nm to 700 nm in order to suppress coloring of the coloring material by addition. is preferred, and more preferably 93% or more.
That is, the nitrogen-containing basic compound having a pKa of 11.5 or higher used in the present invention is preferably different from a colorant derivative such as a pigment derivative.
In the present invention, the transmittance in the wavelength range of 400 nm to 700 nm is measured with an ultraviolet-visible spectrophotometer (for example, Shimadzu UV-2500PC) with a concentration of 0.01% by mass. It can be measured as a range that includes 700 nm.

The nitrogen-containing basic compound having a pKa of 11.5 or more to be used in the present invention should have a solubility of 0.1 g/100 g solvent or more at 23° C. in the solvent used for the coloring material dispersion described later. It is preferably 0.5 g/100 g solvent or more, more preferably 1.0 g/100 g solvent or more. By selecting a content within the above range, the effects of the present invention can be obtained with the addition of a small amount of the basic heterocyclic compound, and a decrease in coloring power of the colorant dispersion can be suppressed.

The nitrogen-containing basic compound having a pKa of 11.5 or higher is used in an amount of 0.1 to 30.0 parts by mass with respect to 100 parts by mass of the coloring material.
The content of the nitrogen-containing basic compound with a pKa of 11.5 or more is 0 per 100 parts by mass of the colorant, in order to sufficiently obtain the effects of the present invention and to suppress a decrease in coloring power. .1 to 15.0 parts by mass, 0.5 to 10.0 parts by mass, and further 1.0 to 7.0 parts by mass.
The nitrogen-containing basic compounds having a pKa of 11.5 or higher may be used singly or in combination of two or more. When combining two or more, the total content is preferably within the above range.

<Compound containing acidic group with pKa of 4.0 or less>
The acidic group-containing compound having a pKa of 4.0 or less is one or more selected from the group consisting of compounds having an acidic group, and includes compounds having a pKa of 4.0 or less.
As the acidic group-containing compound used in the present invention, a compound having a pKa of 4.0 or less is selected from the viewpoint of suppressing the chromaticity change of the coloring material. The pKa of the acidic group-containing compound is more preferably 3.0 or less, and even more preferably 2.5 or less, because the change in chromaticity during heating is suppressed and the luminance is further improved. . On the other hand, the lower limit of the acid dissociation constant is not particularly limited as long as the effect of the present invention is not impaired, but -20.0 or more can be mentioned.

Examples of the acidic group include a carboxy group (--COOH), a sulfonic acid group (SO ₃ H), a phosphonic acid group (--P(=O)(OH) ₂ ), a phosphoric acid group (--OP(=O ) (OH) ₂ ) and the like.

Among them, the acidic group-containing compound having a pKa of 4.0 or less is represented by the following general formulas (1) and (2), since the change in chromaticity during heating is more suppressed and the luminance is further improved. It is preferably one or more compounds selected from the group consisting of compounds and having a pKa of 4.0 or less.

(In the general formula (1), R ^a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, or -O- R ^b represents 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 C 1 to 4 It represents a (meth)acryloyl group via an alkylene group.
In general formula (2), each of R ^c and R ^d may independently have a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a substituent. represents a phenyl group, a benzyl group, or —O—R ^e , where R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group optionally having a substituent, or It represents a benzyl group or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms. However, at least one of ^Rc and ^Rd contains a carbon atom. )

In the general formulas (1) and (2), the straight-chain, branched-chain or cyclic alkyl group having 1 to 20 carbon atoms in R ^a , R ^b , R ^c , R ^d and R ^e is a straight-chain or Any branched chain may be used, and a cyclic structure may be included. Specifically, methyl group, ethyl group, n-propyl group, 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-undecyl group, dodecyl group, cyclopentyl group, cyclohexyl group , tetradecyl group, octadecyl group and the like. A straight, branched or cyclic alkyl group having 1 to 15 carbon atoms is preferred, and a straight, branched or cyclic alkyl group having 1 to 8 carbon atoms is more preferred.
Further, in R ^a , R ^b , 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.

When at least one of R ^a in the general formula (1) and at least one of R ^c and R ^d in the general formula (2) has an aromatic ring, the affinity with the skeleton of the colorant described later is improved. , the dispersibility and dispersion stability of the coloring material are excellent, and a colored composition excellent in contrast can be obtained.

Examples of the acidic group-containing compound having a pKa of 4.0 or less and the carboxyl group-containing compound having a pKa of 4.0 or less include acetic acid (pKa: 3.8).
Examples of the acidic group-containing compound having a pKa of 4.0 or less and the sulfonic acid group-containing compound having a pKa of 4.0 or less include benzenesulfonic acid (pKa: 0.7), vinylsulfonic acid (pKa: - 2.7), methanesulfonic acid (pKa: -1.9), p-toluenesulfonic acid (pKa: -2.8), monomethyl sulfate (pKa: -3.3), monoethyl sulfate (pKa: -3. 1) and the like. A hydrate such as p-toluenesulfonic acid monohydrate may also be used.
Examples of the acidic group-containing compound having a pKa of 4.0 or less and the phosphorus-containing compound represented by the general formula (3) having a pKa of 4.0 or less include monobutyl phosphate (pKa: 1.5), Dibutyl phosphate (pKa: 1.5), methyl phosphate (pKa: 2.4), dibenzyl phosphate (pKa: 1.5), diphenyl phosphate (pKa: 1.1), phenylphosphinic acid (pKa: 2.1) ), phenylphosphonic acid (pKa: 1.9), dimethacryloyloxyethyl acid phosphate (pKa: 1.8), and the like.

Phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, dibutylphosphoric acid, vinylsulfonic acid, and One or more selected from the group consisting of p-toluenesulfonic acid monohydrate is preferable, and among them, one selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, and p-toluenesulfonic acid monohydrate It is preferred to use more than one seed.

The acidic group-containing compound having a pKa of 4.0 or less used in the present invention preferably has a molecular weight of 1000 or less, more preferably 800 or less, and further preferably 400 or less, from the viewpoint of coloring power. It is preferably 350 or less, and even more preferably 330 or less. On the other hand, the acidic group-containing compound having a pKa of 4.0 or less preferably has a molecular weight of 60 or more, more preferably 100 or more, from the viewpoint of heat resistance.

The acidic group-containing compound having a pKa of 4.0 or less used in the present invention must have a transmittance of 90% or more in the wavelength range of 400 nm to 700 nm in order to suppress coloring of the coloring material by addition. is preferred, and more preferably 93% or more.
That is, the acidic group-containing compound having a pKa of 4.0 or less used in the present invention is preferably different from a colorant derivative such as a pigment derivative.

The acidic group-containing compound having a pKa of 4.0 or less used in the present invention preferably has a solubility of 0.1 g/100 g solvent or more at 23° C. in the solvent used in the colorant dispersion described later. , more preferably 0.5 g/100 g solvent or more, and even more preferably 1.0 g/100 g solvent or more. By selecting a content within the above range, the effects of the present invention can be obtained with the addition of a small amount of the compound containing an acidic group, and a decrease in coloring power of the coloring liquid can be suppressed.

The acidic group-containing compound having a pKa of 4.0 or less is used in an amount of 0.1 to 30.0 parts by mass with respect to 100 parts by mass of the coloring material.
The content of the acidic group-containing compound having a pKa of 4.0 or less is 0.00 per 100 parts by mass of the coloring material, in order to sufficiently obtain the effects of the present invention and to suppress a decrease in coloring power. It may be from 1 part by mass to 15.0 parts by mass, may be from 0.5 parts by mass to 10.0 parts by mass, and may be from 1.0 part by mass to 7.0 parts by mass.
The acidic group-containing compounds having a pKa of 4.0 or less may be used singly or in combination of two or more. When combining two or more, the total content is preferably within the above range.

<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 is formed. It 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, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 15, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 60, 61, 62, 62:1, 63, 65, 71, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 173, 175, 185, 194, 211, 214, 215, 231, 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, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 53: 1, 57, 57:1, 57:2, 58:2, 58:4, 60, 60:1, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81:1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 150, 151, 166, 168, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 215, 216, 220, 221, 224, 226, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 291;
C. I. Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 61, 79, 80;
C. I.

Pigment Green

1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 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 colored curable 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.

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, coumarin dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes. can.
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, coloring materials include diketopyrrolopyrrole pigments, anthraquinone pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, aluminum phthalocyanine pigments, dioxazine pigments, azomethine pigments, zinc phthalocyanine dyes, triarylmethane dyes, quinophthalone dyes, and coumarin. When at least one selected from the group consisting of dyes, phthalocyanine dyes, and salt-forming compounds of these dyes is contained, the use of the dispersant is preferable because a colored layer with high brightness can be formed. As the coloring material, among others, diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, dioxazine pigments, zinc phthalocyanine dyes, triarylmethane dyes, quinophthalone dyes, and salt-forming compounds of these dyes. It is preferable to contain at least one selected from the group consisting of:

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 ⁴¹ and R ⁴² in the following general formula (i) are each a 4-bromophenyl group are preferred.

(In general formula (i), R ⁴¹ and R ⁴² are each independently a 4-chlorophenyl group or a 4-bromophenyl group.)

Examples of anthraquinone pigments include C.I. I. Pigment Red 177 and the like.
Examples of quinophthalone pigments include C.I. I. Pigment Yellow 138, 231 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 aluminum phthalocyanine pigments include C.I. I. Pigment Green 62, 63 and the like.
Examples of dioxazine pigments include C.I. I. Pigment Violet 23 and the like.
Examples of azomethine pigments include C.I. I. Pigment Yellow 150 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.
Examples of triarylmethane dyes include C.I. I. Basic Red 9, C.I. I. Basic Blue 1, 7 and the like.
Examples of phthalocyanine dyes include C.I. I. Basic Blue 140, and C.I. I. Zinc phthalocyanine dyes obtained by substituting zinc for the central metal of Basic Blue 140, and the like.
Coloring materials represented by the following general formula (A) are also suitably used in combination with the dispersant of the present invention from the viewpoint of brightness.

(In the general formula (A), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group has at least a saturated aliphatic carbonized Represents an aliphatic hydrocarbon group having a hydrogen group, or an aromatic group having the aliphatic hydrocarbon group, and may contain a heteroatom in the carbon chain.B ^c- represents a c-valent polyacid anion. R ⁱ to R ^v each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may combine to form a ring structure, and each of R ^vi and R ^vii is independently an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom or a cyano Ar ¹ represents an optionally substituted divalent aromatic group, and a plurality of R ⁱ to R ^vii and Ar ¹ may be the same or different.
a and c represent integers of 2 or more; b and d represent integers of 1 or more; e is 0 or 1 and when e is 0 there is no bond. f and g represent integers of 0 or more and 4 or less, and f+e and g+e are 0 or more and 4 or less. Multiple e, f and g may be the same or different. )

For explanation of each code of the colorant represented by the general formula (A), reference can be made to the explanation of the code of the corresponding part of the general formula (I) described in International Publication No. 2018/003706. Examples of the partial structure and other structures of the colorant represented by the general formula (A) include structures described in WO 2018/003706, WO 2012/144521, and the like.

Among the coloring materials used in the present invention, C.I. I. Pigment Red 177, 254, 291, C.I. I. Pigment Yellow 138, 150, 231, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Green 58, 59, 62, 63, C.I. I. It is preferably at least one selected from the group consisting of Pigment Violet 23 and the colorant represented by the general formula (A).

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 diameter of the colorant is within the above range, the display device equipped with the color filter manufactured using the colorant dispersion according to the present invention has high brightness, high contrast, and high quality. can do.

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 recrystallization and solvent salt milling. 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 colorant is, for example, preferably 5% to 80% by mass, more preferably 8% to 70% by mass, based on the total solid content in the colorant dispersion. %.
In particular, when forming a coating film or a colored layer having a high colorant concentration, the solid content in the colorant dispersion is preferably 30% to 80% by mass, more preferably 40% to 75% by mass. It is within the range of % by mass.
The coloring materials 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.
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.

<Modification color material>
The modified colorant of the present invention contains a colorant, a nitrogen-containing basic compound with a pKa of 11.5 or more, and an acidic group-containing compound with a pKa of 4.0 or less. A modified color containing 0.1 parts by mass to 30.0 parts by mass of a nitrogen-containing basic compound and an acidic group-containing compound having a pKa of 4.0 or less with respect to 100 parts by mass of the coloring material. It is wood.
In the modified colorant of the present invention, a nitrogen-containing basic compound having a pKa of 11.5 or more and an acidic group-containing compound having a pKa of 4.0 or less are combined with the colorant, an acid-base interaction, and a π-π interaction. Since the coloring material is modified by hydrogen bonding or the like, the stability of the coloring material is improved and the heat resistance is improved.
Further, the nitrogen-containing basic compound having a pKa of 11.5 or more and the acidic group-containing compound having a pKa of 4.0 or less contained in the modified colorant of the present invention each have a wavelength in the range of 400 nm to 700 nm. Since a compound having a transmittance of 90% or more and having no colored skeleton such as a pigment derivative can be selected, coloring is very little and the brightness is not lowered by addition, so the modified colorant tends to have high brightness.

The colorant used in the modified colorant of the present invention, the nitrogen-containing basic compound having a pKa of 11.5 or more, and the acidic group-containing compound having a pKa of 4.0 or less may be the same as those described above. Therefore, the description here is omitted.

In the modified colorant of the present invention, a nitrogen-containing basic compound having a pKa of 11.5 or more and an acidic group-containing compound having a pKa of 4.0 or less are added to 100 parts by mass of the colorant, respectively. Contains 0.1 to 30.0 parts by mass. Among them, from the viewpoint of improving heat resistance, the modified colorant of the present invention comprises a nitrogen-containing basic compound having a pKa of 11.5 or more and an acidic group-containing compound having a pKa of 4.0 or less. It is preferable to contain 0.1 parts by mass or more, and more preferably 1.0 parts by mass or more, based on 100 parts by mass. On the other hand, from the viewpoint of coloring power, the modified colorant of the present invention comprises a nitrogen-containing basic compound having a pKa of 11.5 or more and an acidic group-containing compound having a pKa of 4.0 or less. It is preferable to contain 20 parts by mass or less, and more preferably 10 parts by mass or less, based on the mass.
The nitrogen-containing basic compound having a pKa of 11.5 or more and the acidic group-containing compound having a pKa of 4.0 or less may be used alone or in combination with each other in the modification colorant. The above may be combined. When combining two or more, the total content is preferably within the above range.

In the modified colorant of the present invention, at least part of the nitrogen-containing basic compound having a pKa of 11.5 or more and at least part of the acidic group-containing compound having a pKa of 4.0 or less form a salt. It is preferable from the viewpoint that the heat resistance of the nitrogen-containing basic compound having a pKa of 11.5 or more and the acidic group-containing compound having a pKa of 4.0 or less are mutually improved, and the heat resistance of the coloring material is improved. .

As a method for preparing the modified colorant of the present invention, for example, after mixing the nitrogen-containing basic compound having a pKa of 11.5 or more, the acidic group-containing compound having a pKa of 4.0 or less, and the colorant, , and dry grinding. In this case, a ball mill, a vibrating mill, an attritor, or the like can be used as a dry pulverizer, and the pulverization temperature can be freely set between 20 and 130°C.
Further, as a method for preparing the modified colorant of the present invention, a nitrogen-containing basic compound having a pKa of 11.5 or more, an acidic group-containing compound having a pKa of 4.0 or less, a colorant, and sodium chloride , a method of mixing a water-soluble inorganic salt such as calcium chloride or ammonium sulfate with a water-soluble organic solvent such as a glycol-based organic solvent, and kneading the mixture with a kneader type grinder by a solvent salt milling method.
Further, as a method for preparing the modified colorant of the present invention, the nitrogen-containing basic compound having a pKa of 11.5 or more, the acidic group-containing compound having a pKa of 4.0 or less, a dye, and a lake agent and pulverize the modified colorant obtained by mixing and forming a lake by various methods.
Further, as a method for preparing the modified colorant of the present invention, the nitrogen-containing basic compound having a pKa of 11.5 or more, the acidic group-containing compound having a pKa of 4.0 or less, and a dye are mixed in a solvent. After dissolving, it is dried and pulverized by various methods.

The average primary particle size of the modified colorant of the present invention is not particularly limited as long as it enables desired color development, and varies depending on the type of colorant used. It is preferably in the range of 10-100 nm, more preferably 15-60 nm. When the average primary particle size of the colorant is within the above range, the colored layer produced using the modified colorant according to the present invention can have high brightness and high quality.
The average primary particle size represents the volume distribution median diameter (D50). The particle size of the modified colorant was measured by attaching a dedicated bright-field STEM sample stage and an optional detector to a field emission scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation. (hereinafter abbreviated as "STEM"), take a STEM photograph of 200,000 times, import it into the software below, select 100 pigments arbitrarily on the photograph, and measure the diameter (length across) is measured, and the volume-based 50% cumulative particle diameter is obtained from the volume-based distribution.
A measurement sample to be subjected to STEM is prepared by mixing a modified coloring material and toluene and dropping the mixture onto a mesh attached with a collodion film. In addition, when obtaining the volume-based particle size distribution and the volume distribution median diameter (D50) from the STEM photograph, the image analysis type particle size distribution measurement software "Mac-View Ver.4" manufactured by Mountec Co., Ltd. is used. can do.

The modified colorant of the present invention contains a colorant, a nitrogen-containing basic compound with a pKa of 11.5 or more, and an acidic group-containing compound with a pKa of 4.0 or less, and the ratio thereof is , for example, mass spectroscopy, elemental analysis, surface analysis, potentiometric titration, and combinations thereof. More specifically, for example, after washing the modified colorant with an alcoholic solvent such as methanol, ethanol, isopropanol, or a solvent such as N-methylpyrrolidone, the washed colorant is analyzed by mass spectrometry, and the pKa is 11.5. It can be confirmed by detecting a peak derived from the structure derived from the nitrogen-containing basic compound or the acidic group-containing compound having a pKa of 4.0 or less and a peak of the coloring material.

<Dispersant>
In the present invention, a polymer having a constitutional unit represented by the general formula (I) and having an amine value of less than 10 mgKOH/g before salt formation is used as the dispersant.
A polymer having a structural unit represented by the general formula (I) and having an amine value of less than 10 mgKOH/g before salt formation contains at least part of the acidic groups contained in the general formula (I) and a base It may be a salt-type polymer in which a salt is formed with a polar compound. The basic compound forming a salt with at least part of the acidic groups in the salt-type polymer may be a nitrogen-containing basic compound having a pKa of 11.5 or more, or a basic compound having a pKa of 11.5. A basic compound different from the above nitrogen-containing basic compounds may be included.

[Polymer having a structural unit represented by the general formula (I)]
(Structural Unit Represented by Formula (I))
In general formula (I), ^R1 represents a hydrogen atom or a methyl group, A represents a direct bond or a divalent linking group, and Q is an acidic group.
In A, the divalent linking group includes, for example, a linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group, a linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group having a hydroxyl group Hydrogen group, aromatic hydrocarbon group, -CONH- group, -COO- group, -NHCOO- group, ether group (-O- group), thioether group (-S- group), 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.

Specific examples of the aliphatic hydrocarbon group include linear groups such as a methylene group, a dimethylene group (ethylene group), a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a decamethylene group. branched alkylene groups such as a branched alkylene group, methylmethylene group, methylethylene group, 1-methylpentylene group and 1,4-dimethylbutylene group; and cyclic alkylene groups such as a cyclopentylene group and a cyclohexylene group.
The number of carbon atoms in the aliphatic hydrocarbon group is 1 to 20, preferably 1 to 16, more preferably 1 to 12, and even more preferably 2 to 8, from the viewpoint of dispersion stability.
Specific examples of the aromatic hydrocarbon group include a phenylene group and a naphthylene group.

Among them, from the viewpoint of dispersibility, A in the general formula (I) is preferably a divalent linking group containing at least one of -CONH- group and -COO- group, -CONH- group and -COO A divalent linking group containing at least one - group and an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may contain an oxygen atom is more preferable.

Examples of the acidic group represented by Q include a carboxy group (--COOH), a sulfonic acid group (SO ₃ H), a phosphonic acid group (--P(=O)(OH) ₂ ), a phosphoric acid group (--O -P(=O)(OH) ₂ ) and the like.
Among the acidic groups represented by Q are, from the standpoint of dispersion stability, a carboxy group (--COOH), a sulfonic acid group (SO ₃ H), and a phosphoric acid group (--OP (=O) (OH ) ₂ ) is preferably at least one selected from the group consisting of 2).
Phosphate group-containing ethylenically unsaturated monomers include, for example, 2-(meth)acryloyloxyethyl acid phosphate, acid phosphooxypolyoxyethylene glycol mono(meth)acrylate and the like.
Sulfonic acid group-containing ethylenically unsaturated monomers include (meth)acryloyloxyethylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid and the like.
The acidic group represented by Q is preferably a carboxy group from the viewpoint of brightness, and the structural unit represented by the general formula (I) includes a structural unit represented by the following general formula (II). is preferred.

(In general formula (II), R ¹ represents a hydrogen atom or a methyl group, and A represents a direct bond or a divalent linking group.)

R ¹ and A in general formula (II) may be the same as in general formula (I).
Examples of the structural unit represented by the general formula (II) include a structural unit derived from (meth)acrylic acid, a structural unit derived from vinylbenzoic acid, and a structural unit derived from (meth)acrylic acid ester.
From the viewpoint of dispersibility and dispersion stability, the general formula (II) includes structural units represented by the following general formula (II-1) and structural units represented by the following general formula (II-2). At least one selected from the group consisting of is preferred.
Among them, from the viewpoint of dispersibility and dispersion stability, solvent re-solubility, and brightness improvement, the structural unit represented by the following general formula (II-1) and the following general formula (II-2) It is preferable to have a structural unit that is

(In general formula (II-1), R ¹ represents a hydrogen atom or a methyl group,
In general formula (II-2), R ¹ represents a hydrogen atom or a methyl group, R ² represents an aliphatic hydrocarbon group which may contain an oxygen atom, and R ³ represents a hydrocarbon group. )

The structural unit represented by general formula (II-1) is a structural unit derived from (meth)acrylic acid.
In the structural unit represented by general formula (II-2), R ² represents an aliphatic hydrocarbon group which may contain an oxygen atom.
The aliphatic hydrocarbon group for R ² may be the same as described above.
The aliphatic hydrocarbon group containing an oxygen atom in R ² has a structure in which the carbon atoms in the aliphatic hydrocarbon group are replaced with oxygen atoms, or the hydrogen atoms in the aliphatic hydrocarbon group are oxygen atoms has a structure substituted with a substituent containing The aliphatic hydrocarbon group which may contain an oxygen atom includes, for example, a structure in which a connecting group such as -O-, -COO-, -OCO- is included in the carbon chain of the hydrocarbon group. Specific examples of the oxygen atom-containing aliphatic hydrocarbon group include -R ²⁰ -(OR ²¹ )s- (wherein R ²⁰ and R ²¹ are each independently an aliphatic hydrocarbon group, s represents a number from 1 to 80), -R ²² -(OCO-R ²³ )t- (wherein R ²² and R ²³ are each independently an aliphatic hydrocarbon group, t is a number from 1 to 40 represents). The aliphatic hydrocarbon groups for R ²⁰ , R ²¹ , R ²² and R ²³ may be the same as the above aliphatic hydrocarbon groups. From the viewpoint of dispersion stability, R ²⁰ is preferably an alkylene group having 1 to 20 carbon atoms, R ²¹ is preferably an alkylene group having 1 to 20 carbon atoms, s is 1 to 40, and A number between 2 and 25, more preferably between 2 and 10 is preferred. From the viewpoint of dispersion stability, R ²² is preferably an alkylene group having 1 to 20 carbon atoms, R ²³ is preferably an alkylene group having 1 to 20 carbon atoms, and t is 1 to 30. , more preferably a number from 1 to 20, even more from 1 to 10.
R ²⁰ and R ²² are each independently preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms.
R ²¹ is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an ethylene group or a propylene group.
R ²³ is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 3 to 7 carbon atoms.
Moreover, examples of the substituent containing an oxygen atom include a hydroxyl group and an alkoxy group.
In the structural unit represented by the general formula (II-2), R ² may be an aliphatic hydrocarbon group from the viewpoint of solvent resolubility, and an aliphatic hydrocarbon group having 1 to 20 carbon atoms. can be

In the structural unit represented by general formula (II-2), R ³ represents a hydrocarbon group. The hydrocarbon group for R ³ includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group and a combination thereof, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may be the same as those described above.
The number of carbon atoms in the hydrocarbon group of R ³ is 1 to 20, preferably 1 to 16, more preferably 2 to 12, and even more preferably 2 to 6, from the viewpoint of dispersion stability.

The structural unit represented by general formula (II-2) can be derived from, for example, a monomer that is an addition reaction product of a (meth)acrylate having a hydroxyl group and a dicarboxylic acid or a dicarboxylic acid anhydride.
(Meth)acrylates having a hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6- Hydroxyhexyl (meth)acrylate, (poly)ethylene glycol mono(meth)acrylate, (poly)propylene glycol mono(meth)acrylate, unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone and the like.
Aliphatic dicarboxylic acids or aliphatic dicarboxylic anhydrides include malonic acid, succinic acid, glutaric acid, adipic acid, 1,6-hexanedicarboxylic acid, hexahydrophthalic acid, succinic anhydride and adipic anhydride. , hexahydrophthalic anhydride, maleic anhydride, and the like. Aromatic dicarboxylic acids or aromatic dicarboxylic anhydrides include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 4,4'-dicarboxy diphenyl ether, phthalic anhydride, naphthalic anhydride and the like.

The pKa of the monomer from which the structural unit represented by general formula (I) is derived is preferably 3.0 or more and less than 6.0, more preferably 3.5 or more and less than 5.0. Further, the pKa of the monomer that induces the structural unit represented by general formula (I) is preferably higher than the pKa of the acidic group-containing compound used in combination with the pKa of 4.0 or less.
A structural unit having a strong acid group with a pKa of less than 3.0 tends to deprive a nitrogen-containing basic compound with a pKa of 11.5 or more from an acidic group-containing compound with a pKa of 4.0 or less by salt exchange. , may inhibit salt formation between an acidic group-containing compound having a pKa of 4.0 or less and a nitrogen-containing basic compound having a pKa of 11.5 or more, and as a result, sufficient improvement in heat resistance and brightness may not be obtained. There is If the structural unit represented by the general formula (I) has a higher pKa than the acidic group-containing compound having a pKa of 4.0 or less to be used in combination, the acidic group-containing compound having a pKa of 4.0 or less can be converted to pKa is less likely to deprive the nitrogen-containing basic compound of 11.5 or more by salt exchange, and sufficient improvement in heat resistance and brightness can be easily obtained.

In the polymer, the structural unit represented by general formula (I) may consist of one type, or may contain two or more types of structural units. When the structural unit represented by the general formula (I) contains two or more structural units, the structural units represented by the general formula (I) are derived from all the structural units represented by the general formula (I). The pKa of the monomer to be used is preferably 3.0 or more and less than 6.0, more preferably 3.5 or more and less than 5.0.

The polymer having the structural unit represented by the general formula (I) is preferably a copolymer from the viewpoint of dispersibility and dispersion stability, and the structural unit represented by the general formula (I) is and a block copolymer having an A block containing a structural unit represented by the general formula (I).

{graft copolymer}
The graft copolymer used in the present invention has, in the main chain, a structural unit represented by the general formula (I) that functions as an adsorption site for a coloring material, and in the side chain, it functions as a solvent affinity site. It is preferably a copolymer having a graft polymer chain that

(Structural Unit Having a Graft Polymer Chain)
The graft copolymer has a graft polymer chain functioning as a solvent affinity site in a side chain.
As a guideline, the polymer chain preferably has a solubility of 20 (g/100 g solvent) or more at 23° C. in the 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 when preparing the graft copolymer. For example, when using a polymerizable oligomer (macromonomer) containing a group having an ethylenically unsaturated double bond at the polymer chain and its terminal in order to introduce a polymer chain into the graft copolymer, the polymerizable oligomer is the above 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, it is sufficient that the polymer chain containing the reactive group has the aforementioned solubility.

The graft copolymer used in the present invention has, in the main chain, a structural unit represented by the general formula (I) that functions as an adsorption site for a coloring material, and further has a side chain as a solvent affinity site. It preferably has a structural unit represented by the following general formula (III) having a functional polymer chain.

(In general formula (III), R ^1″ represents a hydrogen atom or a methyl group, A ¹ represents a direct bond or a divalent linking group, and Polymer represents a polymer chain.)

In the general formula (III), A ¹ is a direct bond or a divalent linking group. The divalent linking group for A ¹ is not particularly limited as long as it can link the carbon atom derived from the ethylenically unsaturated double bond and the polymer chain. The divalent linking group may be the same as A in formula (I).
Among them, from the viewpoint of dispersibility and dispersion stability, A ¹ in the general formula (III) is preferably a divalent linking group containing a -CONH- group or a -COO- group, a -CONH- group or - A divalent linking group containing a COO- group and an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may contain an oxygen atom is more preferable.

From the viewpoint of the dispersibility and dispersion stability of the colorant, the polymer chain preferably contains at least one structural unit represented by the following general formula (IV).

(In general formula (IV), R ¹¹ is a hydrogen atom or a methyl group, A ² is a divalent linking group, and R ⁴ is a hydrocarbon group which may have a substituent and which may contain a hetero atom. .)

In general formula (IV), ^A2 is a divalent linking group. Examples of the divalent linking group for A ² include those similar to the divalent linking group for A ¹ .
Among them, from the viewpoint of the dispersibility and dispersion stability of the colorant, A ² in the general formula (IV) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and -CONH- group or -COO- group is more preferred.

The hydrocarbon group in the hydrocarbon group optionally containing a heteroatom in R ⁴ is, for example, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group or an alkyl-substituted aryl group. and the like.
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, 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 viewpoint of dispersibility and dispersion stability, the hydrocarbon group for R ⁴ 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 The alkyl group is preferably one or more selected from the group consisting of optionally substituted aralkyl groups having 7 to 14 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. It is preferably one or more selected from the group consisting of groups, n-nonyl groups, n-lauryl groups, n-stearyl groups, phenyl groups optionally substituted with alkyl groups, and benzyl groups.

The heteroatom-containing hydrocarbon group for R ⁴ has a structure in which a carbon atom in the hydrocarbon group is replaced with a heteroatom, or a hydrogen atom in the hydrocarbon group is replaced with a heteroatom-containing substituent. It has a well-defined structure. 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 for R ⁴ 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 ² -R ⁴ 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 ⁴ in 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 the structure shown.

Examples of monomers that derive 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 (meth)acrylate and polyethylene glycol (meth)acrylate , phenoxyethylene glycol (meth)acrylate, unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone, and the like. However, it is not limited to these.

In the present invention, it is preferable to use one having excellent solubility in the solvent described later as the ^R4 , and it may be appropriately selected according to the solvent used in the colorant dispersion. Specifically, for example, when the solvent is an ether-alcohol acetate-based, ether-based, ester-based, or alcohol-based organic solvent generally used as a solvent for a colorant dispersion, a 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 groups 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 based on the total structural units (100% by mass) of the polymer chain. , 100% by mass. From the viewpoint of 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 40% by mass or more with respect to all structural units of the polymer chain. and more preferably 70% by mass or more.

Further, the polymer chain of the macromonomer, among the structural units represented by the general formula (IV), from the structural unit represented by the following general formula (V) and the structural unit represented by the following general formula (V') It is preferable to contain at least one kind of structural unit selected from the group consisting of the point of suppressing the generation of foreign substances, the point of improving the adhesion to the substrate, and the point of shortening the development time.

(In general formula (V), R ^11′ is a hydrogen atom or a methyl group, A ^2′ is a divalent linking group, R ⁵ is an ethylene group or a propylene group, and R ⁶ is a hydrogen atom or a hydrocarbon group. , m represents a number of 2 or more and 80 or less.
In general formula (V'), R ^{11 ″} is a hydrogen atom or a methyl group, A ^{2 ″} is a divalent linking group, R ⁷ is an alkylene group having 1 to 10 carbon atoms, and R ⁸ has 3 to 7 carbon atoms. is a hydrogen atom or a hydrocarbon group, and n represents a number of ¹ or more and 40 or less. )

In the structural unit represented by general formula (V) and the structural unit represented by general formula (V′), A ^2′ and A ^2″ are each independently a divalent linking group. A ² The divalent linking group for ^' and ^A2 '' includes, for example, the same ^divalent linking groups for A2.
Among them, from the viewpoint of solubility in solvents used for color filters, A ^2′ and A ^2″ are each independently a divalent linking group containing a —CONH— or —COO— group. is preferred, and -CONH- or -COO- is more preferred.

The m in the general formula (V) represents the number of repeating units of an ethylene oxide chain or a propylene oxide chain, and represents a number of 2 or more. It is preferably 4 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 solvents used for color filters.

R ⁶ is a hydrogen atom or a hydrocarbon group, and examples of the hydrocarbon group for R ⁶ include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, and Combinations thereof, such as aralkyl groups and alkyl-substituted aryl groups, are included.
Examples of the hydrocarbon group for R ⁶ include the same hydrocarbon groups as those for R ⁴ .
Among the hydrocarbon groups for R ⁶ , from the viewpoint of dispersion stability, 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 general formula (V′), R ⁷ is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 2 to 8 carbon atoms from the viewpoint of solvent resolubility.
R ⁸ is an alkylene group having 3 to 7 carbon atoms. Among them, an alkylene group having 3 to 5 carbon atoms, and more preferably an alkylene group having 5 carbon atoms are preferable from the standpoint of substrate adhesion.
R ⁹ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group for R ⁹ may be the same as the hydrocarbon group for R ⁶ above.

The n in the general formula (V′) represents the number of repeating units of the lactone chain, and represents a number of 1 or more, preferably 2 or more, more preferably 3 or more, from the viewpoint of substrate adhesion. is preferred.
On the other hand, the upper limit of n is 40 or less, but preferably 20 or less in terms of solubility in solvents used for color filters.

In the polymer chain, at least one structural unit selected from the group consisting of structural units represented by the general formula (V) and structural units represented by the following general formula (V') may be used alone. Although it is good, two or more kinds may be mixed.
From the viewpoint of improving adhesion to a substrate and shortening the development time, the structural unit represented by the general formula (V) and the following are added to all the structural units of the polymer chain in the macromonomer of the graft copolymer. The total proportion of at least one structural unit selected from the group consisting of structural units represented by general formula (V′) is preferably 5% by mass or more, more preferably 10% by mass or more. , more preferably 15% by mass or more. The total proportion of at least one structural unit selected from the group consisting of the structural unit represented by the general formula (V) and the structural unit represented by the following general formula (V') is the solvent re-solubility point Therefore, it is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, based on the total structural units of the polymer chain.

The structural unit of the polymer chain in the structural unit represented by the general formula (III) of the graft copolymer includes the structural unit represented by the general formula (V) and the following general formula (V'). In addition to the structural unit represented by the general formula (IV), which includes at least one structural unit selected from the group consisting of the structural units described above, other structural units may be included.
Examples of other structural units include structural units derived from ethylenically unsaturated monomers that are copolymerizable with the ethylenically unsaturated monomers from which the structural units represented by general formula (IV) are derived.
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 (III) of the graft copolymer, the total ratio of the other structural units to the total structural units of the polymer chain is is preferably 30% by mass or less, more preferably 10% by mass or less.

Further, the weight average molecular weight Mw of the polymer chain 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. It is preferably 15,000 or less, and even more preferably 12,000 or less.
Within the above range, a sufficient steric repulsion effect as a dispersant can be maintained, and the above-described effects can be improved by increasing the specific surface area of the solvent affinity portion of the dispersant.
The mass-average molecular weight Mw of the polymer chain can be measured in the same manner as for the dispersant, which will be described later, for the polymer chain containing the polymerizable oligomer or the reactive group.

In addition, the polymer chain preferably has an acid value of 10 mgKOH/g or less, more preferably 0 mgKOH/g or less, from the viewpoint of suppressing the generation of foreign matter and dispersion stability. Here, the acid value of the polymer chain containing the polymerizable oligomer or the reactive group can be measured in the same manner as the acid value of the dispersant, which will be described later.
The polymer chain may contain a structural unit represented by the general formula (I) as long as the effects of the present invention are not impaired, but from the viewpoint of dispersion stability, all structural units of the polymer chain On the other hand, the total proportion of structural units containing acidic groups is preferably 5% by mass or less, more preferably 0% by mass.

The polymer chain preferably has an amine value of less than 10 mgKOH/g, more preferably 0 mgKOH/g or less, from the viewpoint of dispersibility and dispersion stability. Here, the amine value of the polymer chain is the mass (mg) of potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize 1 g of the solid content of the polymer chain containing the polymerizable oligomer or the reactive group. and is a value measured by the method described in JIS K 7237:1995.
The polymer chain may contain a nitrogen atom-containing structural unit as long as the effects of the present invention are not impaired. The total proportion of the structural units is preferably 5% by mass or less, more preferably 0% by mass.

In the graft copolymer, the content of the structural unit represented by the general formula (I) is preferably 3% by mass or more and 60% by mass or less with respect to the total structural units of the main chain of the graft copolymer, It is more preferably 6% by mass or more and 45% by mass or less, and even more preferably 9% by mass or more and 35% by mass or less. If the content of the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the portion having an affinity for the colorant in the graft copolymer is appropriate, and Since it is possible to suppress the deterioration of the solubility in solvents, the adsorptivity to coloring materials is improved, and excellent dispersibility, dispersion stability, and solvent re-solubility can be obtained.
On the other hand, in the graft copolymer, the total content ratio of the structural units containing the graft polymer chain and the structural units represented by the general formula (III) is 40% by mass or more and 97% by mass or less is preferable, 55% by mass or more and 94% by mass or less is more preferable, and 65% by mass or more and 91% by mass or less is even more preferable. If the total content of the structural units containing the graft polymer chain in the graft copolymer and the structural units represented by the general formula (III) is within the above range, the ratio of the solvent affinity portion in the graft copolymer becomes appropriate, 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, so that the above effect can be improved.
In addition, the content ratio of the structural unit is derived from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (III) when synthesizing the graft copolymer. It is calculated from the charged amount of the monomer.

The graft copolymer used in the present invention is a structural unit represented by the general formula (I) and a structural unit represented by the general formula (III) within a range that does not impair the effects of the present invention. Besides, it may have other structural units. As the other structural unit, an ethylenically unsaturated monomer that can be copolymerized with the ethylenically unsaturated monomer or the like that induces the structural unit represented by the general formula (I) is appropriately selected and copolymerized. can be introduced.
Other structural units copolymerized with the structural units represented by the general formula (I) in the main chain include, for example, the structural units represented by the general formula (IV) and the general formula (I ), and structural units containing acidic groups different from the structural units represented by ).
Examples of monomers from which a structural unit containing an acidic group different from the structural unit represented by the general formula (I) is derived include maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, and cinnamon. acids and the like.
In the graft copolymer, the total content of other structural units copolymerized in the main chain is preferably 40% by mass or less with respect to all structural units in the main chain of the graft copolymer, It is more preferably 20% by mass or less, and may be 0% by mass.

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

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

Further, when producing a graft copolymer having a structural unit represented by the general formula (I), the monomer represented by the general formula (Ia) and other ethylenically unsaturated monomers are addition-polymerized. After the copolymer is formed by using a polymer chain containing a reactive group capable of reacting with the reactive group contained in the copolymer, a polymer chain may be introduced. 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.

{block copolymer}
The block copolymer used in the present invention has an A block containing the structural unit represented by the general formula (I), which functions as an adsorption site for the colorant.
The block copolymer used in the present invention preferably further has a B block functioning as a solvent affinity site.

(A block)
In the A block, the structural unit represented by the general formula (I) is the same as described above, so the description is omitted here.
In block A, the structural unit represented by general formula (I) may consist of one type, or may contain two or more types of structural units.

In addition to the structural units represented by the general formula (I), the A block may further contain other structural units as long as the effects of the present invention are not impaired. As the other structural unit, an ethylenically unsaturated monomer that can be copolymerized with the ethylenically unsaturated monomer or the like that derives the structural unit represented by the general formula (I) is appropriately selected and copolymerized. can be introduced.
Other structural units contained in the A block within a range that does not impair the effects of the present invention include, for example, structural units represented by the general formula (IV) and structures represented by the general formula (I) Structural units containing acidic groups different from the units are included.
The structural unit represented by the general formula (IV) and the structural unit containing an acidic group different from the structural unit represented by the general formula (I) are the same as those described for the graft copolymer. Since it is acceptable, the explanation here is omitted.
The total content of other structural units contained in the A block is not particularly limited as long as it does not impair the effects of the present invention, but from the viewpoint of dispersibility and dispersion stability, It is preferably 40% by mass or less, more preferably 20% by mass or less, and may be 0% by mass.

That is, the content of the structural unit represented by the general formula (I) contained in the A block should be 60% by mass or more based on the total structural units of the A block from the viewpoint of dispersibility and dispersion stability. is preferred, more preferably 80% by mass or more, and may be 100% by mass.

(B block)
In the block copolymer used in the present invention, the B block is a block that functions as a solvent affinity site. The B block is selected from among ethylenically unsaturated monomers copolymerizable with the ethylenically unsaturated monomers from which the structural unit represented by the general formula (I) is derived, depending on the solvent so as to have solvent affinity. It is preferable to select and use them as appropriate. As a guideline, it is preferable to introduce the B block so that the solubility of the block copolymer at 23° C. in the solvent used in combination is 20 (g/100 g solvent) or more.

In the block copolymer used in the present invention, the B block, which functions as a solvent affinity site, improves the solvent affinity and improves the dispersibility and dispersion stability of the coloring material. ) preferably contains at least one structural unit represented by
Since the structural unit represented by the general formula (IV) contained in the B block may be the same as those described in the graft copolymer, the description thereof is omitted here.

In the B block, the structural unit represented by the general formula (IV) may be used singly or in combination of two or more.
From the viewpoint of dispersibility and dispersion stability of the coloring material, the total proportion of the structural units represented by the general formula (IV) in the B block is 100% by mass with respect to all the structural units of the B block. There may be. From the viewpoint of dispersibility and dispersion stability of the coloring material, the total proportion of the structural units represented by the general formula (IV) in the B block is 40% by mass or more with respect to all the structural units of the B block. and more preferably 70% by mass or more.

Further, the B block is a group consisting of structural units represented by the general formula (V) and structural units represented by the general formula (V') among the structural units represented by the general formula (IV). It is preferable to contain at least one structural unit selected from from the viewpoint of suppressing the generation of foreign matter, improving the adhesion to the substrate, and shortening the development time.
At least one structural unit selected from the group consisting of the structural unit represented by the general formula (V) and the structural unit represented by the general formula (V') contained in the B block includes a graft Since it may be the same as that described in the polymer, the description here is omitted.

In the B block, at least one structural unit selected from the group consisting of structural units represented by the general formula (V) and structural units represented by the following general formula (V') may be Although it is good, two or more kinds may be mixed.
From the viewpoint of suppressing the generation of foreign matter and improving the adhesion to the substrate and shortening the development time, the structural unit represented by the general formula (V) and the structure represented by the following general formula (V') The total proportion of at least one structural unit selected from the group consisting of units is preferably 5% by mass or more, more preferably 10% by mass or more, relative to all the structural units of the B block. , more preferably 15% by mass or more. The total proportion of at least one structural unit selected from the group consisting of the structural unit represented by the general formula (V) and the structural unit represented by the following general formula (V') is the solvent re-solubility point Therefore, it is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, based on all structural units of the B block.

The B block includes at least one structural unit selected from the group consisting of structural units represented by the general formula (V) and structural units represented by the following general formula (V′). Other structural units may be included in addition to the structural units represented by general formula (IV).
Examples of other structural units include structural units derived from ethylenically unsaturated monomers that are copolymerizable with the ethylenically unsaturated monomers from which the structural units represented by general formula (IV) are derived.
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 B block, the total proportion of other structural units is preferably 30% by mass or less, and 10% by mass or less, relative to all the structural units of the B block, from the viewpoint of the effects of the present invention. is more preferred.

The mass average molecular weight Mw of the B block 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 coloring material, It is more preferably 15,000 or less, and even more preferably 12,000 or less.
Within the above range, a sufficient steric repulsion effect as a dispersant can be maintained, and the above-described effects can be improved by increasing the specific surface area of the solvent affinity portion of the dispersant.
The mass-average molecular weight Mw of only the B block can be measured in the same manner as for the dispersant, which will be described later, for the polymer of only the B block.

The B block preferably has an acid value of 10 mgKOH/g or less, more preferably 0 mgKOH/g, from the viewpoint of suppressing the generation of foreign matter and dispersion stability. Here, the acid value can be measured in the same manner as the acid value of the dispersant, which will be described later, for the polymer having only the B block.
The B block is at least one selected from the group consisting of structural units represented by the general formula (I) and structural units represented by the general formula (II), as long as the effects of the present invention are not impaired. Structural units containing acidic groups such as seed structural units may be contained, but from the viewpoint of dispersion stability, the total ratio of structural units containing acidic groups to all structural units of the B block is preferably 5% by mass or less, more preferably 0% by mass.

The B block preferably has an amine value of less than 10 mgKOH/g, more preferably 0 mgKOH/g, from the viewpoint of dispersion stability. Here, the amine value of the B block can be measured in the same manner as the amine value of the polymer chain described above for a polymer having only the B block.
The B block may contain a nitrogen atom-containing structural unit as long as the effects of the present invention are not impaired. The total proportion of the structural units is preferably 5% by mass or less, more preferably 0% by mass.

In addition, the B block may be selected so as to function as a solvent affinity site, and the structural unit may consist of one type, or two or more types may be mixed. When the B block contains two or more structural units, the two or more structural units may be randomly copolymerized within the B block.

The bonding order of the block copolymer is not particularly limited as long as it can stably disperse the coloring material, but the A block is bonded to one end of the block copolymer. However, the AB type block copolymer, the ABA type block copolymer, and the BAB type block copolymer are preferred from the viewpoint that they are excellent in interaction with the colorant and can effectively suppress aggregation between dispersants. AB type block copolymers and BAB type block copolymers are particularly preferred.

In the block copolymer, the total content of the A block is preferably 3% by mass or more and 60% by mass or less, and 6% by mass or more and 45% by mass or less, based on the total structural units of the main chain of the block copolymer. More preferably, 9% by mass or more and 35% by mass or less is even more preferable. If the total content of the A block in the block copolymer is within the above range, the ratio of the portion having an affinity for the coloring material in the block copolymer becomes appropriate, and a decrease in solubility in solvents can be suppressed. Therefore, the adsorption to the coloring material is improved, and excellent dispersibility, dispersion stability and solvent re-solubility are obtained.
In the block copolymer, the content of the structural unit represented by the general formula (I) is preferably 3% by mass or more and 60% by mass or less with respect to all the structural units of the main chain of the block copolymer, It is more preferably 6% by mass or more and 45% by mass or less, and even more preferably 9% by mass or more and 35% by mass or less. If the content ratio of the structural unit represented by the general formula (I) in the block copolymer is within the above range, the proportion of the affinity portion with the colorant in the block copolymer becomes appropriate, and Since it is possible to suppress the deterioration of the solubility in solvents, the adsorptivity to coloring materials is improved, and excellent dispersibility, dispersion stability and solvent re-solubility can be obtained.

On the other hand, in the block copolymer, the total content of the B block is preferably 40% by mass or more and 97% by mass or less, and 55% by mass or more and 94% by mass, based on the total structural units of the main chain of the block copolymer. The following are more preferable, and 65% by mass or more and 91% by mass or less are even more preferable. When the total content of the B block in the block copolymer is within the above range, the ratio of the solvent affinity portion in the block copolymer becomes appropriate, and a sufficient steric repulsion effect as a dispersant can be maintained. In addition, by increasing the specific surface area of the solvent-affinitive portion of the dispersant, the above effects can be improved.
In addition, the content ratio of the structural unit is derived from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (IV) when synthesizing the block copolymer. It is calculated from the charged amount of the monomer.

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

{Characteristics of polymer having structural unit represented by general formula (I)}
The amine value of the polymer having the structural unit represented by the general formula (I) before salt formation is less than 10 mgKOH/g in order to form a coating film in which generation of foreign matter is suppressed. The amine value of the polymer having the structural unit represented by formula (I) before salt formation may be less than 3 mgKOH/g, preferably 0 mgKOH/g from the viewpoint of dispersion stability.
The amine value of the polymer having the structural unit represented by formula (I) before salt formation can be measured in the same manner as the amine value of the polymer chain described above.

Further, the acid value of the polymer having the structural unit represented by the general formula (I) before salt formation is preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g or more, from the viewpoint of dispersion stability. more preferably 40 mgKOH/g or more, still more preferably 50 mgKOH/g or more, and even more preferably 60 mgKOH/g or more.
On the other hand, the acid value of the polymer having the structural unit represented by the general formula (I) before salt formation is preferably 250 mgKOH/g or less, preferably 180 mgKOH/g or less, from the viewpoint of solvent resolubility. more preferably 160 mgKOH/g or less, even more preferably 120 mgKOH/g or less.
The acid value of the polymer having the structural unit represented by the general formula (I) before salt formation is the mass of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid content of the copolymer. (mg) and is a value measured by the method described in JIS K 0070:1992.

The mass-average molecular weight Mw of the polymer having the structural unit represented by the general formula (I) before salt formation is preferably 4000 or more, more preferably 5000 or more, from the viewpoint of dispersibility and dispersion stability. is more preferable, and 6000 or more is even more preferable. 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 ratio (Mw/Mn) between the mass average molecular weight Mw and the number average molecular weight Mn of the dispersant, which is the graft copolymer, is preferably 4.0 or less, and 3.5 from the viewpoint of dispersion stability. It is more preferably 3.0 or less.
In addition, the ratio (Mw/Mn) between the mass average molecular weight Mw and the number average molecular weight Mn of the dispersant, which is the block copolymer, is preferably 1.8 or less, and 1.6 from the viewpoint of dispersion stability. It is more preferably 1.4 or less, more preferably 1.4 or less.
In the present invention, the mass average molecular weight Mw and number average molecular weight Mn are values measured by GPC (gel permeation chromatography). The measurement was carried out using Tosoh's HLC-8120GPC, the elution solvent was N-methylpyrrolidone to which 0.01 mol/liter of lithium bromide was added, 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.

[Salt polymer]
The salt-type polymer used as a dispersant in the present invention includes at least part of the acidic groups contained in the general formula (I) of the polymer having the structural unit represented by the general formula (I), and a basic It is a salt-type polymer in which a compound forms a salt.
The basic compound forming a salt with at least part of the acidic groups in the salt-type polymer may be a nitrogen-containing basic compound having a pKa of 11.5 or more, or a basic compound having a pKa of 11.5. A basic compound different from the above nitrogen-containing basic compounds may be included.

Since the nitrogen-containing basic compound having a pKa of 11.5 or more may be the same as described above, the description thereof is omitted here.
Examples of the basic compound different from the nitrogen-containing basic compound having a pKa of 11.5 or more include a nitrogen-containing basic compound having a pKa of less than 11.5.

Basic compounds different from nitrogen-containing basic compounds having a pKa of 11.5 or more include, for example, N,N,N′,N″,N″-pentamethyldiethylenetriamine (pKa: 8.8), tetramethylethylenediamine (pKa: 8.3), dimethylaminoethyl methacrylate (pKa: 8.2), dimethylbenzylamine (pKa: 9), triethylamine (pKa: 10.8), tributylamine (pKa: 10), bis(2- dimethylaminoethyl) ether (pKa: 9.1), N,N,N',N'-tetramethylpropanediamine (pKa: 9.9), N,N,N',N'-tetramethyl-1, 6-hexanediamine (pKa: 10.1), 2-(dimethylamino)ethanol (pKa: 9.3), N,N,N',N',N''-pentamethyldipropylenetriamine (pKa: 9. 9), tertiary amino group-containing basic compounds such as N,N-dimethylcyclohexylamine (pKa: 10.7), N-[3-(dimethylamino)propyl]acrylamide (pKa: 10.4), and 2 -methylimidazole (pKa: 7.8), 1-isobutyl-2-methylimidazole (pKa: 7.8), and basic heterocyclic compounds such as triethylenediamine (pKa: 8.8).

The basic compound forming a salt with at least part of the acidic groups in the salt-type polymer preferably has a molecular weight of 800 or less, more preferably 650 or less, from the viewpoint of dispersibility and dispersion stability. More preferably, it is 500 or less, and even more preferably 350 or less. On the other hand, the basic compound preferably has a molecular weight of 60 or more from the viewpoint of heat resistance.

In the salt-type polymer, the content of the basic compound forming a salt with at least a part of the acidic groups forms a salt with the terminal acidic group of the structural unit represented by general formula (I). Therefore, the total amount of at least one selected from basic compounds is preferably 0.01 molar equivalent or more with respect to the terminal acidic group of the structural unit represented by general formula (I). , more preferably 0.05 molar equivalents or more, more preferably 0.10 molar equivalents or more, and particularly preferably 0.15 molar equivalents or more. If it is at least the above lower limit, the effect of improving colorant dispersibility, contrast, substrate adhesion and brightness by salt formation is likely to be obtained. Similarly, it is preferably 1.0 molar equivalents or less, more preferably 0.9 molar equivalents or less, even more preferably 0.8 molar equivalents or less, and 0.7 molar equivalents or less. is particularly preferred. When it is at most the above upper limit, excellent alkali developability and solvent re-solubility can be obtained.
In addition, a basic compound may be used individually by 1 type, and may combine 2 or more types. When combining two or more, the total content is preferably within the above range.

As a method for preparing the salt-type polymer, the basic compound is added to a solvent in which the polymer having the structural unit represented by the general formula (I) before salt formation is dissolved or dispersed, and the mixture is stirred. A method of heating, if necessary, and the like can be mentioned.
The fact that the terminal acidic group of the structural unit represented by the general formula (I) of the polymer and the basic compound form a salt, and the ratio thereof can be determined by known methods such as NMR. It can be confirmed by the method.

{Preferred Embodiment of Polymer Having Structural Unit Represented by Formula (I)}
From the viewpoint of dispersibility and dispersion stability, the polymer having a structural unit represented by the general formula (I) and having an amine value of less than 10 mgKOH/g before salt formation is
A graft copolymer having a structural unit represented by the general formula (I), and at least part of the acidic groups contained in the general formula (I) in the graft copolymer and a basic compound form a salt. a salt-type graft copolymer, and
A block copolymer having an A block containing a structural unit represented by the general formula (I), and at least part of the acidic groups contained in the general formula (I) in the block copolymer and a basic compound is at least one of salt-type block copolymers forming a salt.
In addition, the polymer having the structural unit represented by the general formula (I) and having an amine value of less than 10 mgKOH/g before salt formation has good dispersibility and dispersion stability, and suppresses the generation of foreign matter, A graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (III), wherein the polymer chain in the general formula (III) is the general formula ( V) and a graft copolymer containing at least one structural unit selected from the group consisting of structural units represented by the general formula (V′), and in the graft copolymer, the A salt-type graft copolymer in which at least part of the acidic groups contained in the general formula (I) and a basic compound form a salt, and
An A block containing a structural unit represented by the general formula (I) and a B block containing a structural unit represented by the general formula (IV), wherein the B block is represented by the general formula (V) and a block copolymer containing at least one structural unit selected from the group consisting of structural units represented by the general formula (V′), and in the block copolymer, the general formula (I A more preferred embodiment is at least one salt-type block copolymer in which at least part of the acidic groups contained in ) and the basic compound form a salt.

In the dispersant used in the colorant dispersion according to the present invention, the content of the polymer having the structural unit represented by the general formula (I) and having an amine value of less than 10 mgKOH/g before salt formation is , preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and may be 100% by mass.

In the colorant dispersion according to the present invention, the dispersant contains at least a polymer having a structural unit represented by the general formula (I) and having an amine value of less than 10 mgKOH/g before salt formation. , other dispersants may be contained as long as the effects of the present invention are not impaired. As another dispersant, for example, a known dispersant can be appropriately selected and used.

Since the colorant dispersion according to the present invention contains an acidic group-containing compound having a pKa of 4.0 or less, a basic dispersant capable of forming a salt with an acidic group-containing compound having a pKa of 4.0 or less is further added. may contain.
As the basic dispersant, among others, a polymer having a constitutional unit represented by the following general formula (VI) and having an amine value of 35 mgKOH/g or more before forming a salt is preferred in terms of dispersibility and dispersion stability. , is preferred from the point of solvent re-solubility.

(In general formula (VI), R ³¹ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ³² and R ³³ are each independently a hydrogen atom, or a carbon atom that may contain a hetero atom. represents a hydrogen group, and R ³² and R ³³ may combine with each other to form a ring structure.)

[Polymer having structural unit represented by general formula (VI)]
In general formula (VI) ^, A3 is a divalent linking group. The divalent linking group in A3 may be the same as A in the general formula ⁽ I).

Examples of the hydrocarbon group in the hydrocarbon group optionally containing a heteroatom for R ³² and R ³³ 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, a benzyl group, a phenethyl group, a naphthylmethyl group, a 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 heteroatom-containing hydrocarbon group has a structure in which a carbon atom in the above hydrocarbon group is replaced with a heteroatom. Examples of the heteroatom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like.
A hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as an alkyl group having 1 to 5 carbon atoms, fluorine atom, chlorine atom or bromine atom.

The expression that R ³² and R ³³ are bonded to each other to form a ring structure means that R ³² and R ³³ form a ring structure via a nitrogen atom. A heteroatom may be included in the ring structure formed by R ³² and R ³³ . 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 ³² and R ³³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R ³² and R ³³ are bonded to form a pyrrolidine ring, It preferably forms a piperidine ring or a morpholine ring, in which at least one of R ³² and R ³³ is an alkyl group having 1 to 5 carbon atoms or a phenyl group, or R ³² and R ³³ are bonded preferably form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

Examples of structural units represented by the general formula (VI) include alkyl group-substituted amino groups such as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate and diethylaminopropyl (meth)acrylate. Examples thereof include 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 general formula (VI) may consist of one type, or may contain two or more types of structural units.

The polymer having the structural unit represented by the general formula (VI) is preferably a copolymer from the viewpoint of dispersibility and dispersion stability, and the structural unit represented by the general formula (VI) is and a block copolymer having an A block containing a structural unit represented by the general formula (VI).

In the graft copolymer having a structural unit represented by the general formula (VI), the structural unit having a graft polymer chain that functions as a solvent affinity site has a structural unit represented by the general formula (I). It may be the same as the structural unit having a graft polymer chain in the graft copolymer or the structural unit represented by the general formula (III).

Further, in the graft copolymer having the structural unit represented by the general formula (VI), the content ratio of the structural unit represented by the general formula (VI) to the total structural units of the main chain of the graft copolymer may be the same as the content ratio of the structural unit represented by the general formula (I) in the graft copolymer having the structural unit represented by the general formula (I).
Further, in the graft copolymer having a structural unit represented by the general formula (VI), the structural unit containing the graft polymer chain or the general formula (III) for all the structural units of the main chain of the graft copolymer The total content of the structural units represented by the above general formula (I) is a structural unit containing a graft polymer chain in a graft copolymer having a structural unit represented by the general formula (I) or a structural unit represented by the general formula (III). may be the same as the total content ratio of
Furthermore, the method for producing the graft copolymer having the structural unit represented by the general formula (VI) is the same as the method for producing the graft copolymer having the structural unit represented by the general formula (I). It's fine.

Further, in the block copolymer having the A block containing the structural unit represented by the general formula (VI), the B block functioning as a solvent affinity site is the structural unit represented by the general formula (I). It may be the same as the B block in the block copolymer having the A block containing.
Also, the bonding order of the block copolymer may be the same as that of the block copolymer containing the structural unit represented by the general formula (I).

In the block copolymer having a structural unit represented by the general formula (VI), the total content of the A block with respect to all the structural units of the main chain of the block copolymer, or the general formula (VI) The content ratio of the structural unit represented by the general formula (I) is the total content ratio of the A block in the block copolymer having the structural unit represented by the general formula (I), or the content ratio of the structural unit represented by the general formula (I) may be similar to
Further, in the block copolymer having the structural unit represented by the general formula (VI), the total content of the B block with respect to all the structural units of the main chain of the block copolymer is represented by the general formula (I). It may be the same as the total content of B blocks in the graft copolymer having the represented structural units.
Furthermore, the method for producing the block copolymer having the structural unit represented by the general formula (VI) is the same as the method for producing the block copolymer having the structural unit represented by the general formula (I). It's fine.

{Characteristics of polymer having structural unit represented by general formula (VI)}
The mass average molecular weight Mw of the polymer having the structural unit represented by the general formula (VI) is preferably 4000 or more, more preferably 5000 or more, from the viewpoint of dispersibility and dispersion stability. 6000 or more is even more preferable. 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 ratio (Mw/Mn) between the mass average molecular weight Mw and the number average molecular weight Mn of the dispersant, which is the graft copolymer, is preferably 4.0 or less, and 3.5 from the viewpoint of dispersion stability. It is more preferably 3.0 or less.
In addition, the ratio (Mw/Mn) between the mass average molecular weight Mw and the number average molecular weight Mn of the dispersant, which is the block copolymer, is preferably 1.8 or less, and 1.6 from the viewpoint of dispersion stability. It is more preferably 1.4 or less, more preferably 1.4 or less.
The mass-average molecular weight Mw and number-average molecular weight Mn can be measured in the same manner as for the polymer having the structural unit represented by formula (I).

From the viewpoint of colorant dispersibility and dispersion stability, the lower limit of the amine value of the polymer having the structural unit represented by the general formula (VI) is 35 mgKOH/g or more, but 40 mgKOH/g or more. preferably 50 mgKOH/g or more, and even more preferably 60 mgKOH/g or more. Further, the upper limit is 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 polymer having the structural unit represented by the general formula (VI) means that 1 g of the solid content of the polymer having the structural unit represented by the general formula (VI) is neutralized. It represents the mass (mg) of potassium hydroxide that is equivalent to the amount of hydrochloric acid required to do so, and is a value measured by the method described in JIS K 7237.

{Salt-type polymer of a polymer having a structural unit represented by the general formula (VI)}
As a dispersant, from the viewpoint of dispersibility and dispersion stability, the terminal nitrogen site of the structural unit represented by the general formula (I) of the polymer having the structural unit represented by the general formula (VI) and at least a part of and one or more compounds selected from the group consisting of the following general formulas (1) to (3) may form a salt.
Further, at least part of the terminal nitrogen portion of the structural unit represented by the general formula (I) of the polymer having the structural unit represented by the general formula (VI), and the pKa of 4.0 or less It may be a salt-type polymer in which a salt is formed with an acidic group-containing compound.

As the salt-type polymer, a graft copolymer having a structural unit represented by the general formula (VI), or a block copolymer having an A block containing a structural unit represented by the general formula (VI) In coalescence, one selected from the group consisting of at least part of the terminal nitrogen portion possessed by the structural unit represented by the general formula (VI) and the compounds represented by the following general formulas (1) to (3) A salt-type graft copolymer or a salt-type block copolymer in which the above compounds form a salt is preferable.
Among them, as the salt-type polymer, a graft copolymer having a structural unit represented by the general formula (VI), or a block having an A block containing a structural unit represented by the general formula (VI) A salt-type graft copolymer in which at least part of the terminal nitrogen portion of the structural unit represented by the general formula (VI) in the copolymer forms a salt with the acidic group-containing compound having a pKa of 4.0 or less. Polymers or salt-type block copolymers are preferred.

(In the general formula (1), R ^a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, or -O- R ^b represents 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 C 1 to 4 It represents a (meth)acryloyl group via an alkylene group.
In general formula (2), each of R ^c and R ^d may independently have a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a substituent. represents a phenyl group, a benzyl group, or —O—R ^e , where R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group optionally having a substituent, or It represents a benzyl group or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms. However, at least one of ^Rc and ^Rd contains a carbon atom.
In the general formula (3), R ^f , R ^f′ and R ^f″ are each independently a hydrogen atom, an acidic group or an ester group thereof, a linear chain having 1 to 20 carbon atoms which may have a substituent, represents a branched or cyclic alkyl group, a vinyl group optionally having a substituent, a phenyl group or a benzyl group optionally having a substituent, or —OR ^{g, wherein R g} ^has a substituent; a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group optionally having substituents, a phenyl group or benzyl group optionally having substituents, or 1 carbon atom represents a (meth)acryloyl group via an alkylene group of ~4, and X represents a chlorine atom, a bromine atom, or an iodine atom.)

For the explanation of each symbol of the compound represented by (3), the explanation of the symbol corresponding to the general formula (2) described in International Publication No. 2016/104493 can be referred to. Structures and examples of one or more compounds selected from the group consisting of the general formulas (1) to (3) include structures described in WO 2016/104493.

In the salt-type polymer, the content of one or more compounds selected from the group consisting of the general formulas (1) to (3) is the terminal nitrogen portion of the structural unit represented by the general formula (VI). Since it forms a salt, it is selected from the group consisting of the general formulas (1) to (3) with respect to 1 mol of the terminal nitrogen site of the structural unit represented by the general formula (VI). It is preferable that the one or more compounds to be used is 0.05 mol or more, more preferably 0.10 mol or more, further preferably 0.20 mol or more, and 0.30 mol or more. is particularly preferred. 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 0.95 mol or less, even more preferably 0.90 mol or less, and particularly preferably 0.85 mol or less. It should be excellent in solvent resolubility as it is below the said upper limit.
One or more compounds selected from the group consisting of the general formulas (1) to (3) may be used singly or in combination of two or more. When combining two or more, the total content is preferably within the above range.

In the present invention, the content ratio and structure of each structural unit of the dispersant can be determined using various mass spectrometry, NMR, and the like. In addition, if necessary, the dispersant is decomposed by thermal decomposition or the like, and the obtained decomposition product is subjected to high performance liquid chromatography, gas chromatograph mass spectrometer, NMR, elemental analysis, XPS / ESCA, TOF-SIMS, etc. can ask.

In the colorant dispersion liquid according to the present invention, as the dispersant, at least a polymer having a constitutional unit represented by the general formula (I) and having an amine value before salt formation of less than 10 mgKOH/g is used and dispersed. The content of the agent is appropriately selected according to the type of coloring material used, the solid content concentration in the colored curable composition described later, and the like.
The content of the dispersant is, for example, preferably 3% to 60% by mass, more preferably 5% to 45% by mass, based on the total solid content in the colorant dispersion. If it is at least the above lower limit, the dispersibility and dispersion stability of the coloring material and solvent re-solubility tend to be excellent. Moreover, if it is below the said upper limit, developability will become favorable easily.

<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.

The colorant dispersion liquid according to the present invention contains the above solvent in an amount of usually preferably 55% by mass to 95% by mass, more preferably 65% by mass, based on the total amount of the colorant dispersion liquid containing the solvent. to 90% by mass, more preferably 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 colored curable 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.

In the colorant dispersion liquid according to the present invention, the polymer having a constitutional unit represented by the general formula (I) below and having an amine value before salt formation of less than 10 mgKOH/g has the general formula (I) Forming a salt with at least part of the acidic group contained in the above nitrogen-containing basic compound having a pKa of 11.5 or more suppresses the generation of foreign matter, dispersibility and dispersion stability, solvent It is preferable from the point of re-solubility. Even if a salt-type polymer salt-formed with a nitrogen-containing basic compound having a pKa of 11.5 or more is not used, the acidic group contained in the general formula (I) is added to the colorant dispersion liquid. can form a salt with at least part of and the nitrogen-containing basic compound having a pKa of 11.5 or more.
Further, the colorant dispersion according to the present invention further contains a polymer having a structural unit represented by the general formula (VI) and having an amine value of 35 mgKOH/g or more before salt formation, and In a polymer having a structural unit represented by formula (VI) and having an amine value of 35 mgKOH/g or more before salt formation, at least one terminal nitrogen site of the structural unit represented by general formula (II) It is preferable that part and the acidic group-containing compound having a pKa of 4.0 or less form a salt from the viewpoint of suppressing the generation of foreign matter, dispersibility, dispersion stability, and solvent re-solubility.

The coloring material dispersion liquid according to the present invention is used as a preliminary preparation for preparing the colored curable composition described later. That is, the colorant dispersion is preliminarily prepared in the stage prior to preparing the colored curable composition described later, (the mass of the colorant component in the composition) / (the solid content other than the colorant component in the composition) It is a coloring material dispersion with a high mass) 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. By mixing the colorant dispersion and each component described later, a highly dispersible colored curable composition can be prepared.

<Method for Producing Colorant Dispersion>
In the present invention, a method for producing a colorant dispersion comprises a colorant, a dispersant containing the specific polymer, a nitrogen-containing basic compound having a pKa of 11.5 or more, and an acidic compound having a pKa of 4.0 or less. The method is not particularly limited as long as it contains a group-containing compound and a solvent, and the coloring material is dispersed in the solvent by the dispersing agent to obtain a coloring material dispersion.

As described above, the method for producing the colorant dispersion according to the present invention includes, for example, the following aspects.
i) a dispersant containing a coloring material, a specific polymer having a structural unit represented by the general formula (I), a nitrogen-containing basic compound having a pKa of 11.5 or more, and a pKa of 4.0 or less and a solvent are mixed to disperse the coloring material.
ii) a dispersant containing a salt-type polymer obtained by forming a salt of a specific polymer having a structural unit represented by the general formula (I) with a nitrogen-containing basic compound having a pKa of at least 11.5 or more; , an acidic group-containing compound having a pKa of 4.0 or less, a colorant, and a solvent are mixed to disperse the colorant.
iii) a salt-type polymer obtained by forming a salt in advance with a nitrogen-containing basic compound having a pKa of at least 11.5 or more on a specific polymer having a structural unit represented by the general formula (I), and a basic dispersion; A dispersing agent containing a salt-type polymer obtained by forming a salt in advance with an acidic group-containing compound having a pKa of 4.0 or less, a coloring material, and a solvent are mixed to disperse the coloring material.
iv) a modified coloring material obtained by modifying the coloring material in advance with a nitrogen-containing basic compound having a pKa of 11.5 or more and an acidic group-containing compound having a pKa of 4.0 or less; A dispersing agent containing a specific polymer having a structural unit with a solvent is mixed with a solvent to disperse the coloring material.

In the above production 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 with a relatively large bead diameter, and main dispersion is performed with 0.1 mm zirconia beads with a relatively small bead diameter. Moreover, after dispersion, it is preferable to filter through a filter of 0.5 to 2 μm.

<Application>
The coloring material dispersion liquid according to the present invention is a coloring material dispersion liquid capable of forming a coating film in which chromaticity change during heating is suppressed, luminance is improved, and foreign matter generation is suppressed. Since the material is a coloring material with suppressed chromaticity change upon heating and improved brightness, it can be suitably used for color filters.
Moreover, the colorant dispersion liquid and the modified colorant according to the present invention can also be used for a colored resin composition or a thermosetting colored resin composition that does not require a photosensitive component.
The colorant dispersion and the modified colorant according to the present invention are used in various applications that require excellent dispersion stability of fine colorants, such as inkjet inks, printing inks, writing utensils, and cosmetics. Also used for

II. Colored Curable Composition The colored curable composition according to the present invention is characterized by containing the coloring material dispersion liquid according to the present invention, a polymerizable compound, and an initiator.
By using the colorant dispersion according to the present invention, the colored curable composition of the present invention can form a coating film in which the chromaticity change during heating is suppressed, the brightness is improved, and the generation of foreign matter is suppressed. is.

The colored curable composition of the present invention comprises a coloring material, a dispersant, a nitrogen-containing basic compound having a pKa of 11.5 or more, an acidic group-containing compound having a pKa of 4.0 or less, a polymerizable compound, It contains at least an initiator and a solvent, and may contain other components as long as the effects of the present invention are not impaired. Hereinafter, each component contained in the colored curable composition of the present invention will be described. The group-containing compound and the solvent are the same as those described for the colorant dispersion liquid according to the present invention, and thus descriptions thereof are omitted here.

<Polymerizable compound>
The polymerizable compound is not particularly limited as long as it can be polymerized by an initiator described later, and for example, a photopolymerizable compound or a thermally polymerizable compound can be used. As the thermally polymerizable compound, a compound having a thermally polymerizable functional group such as a carboxyl group, amino group, epoxy group, hydroxyl group, glycidyl group, isocyanate group, and alkoxyl group in the molecule can be used. A compound having an ethylenically unsaturated group can also be used as a thermally polymerizable compound by using it in combination with a thermal radical polymerization initiator. As the polymerizable compound, a photopolymerizable compound that can be polymerized by a photoinitiator, which will be described later, is preferable because a pattern can be easily formed by photolithography using an existing process.

The photopolymerizable compound used in the colored curable composition is not particularly limited as long as it can be polymerized by a 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.

These photopolymerizable compounds may be used singly or in combination of two or more. Further, when excellent photocurability (high sensitivity) is required for the colored curable composition of the present invention, the photopolymerizable compound has three (trifunctional) or more polymerizable double bonds. 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 polymerizable compound in the colored curable composition is, for example, preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, based on the total solid content of the colored curable composition. %, more preferably 20% by mass to 40% by mass. When the content of the polymerizable compound is at least the above lower limit, poor curing can be suppressed, so that the exposed portion can be suppressed from eluting during development, and the content of the polymerizable compound is at most the above upper limit. , development defects can be suppressed, and heat shrinkage can be suppressed, so fine wrinkles are less likely to occur on the entire surface of the colored layer.

<Initiator>
The initiator used in the colored curable 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 the initiator include polymerization initiators such as thermal polymerization initiators and photopolymerization initiators, and specific examples thereof include those described in JP-A-2013-029832.

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, 1-(9,9-dibutyl-9H-fluoren-2-yl)-2-methyl-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, for example, preferably 5% by mass to 15% by mass based on the total solid content of the colored curable 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, it is preferable from the viewpoint of improving resistance to development such as water staining.

In the present invention, the photoinitiator preferably contains an oxime ester photoinitiator, among others, from the viewpoint of being able to improve the 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.
As the oxime ester photoinitiator, from the viewpoint of reducing contamination of the colored curable 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 are preferable. More preferably, it has 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-T-2010-527339, JP-T-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 having a diphenyl sulfide skeleton, Adeka Arcules NCI-930, TR-PBG-345, TR-PBG-304 having a carbazole skeleton, Irgacure OXE-02 having a fluorene skeleton, and Adeka Arcules NCI. -831, TR-PBG-365, TR-PBG-3057 having a diphenyl sulfide skeleton (manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.), and the like may also 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. Moreover, it is preferable to use an oxime ester photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.

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 the 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 initiator in the colored curable composition is, for example, preferably 0.1% by mass to 15% by mass, more preferably 1% by mass to 10% by mass, based on the total solid content of the colored curable composition. % by mass. When the content of the initiator is at least the above lower limit, curing proceeds sufficiently, and when the content of the initiator is at most the above upper limit, side reactions can be suppressed and stability over time can be maintained. can.

<Other ingredients>
If necessary, the colored curable composition of the present invention may contain a polymer such as an alkali-soluble resin, an antioxidant, and various additives.

(polymer)
As the polymer, when a photolithography process is used to form the colored layer, an alkali-soluble resin that is soluble in an alkali developer is preferably used. In the present invention, since the dispersant has an acidic group, it can also function as an alkali-soluble resin. Therefore, even when a photolithography process is used, an alkali-soluble resin different from the dispersant is not an essential component.
In the photosensitive colored resin composition of the present invention, it is preferable to further contain an alkali-soluble resin different from the dispersant from the viewpoint of facilitating adjustment of the alkali-solubility.
The alkali-soluble resin has an acidic group, and can be appropriately selected and used as long as it acts as a binder resin and is soluble in the alkali developer used for pattern formation.
In the present invention, the alkali-soluble resin can be defined as having an acid value of 30 mgKOH/g or more.

As the alkali-soluble resin, a conventionally known alkali-soluble resin can be appropriately selected and used. For example, an alkali-soluble resin described in WO2016/104493 can be appropriately selected and used.
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.

The content of the alkali-soluble resin used in the colored curable composition is not particularly limited, but is preferably 1% by mass to 60% by mass, more preferably 5% by mass, based on the total solid content of the colored curable composition. It is in the range of mass % to 40 mass %. When the content of the alkali-soluble resin is at least the above lower limit value, sufficient alkali developability is easily obtained, and when the content of the alkali-soluble resin is at most the above upper limit value, film roughness and pattern chipping occur during development. is easy to suppress.
In the present invention, the solid content includes all substances other than the solvent, including monomers and the like dissolved in the solvent.

Further, the colored curable composition according to the present invention includes, as the polymer, for example, a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, an unsaturated polyester resin, a polyurethane resin, an epoxy resin, an aminoalkyd resin, Thermosetting polymers such as melamine-urea cocondensation resins, silicon resins, and polysiloxane resins may also be contained.

In addition, the said polymer may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the polymer in the colored curable composition is not particularly limited, but is, for example, preferably 1% by mass to 60% by mass, more preferably 5% by mass, based on the total solid content of the colored curable composition. % to 50% by mass. When the polymer content is at least the above lower limit, it is easy to suppress a decrease in film strength, and when the polymer content is at most the above upper limit, components other than the polymer can be sufficiently contained.

(Antioxidant)
It is preferable that the colored curable composition of the present invention further contains an antioxidant from the viewpoint of improving heat resistance, suppressing discoloration of the coloring material, and improving luminance. 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 colored curable composition of the present invention contains the oxime ester photoinitiator and an antioxidant in combination, the synergistic effect improves the brightness and forms a fine line pattern as designed for the mask line width. It is preferable from the point of improving the ability.

The content of the antioxidant is not particularly limited, but is usually preferably 0.1% by mass to 10.0% by mass, more preferably 0, based on the total solid content in the colored curable composition. 0.5 mass % to 5.0 mass %. If it is at least the above lower limit, it tends to be excellent in heat resistance and light resistance. On the other hand, if it is the above upper limit or less, the colored curable composition of the present invention is likely to be a highly sensitive photosensitive resin composition.

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

(Various additives)
The colored curable composition of the present invention may contain various additives.
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.

As the content of the silane coupling agent, the silane coupling agent is preferably 0.05% by mass or more and 10.0% by mass or less with respect to the total solid content in the colored curable composition, and 0.1 More preferably, the content is not less than 5.0% by mass and not more than 5.0% by mass. If it is more than the said lower limit and below the said upper limit, it is excellent in base-material adhesion.

<Ratio of each component in the colored curable composition>
The total content of the coloring material is not particularly limited, but is preferably in the range of 3% to 65% by mass, more preferably 4% to 60% by mass, based on the total solid content of the colored curable composition. is within. If it is at least the above lower limit, the colored layer tends to have a sufficient color density when the colored curable 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, it will be easy to obtain a coloring layer which has sufficient hardness and adhesiveness with a board|substrate. Particularly when forming a colored layer having a high colorant concentration, the content of the colorant is, for example, preferably 15% by mass to 75% by mass, more preferably 25% by mass, based on the total solid content of the colored curable composition. % to 70% by weight.
Further, the content of the dispersant is not particularly limited as long as it can uniformly disperse the coloring material. % to 40% by mass, more preferably 2% to 30% by mass, and even more preferably 3% to 25% by mass. 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 colored curable composition tends to be excellent. Moreover, if it is below the said upper limit, alkali developability will become favorable easily. Especially when forming a colored layer having a high colorant concentration, the content of the dispersant is, for example, preferably 2% by mass to 25% by mass, more preferably 3% by mass, based on the total solid content of the colored curable composition. % to 20% by mass.
Moreover, the content of the solvent may be set as appropriate within a range that allows the colored layer to be formed with high accuracy. For example, it is preferably 55% by mass to 95% by mass, more preferably 65% by mass to 88% by mass, based on the total amount of the colored curable composition containing the solvent. When the content of the solvent is within the above range, excellent applicability can be obtained.

<Method for producing colored curable composition>
The method for producing the colored curable composition of the present invention is not particularly limited. can be obtained by adding the components of and mixing using a known mixing means.

<Application>
The colored curable composition according to the present invention suppresses the chromaticity change during heating, improves the brightness, and can form a coating film in which the generation of foreign matter is suppressed. Therefore, it is particularly suitable for use in color filters. be able to.
The colored curable composition according to the present invention is used for various applications requiring excellent dispersion stability of fine colorants, and is also used for inkjet inks and printing inks.

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 colored curable composition according to the present invention. is a cured product of

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 colored curable composition of 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.
The arrangement of the colored layers is not particularly limited, and may be a general arrangement such as a stripe type, mosaic type, triangle type, four-pixel arrangement type, or the like. Moreover, the width, area, etc. of the colored layer can be arbitrarily set.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and viscosity of the colored curable composition, and is preferably in the range of 1 to 5 μm.

The colored layer can be formed, for example, by the following method.
First, the colored curable 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 depending on the mixing ratio of each component in the colored curable 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 developer is usually washed and the cured coating film of the colored curable 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 to 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 can be used. 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 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 a liquid crystal display device and an organic light emitting display device.

[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 room temperature, thereby aligning the enclosed 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 lamination method of 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.
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 acid value and amine value of the graft copolymer and block copolymer before salt formation were determined according to the measurement methods described in the specification of the present invention.
The weight average molecular weight (Mw) and Mw/Mn of the graft copolymer and block copolymer are standard polystyrene conversion values by GPC (gel permeation chromatography) according to the measurement method described in the specification of the present invention. I asked as

The acid value of the graft copolymer and block copolymer after salt formation (hereinafter sometimes referred to as a salt-type copolymer) was obtained by calculating as follows.
First, the acid value of the copolymer before salt formation is determined by the method described above. In addition, the 1H-NMR spectrum of the basic compound before salt formation is measured using a nuclear magnetic resonance apparatus. Next, the 1H-NMR spectrum of the mixture of the salt-type copolymer and the basic compound after salt formation is measured using a nuclear magnetic resonance apparatus. Among the obtained spectrum data, the ratio of the integrated value of the hydrogen atom peak near the unsalted salt-forming bond in the salt-forming bond of the basic compound before and after salt formation indicates that the salt-type copolymer , the reaction rate of a basic compound with respect to the terminal acidic group site of the structural unit represented by general formula (I) is measured. The terminal acidic group site of the structural unit represented by the general formula (I) formed by salting the basic compound is measured by the method described in JIS K 0070: 1992, assuming that the acid value is 0. acid value of the copolymer before salt formation)×(proportion of unsalted terminal acidic group sites calculated from 1H-NMR spectrum (%)/100).
In the following examples, in all cases, the salt-forming reaction was carried out until the disappearance of the hydrogen atom peak near the salt-forming bond of the basic compound where no salt was formed. be able to. Therefore, the acid value of the salt-type copolymer = {acid value of the copolymer before salt formation measured by the method described in JIS K 0070: 1992} - {JIS K 0070: measured by the method described in 1992 It can also be calculated by: acid value of copolymer before salt formation}×{basic compound consumed in salt formation reaction (mol)/number of acidic groups of copolymer before salt formation (mol)}.

The amine value of the graft copolymer and block copolymer after salt formation was determined as follows.
Among the salt-type copolymers, the amine value of the salt-type copolymer salt-formed by the compound represented by the general formula (3) is the value measured by the method described in JIS K 7237:1995. did. In the compound of the general formula (3), for example, the terminal nitrogen site of the structural unit represented by the general formula (VI) and the hydrocarbon on the halogen atom side form a salt. This is because the amine value can be measured without causing a change in the
On the other hand, among the salt-type copolymers, the amine value of the salt-type copolymer salt-formed with the compound represented by the general formula (1) or (2) is the copolymerization before the salt formation described above. It was obtained by calculating as follows from the combined amine value. In the compound represented by the general formula (1) or (2), for example, the terminal nitrogen site and the acidic group of the structural unit represented by the general formula (VI) form a salt. This is because when the amine value of the copolymer is measured by the method described in JIS K 7237:1995, the state of salt formation changes, and an accurate value cannot be measured.
First, the amine value of the copolymer before salt formation is determined by the method described above. In addition, the 1H-NMR spectrum of the copolymer before salt formation is measured using a nuclear magnetic resonance apparatus. Next, the 1H-NMR spectrum of the salt-type copolymer after salt formation is measured using a nuclear magnetic resonance apparatus. Among the obtained spectrum data, the ratio of the integrated value of the hydrogen atom peak near the non-salted nitrogen atom at the terminal nitrogen site of the structural unit represented by the general formula (VI) before and after salt formation One or more compounds selected from the group consisting of the general formula (1) or (2) for the terminal nitrogen site of the structural unit represented by the general formula (VI) of the salt-type copolymer. measure the reaction rate of The terminal nitrogen portion of the structural unit represented by the general formula (VI), which is a salt formed by one or more compounds selected from the group consisting of the general formula (1) or (2), has an amine value of 0. (Amine value of copolymer before salt formation measured by the method described in JIS K 7237: 1995) × (Non-salted end nitrogen site ratio (%) calculated from 1H-NMR spectrum )/100).

(Synthesis Example 1: Production of graft copolymer A)
(1) Synthesis of macromonomer m1 A reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 100.0 parts by mass of propylene glycol methyl ether acetate (PGMEA). The mixture was heated to 90° C. while stirring under an air stream. Methyl methacrylate (MMA) 50.0 parts by mass, butyl methacrylate (BMA) 5.0 parts by mass, benzyl methacrylate (BzMA) 5.0 parts by mass, methoxypolyethylene glycol monomethacrylate (manufactured by NOF Corporation, trade name Blenmer PME-200, ethyleneoxy group repeating number = 4) (PME-200) 40.0 parts by mass, mercaptopropionic acid 7.0 parts by mass, α,α'-azobisisobutyronitrile (AIBN)1. 0 parts by mass of the mixed solution was added dropwise over 1.5 hours, and the reaction was further continued for 3 hours. After cooling, the reaction solution was diluted with 200 parts by mass of tetrahydrofuran (THF) and reprecipitated with 3000 parts by mass of hexane to obtain 106.0 parts by mass of white powder. Next, 50.0 parts by weight of PGMEA, 7.4 parts by weight of glycidyl methacrylate (GMA), 0.30 parts by weight of N,N-dimethyldodecylamine and 0.2 parts by weight of p-methoxyphenol were added to 100.0 parts by weight of this white powder. Parts by mass were added, and the mixture was stirred at 110° C. for 24 hours while performing air bubbling. After cooling, this reaction solution was reprecipitated with 3000 parts by mass of hexane to obtain 106.0 parts by mass of macromonomer m1.
The obtained macromonomer m1 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.

(2) Preparation of graft copolymer A A reactor equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer was charged with 100.0 parts by mass of PGMEA, and stirred under a stream of nitrogen. Warmed to a temperature of 85°C. 81.6 parts by mass of the macromonomer m1 of Synthesis Example 1, 12.3 parts by mass of methacrylic acid (MAA), 2-methacryloyloxyethyl succinic acid (2-MOES, represented by the general formula (II-2) A mixed solution of 6.1 parts by mass of derived structural units, 1.3 parts by mass of n-dodecyl mercaptan, 50.0 parts by mass of PGMEA, and 1.0 parts by mass of AIBN was added dropwise over 1.5 hours, followed by heating and stirring for 3 hours. After that, a mixed solution of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA was added dropwise over 10 minutes, followed by aging at the same temperature for 1 hour. After cooling, this reaction solution was reprecipitated with 3000 parts by mass of hexane to obtain 99.0 parts by mass of graft copolymer A. The resulting graft copolymer A had a weight average molecular weight (Mw) of 14,300, an Mw/Mn of 2.5, and an acid value of 95 mgKOH/g.

(3) Preparation of salt-type graft copolymer A To 40.0 parts by mass of PGMEA, 25.0 parts by mass of graft copolymer A, 1,8-diazabicyclo[5.4.0]undecene-7 (manufactured by San-Apro Co., Ltd., "DBU") was added (0.3 molar equivalents with respect to the carboxy group structural unit of the graft copolymer A) and stirred at room temperature for 6 hours to form a salt-type graft copolymer A solution. prepared. This reaction solution was reprecipitated with 1000 parts by mass of hexane to obtain 27.3 parts by mass of a salt-type graft copolymer A.

(Synthesis Example 2: Production of block copolymer B)
150.0 parts by weight of PGMEA, 3.0 parts of iodine, 2,2'-azobis(4-methoxy-2 , 4-dimethylvaleronitrile) (trade name: V-70, manufactured by Wako Pure Chemical Industries, Ltd.), MMA 16.8 parts by mass, unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone (PCL-FM5) (trade name: Plaxel FM5, 52.3 parts by mass of caprolactone chain repeating number = 5) manufactured by Daicel Corporation and 0.04 parts by mass of succinimide were charged and stirred at 40°C for 5 hours while stirring under a nitrogen stream to obtain a B block copolymer. manufactured.
Subsequently, 11.0 parts by mass of MAA and 19.9 parts by mass of 2-MOES were added and stirred at 40° C. for 5 hours. When the solid content was measured and converted from the non-volatile content, the polymerization conversion rate was 99%. By reprecipitating this reaction solution with 3000 parts by mass of hexane, 99.0 parts by mass of AB block copolymer B was obtained. Block copolymer B thus obtained had a weight average molecular weight (Mw) of 8100, Mw/Mn of 1.2, and an acid value of 120 mgKOH/g.

(Synthesis Example 3: Production of block copolymer C)
In Synthesis Example 2, instead of using 16.8 parts by mass of MMA and 52.3 parts by mass of unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone (PCL-FM5), 62.3 parts by mass of MMA and 30.0 parts by mass of BMA were used. , MAA 11.0 parts by mass, and 2-MOES 19.9 parts by mass, except that MAA was changed to 7.7 parts by mass, in the same manner as in Synthesis Example 2 to produce a block copolymer C. Table 2 shows the weight average molecular weight (Mw), Mw/Mn, acid value and amine value of the block copolymer C thus obtained.

(Synthesis Example 4: Production of block copolymer D)
(1) Preparation of block copolymer D In a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 150.0 parts by mass of PGMEA, 3.0 parts of iodine, V- 11.0 parts by mass of 70, 50.4 parts by mass of MMA, 30.0 parts by mass of methoxypolyethylene glycol monomethacrylate (PME-200), and 0.04 parts by mass of succinimide were charged and heated to 40°C while stirring under a nitrogen stream. for 5 hours to produce a B block copolymer.
Subsequently, 19.6 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMMA) was added and stirred at 40° C. for 5 hours. When the solid content was measured and converted from the non-volatile content, the polymerization conversion rate was 99%. By reprecipitating this reaction solution with 3000 parts by mass of hexane, 99.0 parts by mass of block copolymer D was obtained. Block copolymer D thus obtained had a weight average molecular weight (Mw) of 7500, an Mw/Mn of 1.2, and an amine value of 70 mgKOH/g. Table 2 shows the weight average molecular weight (Mw), Mw/Mn, acid value and amine value of the block copolymer D thus obtained.

(2) Preparation of salt-type block copolymer D To 40.0 parts by mass of PGMEA, 25.0 parts by mass of block copolymer D, and 3.45 parts by mass of phenylphosphonic acid (PPA, manufactured by Nissan Chemical Industries, Ltd.) (0.7 molar equivalents relative to the DMMA constitutional unit of block copolymer D) was added and stirred at 60°C and room temperature for 6 hours to prepare a salt-type block copolymer D solution. This reaction solution was reprecipitated with 1000 parts by mass of hexane to obtain 27.8 parts by mass of a salt-type block copolymer D.

(Synthesis Example 5: Production of salt-type block copolymer E)
With reference to paragraphs 0188 to 0191 of Japanese Patent No. 6605783 (the aforementioned Patent Document 1), block copolymer E and salt-type block copolymer E used in the examples were produced.
Table 2 shows numerical values converted so that the total parts by mass of the A block and the B block is 100.0 parts by mass.
Table 2 shows the weight average molecular weight (Mw), Mw/Mn, acid value before and after salt formation, and amine value before and after salt formation of the resulting salt-type block copolymer E.

(Preparation Example 1: Preparation of alkali-soluble resin α)
A reactor equipped with a cooling pipe, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 300 parts by mass of PGMEA, heated to 100° C. under a nitrogen atmosphere, and then 2-phenoxyethyl methacrylate was added. (PhEMA) 90 parts by mass, MMA 54 parts by mass, methacrylic acid (MAA) 36 parts by mass and Perbutyl O (manufactured by NOF Corporation) 6 parts by mass, chain transfer agent (n-dodecyl mercaptan) 2 parts by mass for 1.5 hours It was continuously added dropwise over a period of time. Thereafter, 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 dropping 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 temperature was maintained at 110°C for 15 hours. An addition reaction was carried out to obtain an alkali-soluble resin α solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH/g, solid content 40% by mass).

(Preparation Example 2: Synthesis of blue lake colorant 1)
(1) Synthesis of Intermediate 1 With reference to the method for producing Intermediate A-2, Intermediate B-1, and Compound 1-3 described in JP-A-2018-3013, the following chemical formula (a) is used. Intermediate 1 was obtained (87% yield).
The obtained compound was confirmed to be the target compound from the following analysis results.
・MS (ESI) (m / z): 677 (+), divalent ・Elemental analysis value: CHN measured value (81.81%, 7.31%, 5.85%); theoretical value (81.77%) , 7.36%, 5.90%)

(2) Synthesis of blue lake colorant 1 2.59 g (0.76 mmol) of Kanto Chemical 12 tungstophosphoric acid n-hydrate was dissolved by heating in a mixture of 40 mL of methanol and 40 mL of water. 6 g (1.19 mmol) was added and stirred for 1 hour. The precipitate was collected by filtration and washed with water. The resulting precipitate was dried under reduced pressure to obtain a lake coloring material 1 represented by the following chemical formula (b) (yield 95%).
The obtained compound was confirmed to be the target compound from the following analysis results.
・31P NMR (d-dmso, ppm) δ-15.15
・MS (MALDI) (m/z): 1355 (M ⁺ ), 2879 (MH ₂ ⁻ )
Elemental analysis values: CHN measured values (35.55%, 3.24%, 2.61%); theoretical values (35.61%, 3.20%, 2.57%)
・Fluorescent X-ray analysis: MoW actual measurement ratio (0%, 100%); theoretical value (0%, 100%)

(Example 1)
(1-1) Production of colorant dispersion G-1 8.25 parts by mass of the graft copolymer A of Synthesis Example 1, 8-diazabicyclo[5.4.0]undecene-7 (manufactured by San-Apro Co., Ltd., "DBU ”) 0.38 parts by mass, 0.15 parts by mass of phenylphosphonic acid (PPA, manufactured by Nissan Chemical Industries, Ltd.), C.I. I. 13.0 parts by mass of Pigment Green 58 (PG58), 78.22 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm are placed in a mayonnaise bottle, and a paint shaker (manufactured by Asada Iron Works Co., Ltd.) is used for preliminary crushing. ) for 1 hour, then take out zirconia beads with a particle size of 2.0 mm, add 200 parts by mass of zirconia beads with a particle size of 0.1 mm, and similarly disperse for 4 hours with a paint shaker as main disintegration. , to obtain a coloring material dispersion liquid G-1.
(1-2) Production of Colorant Dispersion Y-1 In the colorant dispersion G-1, C.I. I. A coloring material dispersion liquid Y-1 was obtained in the same manner as the coloring material dispersion liquid G-1 except that Pigment Yellow 138 (PY138) was used.

(2) Production of colored curable composition G-1 6.86 parts by mass of the colorant dispersion G-1 obtained in (1-1) above, and the colorant dispersion obtained in (1-2) above 2.94 parts by mass of liquid Y-1, 0.69 parts by mass of the alkali-soluble resin α solution obtained in Preparation Example 1, and a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.) 0.83 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Co., Ltd.) 0.05 mass part, 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-octane Dione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)] (photoinitiator: trade name Irgacure OXE01, manufactured by BASF Japan Co., Ltd.) 0.02 parts by mass, a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation) and 8.48 parts by mass of PGMEA were added to obtain a colored curable composition G-1.

(Examples 2 to 11)
(1) Production of Colorant Dispersions G-2 to G-11 and Colorant Dispersions Y-2 to Y-11 As shown in Table 3, the graft copolymer A, the block copolymers B to D, the nitrogen-containing basic compound and the acidic group-containing compound were used in combination in the amounts shown in Table 3, and the amount of PGMEA was changed to obtain the total mass Colorant dispersions G-2 to G-11 and colorant dispersions Y-2 to Y-11 were produced in the same manner as in Example 1, except that the content was changed to 100 parts by mass.
(2) Production of colored curable compositions G-2 to G-11 In (2) of Example 1, instead of the colorant dispersion G-1 and the colorant dispersion Y-1, the colorant dispersion Using liquids G-2 to G-11 and colorant dispersions Y-2 to Y-11, colorant dispersions G-2 to G-11 were prepared so that the chromaticity was the same as that of the colored curable composition G-1. Colored curable compositions G-2 to G-11 were obtained in the same manner as in Example 1 (2), except that the amounts of colorant dispersions Y-2 to Y-11 were adjusted.

(Example 12)
(1) Production of Colorant Dispersion G-12 and Colorant Dispersion Y-12 In Example 2, instead of the graft copolymer A, block copolymer D, DBU and PPA, Colorant Dispersion G-12 and Colorant Dispersion Y-12 were produced in the same manner as in Example 2, except that Coalescence A and the salt-type block copolymer D were used. The DBU contained in the salt-type graft copolymer A used in the colorant dispersion and its content, and the PPA contained in the salt-type block copolymer and its content are shown in parentheses in Table 3.
(2) Production of colored curable composition G-12 In (2) of Example 1, instead of the colorant dispersion G-1 and the colorant dispersion Y-1, the colorant dispersion G-12 And the colorant dispersion Y-12 was used, and the amount of the colorant dispersion G-12 and the colorant dispersion Y-12 was adjusted so that the chromaticity was the same as that of the colored curable composition G-1. A colored curable composition G-12 was obtained in the same manner as in Example 1 (2).

(Comparative example 1)
(1) Production of Comparative Colorant Dispersion CG-1 and Comparative Colorant Dispersion CY-1 Same as Example 1, except that phenylphosphonic acid (PPA) was not added in (1) of Example 1. to obtain a comparative colorant dispersion CG-1.
In the comparative colorant dispersion CG-1, C.I. I. A comparative colorant dispersion CY-1 was obtained in the same manner as the colorant dispersion CG-1 except that Pigment Yellow 138 (PY138) was used.
(2) Production of comparative colored curable composition CG-1 In (2) of Example 1, instead of the colorant dispersion G-1 and the colorant dispersion Y-1, the comparative colorant dispersion CG -1 and the comparative colorant dispersion CY-1 were used, and the amounts of the colorant dispersion CG-1 and the colorant dispersion CY-1 were adjusted so that the chromaticity was the same as that of the colored curable composition G-1. obtained a comparative colored curable composition CG-1 in the same manner as in Example 1 (2).

(Comparative Examples 2-5)
(1) Production of Comparative Colorant Dispersions CG-2 to CG-5 and Comparative Colorant Dispersions CY-2 to CY-5 In (1) of Example 1, instead of graft copolymer A, Table 4 As shown in Table 4, the block copolymer D or the salt-type block copolymer E and the nitrogen-containing basic compound and/or the acidic group-containing compound are used in the amounts shown in Table 4, respectively, and the amount of PGMEA is changed. Comparative colorant dispersions CG-2 to CG-5 and comparative colorant dispersions CY-2 to CY-5 were obtained in the same manner as in Example 1, except that the total mass was changed to 100 parts by mass. rice field.
(2) Production of comparative colored curable compositions CG-2 to CG-5 In (2) of Example 1, instead of the colorant dispersion G-1 and the colorant dispersion Y-1, the comparative colors Using the material dispersions CG-2 to CG-5 and the comparative colorant dispersions CY-2 to CY-5, the colorant dispersions CG-2 to so that the chromaticity is the same as the colored curable composition G-1. Comparative colored curable compositions CG-2 to CG-5 were obtained in the same manner as in (2) of Example 1, except that the amounts of CG-5 and colorant dispersions CY-2 to CY-5 were adjusted. .

(Comparative Examples 6-7)
(1) Production of Comparative Colorant Dispersions CG-6 to CG-7 and Comparative Colorant Dispersions CY-6 to CY-7 Comparative colorant dispersions CG-6 to CG-7 and comparative colorant dispersions CG-6 to CG-7 and comparative colors Material dispersions CY-6 to CY-7 were obtained.
(2) Production of comparative colored curable compositions CG-6 to CG-7 In (2) of Example 1, instead of the colorant dispersion G-1, the comparative colorant dispersions CG-6 to CG, respectively -7 and comparative colorant dispersions CY-6 to CY-7, colorant dispersions CG-6 to CG-7 and colorant dispersions so that the chromaticity is the same as that of colored curable composition G-1 Comparative colored curable compositions CG-6 to CG-7 were obtained in the same manner as in (2) of Example 1, except that the amounts of CY-6 to CY-7 were adjusted.

(Comparative Example 8)
(1-1) Production of Comparative Colorant Dispersion CG-8 A phosphoric acid-based resin-type dispersant (b2 -1) solution, carboxylic acid resin type dispersant (b4-1) solution, binder resin (C-1) solution, and basic resin type dispersant (b1-7) solution, JP 2020-169242 prepared with reference to
0.32 parts by mass of a phosphoric acid resin dispersant (b2-1) solution, 0.32 parts by mass of a carboxylic acid resin dispersant (b4-1) solution, a basic resin dispersant (b1-7 ) solution, 10.1 parts by mass of the binder resin (C-1) solution, 76.26 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were placed in a mayonnaise bottle, and predissolved. Shake for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for crushing, then take out zirconia beads with a particle size of 2.0 mm, add 200 parts by mass of zirconia beads with a particle size of 0.1 mm, and repeat the present solution. As crushing, dispersion was carried out for 4 hours using a paint shaker to obtain a coloring material dispersion liquid CG-8.
The solid content weight ratio of the dispersant and the binder resin to the pigment was the same as in Example 1 of JP-A-2020-169242.
(1-2) Production of Comparative Colorant Dispersion CY-8 In the colorant dispersion CG-8, C.I. I. A coloring material dispersion CY-8 was obtained in the same manner as the coloring material dispersion CG-8 except that Pigment Yellow 138 (PY138) was used.
(2) Production of comparative colored curable composition CG-8 In (2) of Example 1, instead of the colorant dispersion G-1 and the colorant dispersion Y-1, the comparative colorant dispersion CG -8 and the comparative colorant dispersion CY-8 were used, and the amount of the colorant dispersion CG-8 and the colorant dispersion CY-8 was adjusted so that the chromaticity was the same as that of the colored curable composition G-1. obtained a comparative colored curable composition CG-8 in the same manner as in Example 1 (2). Although 1,8-diazabicyclo-[5.4.0]-7-undecene was used as a catalyst during the preparation of the carboxylic acid-based resin-type dispersant (b4-1) solution, it is consumed in the reaction. Yes, even assuming that all the added 1,8-diazabicyclo-[5.4.0]-7-undecene remained in the carboxylic acid resin type dispersant (b4-1) solution, the content is 0.0013 parts by mass with respect to 100 parts by mass of the coloring material.

(Comparative Example 9)
(1-1) Production of Comparative Colorant Dispersion CG-9 Phenylphosphonic acid and a base having an amino group, which are dispersants used in Example 41 of JP-A-2020-169242 (above-mentioned Patent Document 2) A salt (b3-1) solution with a curable resin-type dispersant, a carboxylic acid-based resin-type dispersant (b4-1) solution, and a binder resin (C-1) solution, see JP-A-2020-169242. was prepared.
0.95 parts by mass of a salt (b3-1) solution of a phenylphosphonic acid and a basic resin-type dispersant having an amino group, 0.32 parts by mass of a carboxylic acid resin-type dispersant (b4-1) solution, 10.1 parts by mass of binder resin (C-1) solution and C.I. I. 13.0 parts by mass of Pigment Green 58 (PG58), 76.26 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm are placed in a mayonnaise bottle, and a paint shaker (manufactured by Asada Iron Works Co., Ltd.) is used for preliminary crushing. ) for 1 hour, then take out zirconia beads with a particle size of 2.0 mm, add 200 parts by mass of zirconia beads with a particle size of 0.1 mm, and similarly disperse for 4 hours with a paint shaker as main disintegration. , to obtain a coloring material dispersion CG-9.
The solid weight ratio of the dispersant and the binder resin to the pigment was the same as in Example 41 of JP-A-2020-169242.
(1-2) Production of Comparative Colorant Dispersion CY-9 In the colorant dispersion CG-9, C.I. I. A coloring material dispersion CY-9 was obtained in the same manner as the coloring material dispersion CG-9 except that Pigment Yellow 138 (PY138) was used.
(2) Production of comparative colored curable composition CG-9 In (2) of Example 1, instead of the colorant dispersion G-1 and the colorant dispersion Y-1, the comparative colorant dispersion CG -9 and the comparative colorant dispersion CY-9 were used, and the amount of the colorant dispersion CG-9 and the colorant dispersion CY-9 was adjusted so that the chromaticity was the same as that of the colored curable composition G-1. obtained a comparative colored curable composition CG-9 in the same manner as in Example 1 (2). Although 1,8-diazabicyclo-[5.4.0]-7-undecene was used as a catalyst during the preparation of the carboxylic acid-based resin-type dispersant (b4-1) solution, it is consumed in the reaction. Yes, even assuming that all the added 1,8-diazabicyclo-[5.4.0]-7-undecene remained in the carboxylic acid resin type dispersant (b4-1) solution, the content is 0.0013 parts by mass with respect to 100 parts by mass of the coloring material.

(Comparative Example 10)
(1-1) Production of Comparative Colorant Dispersion CG-10 In Comparative Colorant Dispersion CG-9 of Comparative Example 9, the solid content weight ratio of the dispersant and the binder resin to the pigment was adjusted to the dispersion of the pigment of Example 1. It was increased to be similar to the solids weight ratio of the agent.
Specifically, 11.44 parts by mass of a salt (b3-1) solution of a phenylphosphonic acid and a basic resin-type dispersant having an amino group, and 16 parts of a carboxylic acid-based resin-type dispersant (b4-1) solution. .08 parts by mass, and C.I. I. 13.0 parts by mass of Pigment Green 58 (PG58), 59.48 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm are placed in a mayonnaise bottle, and a paint shaker (manufactured by Asada Iron Works Co., Ltd.) is used for preliminary crushing. ) for 1 hour, then take out zirconia beads with a particle size of 2.0 mm, add 200 parts by mass of zirconia beads with a particle size of 0.1 mm, and similarly disperse for 4 hours with a paint shaker as main disintegration. , to obtain a coloring material dispersion CG-10.
(1-2) Production of Comparative Colorant Dispersion CY-10 In the colorant dispersion CG-10, C.I. I. A colorant dispersion CY-10 was obtained in the same manner as the colorant dispersion CG-10 except that Pigment Yellow 138 (PY138) was used.
(2) Production of comparative colored curable composition CG-10 In (2) of Example 1, instead of the colorant dispersion G-1 and the colorant dispersion Y-1, the comparative colorant dispersion CG -10 and the comparative colorant dispersion CY-10 were used, and the amount of the colorant dispersion CG-10 and the colorant dispersion CY-10 was adjusted so that the chromaticity was the same as that of the colored curable composition G-1. obtained a comparative colored curable composition CG-10 in the same manner as in Example 1 (2). Although 1,8-diazabicyclo-[5.4.0]-7-undecene was used as a catalyst during the preparation of the carboxylic acid-based resin-type dispersant (b4-1) solution, it is consumed in the reaction. Yes, even assuming that all the added 1,8-diazabicyclo-[5.4.0]-7-undecene remained in the carboxylic acid resin type dispersant (b4-1) solution, the content is 0.067 parts by mass with respect to 100 parts by mass of the coloring material.

(Example 13)
(1) Production of Colorant Dispersion Liquid R1-1 and Colorant Dispersion Liquid R2-1 In the colorant dispersion liquid G-1 of Example 1, C.I. I. A colorant dispersion R1-1 was obtained in the same manner as the colorant dispersion G-1 except that Pigment Red 177 (PR177) was used. Further, in the colorant dispersion liquid G-1 of Example 1, C.I. I. A colorant dispersion R2-1 was obtained in the same manner as the colorant dispersion G-1 except that Pigment Red 291 (PR291) was used.
(2) Production of colored curable composition R-1 In (2) of Example 1, 6.86 parts by mass of the colorant dispersion G-1 and 2.94 parts by mass of the colorant dispersion Y-1 Coloring was carried out in the same manner as in (2) of Example 1, except that 2.94 parts by mass of the colorant dispersion R1-1 and 6.86 parts by mass of the colorant dispersion R2-1 were used instead. A curable composition R-1 was obtained.

(Examples 14-23)
(1) Production of Colorant Dispersions R1-2 to R1-11 and Colorant Dispersions R2-2 to R2-11 In Example 13, instead of graft copolymer A, DBU and PPA, As shown in Table 5, the graft copolymer A, the block copolymers B to D, the nitrogen-containing basic compound and the acidic group-containing compound were used in combination in the amounts shown in Table 5, and the amount of PGMEA was changed to obtain the total mass Colorant dispersions R1-2 to R1-11 and colorant dispersions R2-2 to R2-11 were produced in the same manner as in Example 13, except that the content was changed to 100 parts by mass.
(2) Production of colored curable compositions R-2 to R-11 In (2) of Example 13, instead of the colorant dispersion R1-1 and the colorant dispersion R2-1, respectively, the colorant dispersion Liquids R1-2 to R1-11 and colorant dispersions R2-2 to R2-11 are used, and colorant dispersions R1-2 to R1-11 are used so that the chromaticity is the same as that of the colored curable composition R-1. And colored curable compositions R-2 to R-11 were obtained in the same manner as in (2) of Example 13, except that the amounts of the colorant dispersions R2-2 to R2-11 were adjusted.

(Example 24)
(1) Production of Colorant Dispersion R1-12 and Colorant Dispersion R2-12 In Example 14, instead of the graft copolymer A, block copolymer D, DBU and PPA, Colorant dispersion R1-12 and colorant dispersion R2-12 were produced in the same manner as in Example 14, except that coalescence A and the salt-type block copolymer D were used. The DBU contained in the salt-type graft copolymer A used in the colorant dispersion and its content, and the PPA contained in the salt-type block copolymer and its content are shown in parentheses in Table 5.
(2) Production of colored curable composition R-12 In (2) of Example 13, instead of the colorant dispersion R1-1 and the colorant dispersion R2-1, the colorant dispersion R1-12 And the colorant dispersion R2-12 was used, and the amount of the colorant dispersion R1-12 and the colorant dispersion R2-12 was adjusted so that the chromaticity was the same as that of the colored curable composition R-1. A colored curable composition R-12 was obtained in the same manner as in Example 1 (2).

(Comparative Examples 11 to 17)
(1) Production of Comparative Colorant Dispersions CR1-1 to CR1-7 and Comparative Colorant Dispersions CR2-1 to CR2-7 In (1) of Example 13, as shown in Table 6, the graft copolymer A, block copolymer D or salt-type block copolymer E, and nitrogen-containing basic compound and/or acidic group-containing compound were used in amounts shown in Table 6, respectively, and the amount of PGMEA was changed to give a total mass of Comparative colorant dispersions CR1-1 to CR1-7 and comparative colorant dispersions CR2-1 to CR2-7 were obtained in the same manner as in Example 13, except that the content was changed to 100 parts by mass.
(2) Production of comparative colored curable compositions CR-1 to CR-7 In (2) of Example 13, instead of the colorant dispersion R1-1 and the colorant dispersion R2-1, the comparative colors Using the material dispersions CR1-1 to CR1-7 and the comparative colorant dispersions CR2-1 to CR2-7, the comparative colorant dispersion CR1-1 is used so that the chromaticity is the same as the colored curable composition R-1. Comparative colored curable compositions CR-1 to CR-7 were prepared in the same manner as in (2) of Example 13, except that the amounts of -CR1-7 and comparative colorant dispersions CR2-1 to CR2-7 were adjusted. Obtained.

(Example 25)
(1) Production of Colorant Dispersion B-1 In the colorant dispersion G-1 of Example 1, instead of PG58, the blue lake colorant 1 of Preparation Example 2 was used, except that the colorant dispersion A coloring material dispersion B-1 was obtained in the same manner as the liquid G-1.
(2) Production of colored curable composition B-1 6.78 parts by mass of the colorant dispersion B-1 obtained in the above (1), and 1.5 parts by mass of the alkali-soluble resin α solution obtained in Preparation Example 1. 46 parts by mass, 1.36 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1 -On (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Co., Ltd.) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) -butanone-1 (light Initiator: 0.09 parts by mass of Irgacure 369 (trade name, manufactured by BASF Japan), 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 a fluorine-based surfactant (trade name, Megafac R-08MH, manufactured by DIC Corporation), and 10 parts by mass of PGMEA. 11 parts by mass were added to obtain a colored curable composition B-1.

(Examples 26-35)
(1) Production of Colorant Dispersions B-2 to B-11 In Example 25, instead of graft copolymer A, DBU and PPA, graft copolymer A, block copolymer Coalescence B to D, the nitrogen-containing basic compound and the acidic group-containing compound were used in combination in the amounts shown in Table 7, respectively, and the amount of PGMEA was changed so that the total mass was 100 parts by mass. , and in the same manner as in Example 25, colorant dispersions B-2 to B-11 were produced.
(2) Production of colored curable compositions B-2 to B-11 In (2) of Example 25, instead of the colorant dispersion B-1, the colorant dispersions B-2 to B-11, respectively Colored curable compositions B-2 to B-11 were obtained in the same manner as in Example 25 (2), except that the was used.

(Example 36)
(1) Production of Colorant Dispersion B-12 In Example 26, instead of the graft copolymer A, the block copolymer D, DBU and PPA, the salt-type graft copolymer A and the salt-type block copolymer A coloring material dispersion B-12 was produced in the same manner as in Example 26, except that polymer D was used. The DBU contained in the salt-type graft copolymer A used in the colorant dispersion and its content, and the PPA contained in the salt-type block copolymer and its content are shown in parentheses in Table 7.
(2) Production of colored curable composition B-12 In (2) of Example 25, instead of the colorant dispersion B-1, the colorant dispersion B-12 was used, respectively. A colored curable composition B-12 was obtained in the same manner as in (2) of 25.

(Comparative Examples 18-24)
(1) Production of Comparative Colorant Dispersions CB-1 to CB-7 In (1) of Example 25, as shown in Table 8, graft copolymer A, block copolymer D or salt-type block copolymer Coalescence E and the nitrogen-containing basic compound and/or the acidic group-containing compound were used in the amounts shown in Table 8, respectively, and the amount of PGMEA was changed so that the total mass was 100 parts by mass. Comparative colorant dispersions CB-1 to CB-7 were obtained in the same manner as in Example 25.
(2) Production of comparative colored curable compositions CB-1 to CB-7 In (2) of Example 25, instead of the colorant dispersion B-1, the comparative colorant dispersions CB-1 to CB, respectively Comparative colored curable compositions CB-1 to CB-7 were obtained in the same manner as in Example 25 (2) except that -7 was used.

(Example 37)
(1) Production of Modified Coloring Material 1 70 parts by mass of PG58, 30 parts by mass of PY138, 2.9 parts by mass of DBU, and 3.6 parts by mass of PPA were placed in a double-arm kneader and kneaded for 3 at 25°C. A modified coloring material 1 was obtained by kneading for a long time.

(2) Production of colorant dispersion liquid G-37 13.85 parts by mass of the modified colorant 1, 4.83 parts by mass of graft copolymer A, 3.43 parts by mass of block copolymer D, and PGMEA 77.90 parts by mass of zirconia beads with a particle size of 2.0 mm and 100 parts by mass of zirconia beads with a particle size of 2.0 mm are placed in a mayonnaise bottle and shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for preliminary crushing, followed by a particle size of 2.0 mm. The zirconia beads were taken out, 200 parts by mass of zirconia beads having a particle size of 0.1 mm were added, and dispersion was similarly carried out for 4 hours using a paint shaker as main pulverization to obtain a colorant dispersion liquid G-37.

(3) Production of Colored Curable Composition G-37 9.80 parts by mass of the colorant dispersion G-37 obtained in (2) above and 0.8 parts by mass of the alkali-soluble resin α solution obtained in Preparation Example 1 were added. 69 parts by mass, 0.83 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1 -On (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Co., Ltd.) 0.05 parts by mass, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) -butanone-1 (light Initiator: 0.05 parts by mass of Irgacure 369, manufactured by BASF Japan), 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)] (photoinitiator: 0.02 parts by mass of Irgacure OXE01 (trade name, manufactured by BASF Japan Co., Ltd.), 0.07 parts by mass of a fluorine-based surfactant (trade name, Megafac R-08MH, manufactured by DIC Corporation), and 8 parts of PGMEA. 48 parts by mass were added to obtain a colored curable composition G-37.

(Comparative Example 25)
(1) Production of Comparative Modified Colorant 1 Comparative modified colorant 1 was obtained in the same manner as Modified Colorant 1 except that DBU was not used in Modified Colorant 1 of Example 37.

(2) Production of colorant dispersion CG-25 and colored curable composition CG-25 In colorant dispersion G-37, instead of modified colorant 1, comparative modified colorant 1 was used. Colorant dispersion CG-25 was obtained in the same manner as material dispersion G-37.
Further, in the colored curable composition G-37, in the same manner as the colored curable composition G-37, except that the colorant dispersion CG-25 was used instead of the colorant dispersion G-37. A sexual composition CG-25 was obtained.

(Example 38)
(1) Production of Modified Colorant 2 Modified except that 30 parts by mass of PR177 and 70 parts by mass of PR291 were used instead of 70 parts by mass of PG58 and 30 parts by mass of PY138 in the modified colorant 1 of Example 37. A modified colorant 2 was obtained in the same manner as the colorant 1.

(2) Production of colorant dispersion liquid R-38 and colored curable composition R-38 In colorant dispersion liquid G-37, instead of modified colorant 1, modified colorant 2 was used. Colorant dispersion R-38 was obtained in the same manner as dispersion G-37.
Further, in the colored curable composition G-37, in the same manner as the colored curable composition G-37, except that the colorant dispersion R-38 was used instead of the colorant dispersion G-37. A sexual composition R-38 was obtained.

(Comparative Example 26)
(1) Production of Comparative Modified Colorant 2 Comparative modified colorant 2 was obtained in the same manner as modified colorant 2 of Example 38, except that DBU was not used.

(2) Production of colorant dispersion liquid CR-26 and colored curable composition CR-26 In colorant dispersion liquid G-37, instead of modified colorant 1, comparative modified colorant 2 was used. Colorant dispersion CR-26 was obtained in the same manner as material dispersion G-37.
Further, in the colored curable composition R-38, instead of the colorant dispersion R-38, except that the colorant dispersion CR-26 was used, in the same manner as the colored curable composition R-38, colored curing A sexual composition CR-26 was obtained.

(Example 39)
(1) Production of modified colorant 3 In modified colorant 1 of Example 37, instead of 70 parts by mass of PG58 and 30 parts by mass of PY138, 100 parts by mass of the blue lake colorant of Preparation Example 2 was used. A modified colorant 3 was obtained in the same manner as the modified colorant 1.

(2) Production of Colorant Dispersion B-39 and Colored Curable Composition B-39 In Colorant Dispersion G-37, instead of Modified Colorant 1, Modified Colorant 3 was used. Colorant dispersion B-39 was obtained in the same manner as dispersion G-37.
6.78 parts by mass of the colorant dispersion B-39 obtained above, 1.46 parts by mass of the alkali-soluble resin α solution obtained in Preparation Example 1, a polyfunctional monomer (trade name Aronix M-403, Toa Synthetic Co., Ltd.) 1.36 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907, BASF Co., Ltd. Japan) is 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) is 0.09 Parts by mass, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)] (photoinitiator: trade name Irgacure OXE01, manufactured by BASF Japan Co., Ltd.) to 0.04 Parts by mass, 0.07 parts by mass of a fluorosurfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 10.11 parts by mass of PGMEA were added to obtain a colored curable composition B-39. .

(Comparative Example 27)
(1) Production of Comparative Modified Colorant 3 Comparative modified colorant 3 was obtained in the same manner as Modified Colorant 3 except that DBU was not used in Modified Colorant 3 of Example 39.

(2) Production of colorant dispersion CB-27 and colored curable composition CB-27 In colorant dispersion G-37, instead of modified colorant 1, comparative modified colorant 3 was used. A coloring material dispersion CB-27 was obtained in the same manner as the material dispersion G-37.
Further, in the colored curable composition B-39, instead of the colorant dispersion B-39, in the same manner as the colored curable composition B-39 except that the colorant dispersion CB-27 was used, colored curing A sexual composition CB-27 was obtained.

[Evaluation method]
<Optical performance, brightness>
The colored curable compositions obtained in Examples and Comparative Examples were each placed on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35"), and after post-baking using a spin coater, Green was y = 0. .575, x = 0.645 for Red, and y = 0.090 for Blue. to form a colored layer. 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.
Chromaticity (x, y) and luminance (Y) of each colored layer after post-baking were measured using an Olympus spectrophotometer OSP-SP200.
Luminance was obtained when y=0.575 for Green, x=0.645 for Red, and y=0.090 for Blue. A larger value indicates a higher brightness.

<Heat resistance>
The colored curable compositions obtained in Examples and Comparative Examples were each placed on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35"), and after post-baking using a spin coater, Green was y = 0. .575, x = 0.645 for Red, and y = 0.090 for Blue. to form a colored layer. 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.
For each colored layer before and after post-baking, the chromaticity (L ₀ , a ₀ , b ₀ ) before post-baking and the chromaticity (L ₁ , a ₁ , b ₁ ) after post-baking were measured using an Olympus spectroscopic spectrometer OSP. - Measured using SP200.
The chromaticity change of the colored film before and after post-baking was evaluated by the following formula. The results are shown in the table.
ΔEab={(L ₁ −L ₀ )2+(a ₁ −a ₀ )2+(b ₁ −b ₀ ) ² } ^1/2
The smaller the value of ΔEab, the more excellent the heat resistance is evaluated.

<Evaluation of Foreign Matter in Coating Film>
Each of the colored curable compositions obtained in Examples and Comparative Examples was coated on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") with a thickness of 2.3 μm after post-baking using a spin coater. 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 to prepare a colored substrate. The presence or absence of foreign matter in the coating film of the prepared colored substrate was observed using an optical microscope.
Evaluation A: Less than 2 objects of 100 nm or more in the range of 10 mm × 10 mm Evaluation B: 2 or more and less than 6 objects of 100 nm or more in the range of 10 mm × 10 mm Evaluation C: Objects of 100 nm or more in the range of 10 mm × 10 mm If the evaluation result of 6 or more is B, the foreign matter evaluation is good, and if the evaluation result is A, the foreign matter evaluation is excellent.

The above evaluation was performed on the colorant dispersions and colored curable compositions obtained in the examples and comparative examples obtained above. Evaluation results are shown in Tables 3 to 9.

The abbreviations in the table are as follows.
DBU: 1,8-diazabicyclo[5.4.0]undecene-7
DMAN: 1,8-bis(dimethylamino)naphthalene MTBD: 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene PPA: phenylphosphonic acid PPH: phenylphosphinic acid PDB : dibutyl phosphate p-TS: p-toluenesulfonic acid DBU, DMAN, MTBD, PPA, PPH, PDB and p-TS all have a transmittance of 90% or more in the wavelength range of 400 nm to 700 nm.

The abbreviations in the table are as follows.
DMAPAA: dimethylaminopropyl acrylamide 2-NA: 2-naphthoic acid MAA: methacrylic acid DMAPAA, 2-NA and MAA all have a transmittance of 90% or more in the wavelength range of 400 nm to 700 nm.

[Summary of results]
By comparing Examples and Comparative Examples, it was found that the coloring material includes a dispersant containing a polymer having a structural unit represented by the following general formula (I) and having an amine value of less than 10 mgKOH/g before salt formation, and a dispersant having a pKa of less than 10 mgKOH/g. In Examples 1 to 39 in which a nitrogen-containing basic compound having a value of 11.5 or more and an acidic group-containing compound having a pKa of 4.0 or less were combined at a specific content ratio, the chromaticity change during heating was suppressed, It was clarified that it is possible to form a coating film with improved brightness and suppressed generation of foreign matter. According to Examples 1 to 39, a dispersant containing a polymer having a constitutional unit represented by the general formula (I) and having an amine value before salt formation of less than 10 mgKOH/g as a colorant, and a pKa of 11.5. When a nitrogen-containing basic compound of 5 or more and an acidic group-containing compound having a pKa of 4.0 or less are combined at a specific content ratio, even if these are mixed during preparation of the colorant dispersion, copolymerization can be performed in advance. The colorant may be dispersed using a dispersant in the form of a salt-type copolymer obtained by forming a salt with a nitrogen-containing basic compound having a pKa of 11.5 or more or an acidic group-containing compound having a pKa of 4.0 or less. First, a modified coloring material is prepared by mixing a nitrogen-containing basic compound having a pKa of 11.5 or more and an acidic group-containing compound having a pKa of 4.0 or less with a coloring material, and the modifying coloring material is dispersed using a dispersant. It has been clarified that, even if the temperature is reduced, it is possible to form a coating film in which the chromaticity change during heating is suppressed, the luminance is improved, and the generation of foreign matter is suppressed.
On the other hand, as in Comparative Examples 1, 6, 11, 16, 18 and 23, polymers having structural units represented by general formula (I) and having an amine value before salt formation of less than 10 mgKOH/g and a nitrogen-containing basic compound having a pKa of 11.5 or more, but not containing an acidic group-containing compound having a pKa of 4.0 or less, the chromaticity change suppressing effect during heating was inferior, and the luminance was inferior.
Further, as in Comparative Examples 7, 17, 24, 25, 26, and 27, a polymer having a structural unit represented by the general formula (I) and having an amine value before salt formation of less than 10 mgKOH/g Even if a dispersant containing a dispersant and an acidic group-containing compound having a pKa of 4.0 or less are combined, if a nitrogen-containing basic compound having a pKa of 11.5 or more is not contained, the effect of suppressing chromaticity change during heating is inferior. , the luminance was inferior.
In addition, as in Comparative Examples 2, 12, and 19, when a basic dispersant and an acidic group-containing compound having a pKa of 4.0 or less were combined, the effect of suppressing chromaticity change during heating was inferior, and luminance was inferior.
Further, as in Comparative Examples 3, 13, and 20, when a basic dispersant, a nitrogen-containing basic compound having a pKa of 11.5 or more, and an acidic group-containing compound having a pKa of 4.0 or less were combined. However, foreign matter was generated in the coating film, the chromaticity change suppressing effect during heating was poor, and the luminance was poor.
Further, as in Comparative Examples 4, 5, 14, 15, 21 and 22, a basic dispersant containing randomly acidic groups in the solvent-soluble site A block used in Examples of Patent Document 1 was used. In this case, when a nitrogen-containing basic compound having a pKa of 11.5 or more and an acidic group-containing compound having a pKa of 4.0 or less are combined, foreign matter is generated in the coating film (Comparative Examples 5, 15, and 22). , When an acidic group-containing compound having a pKa of more than 4 is used instead of an acidic group-containing compound having a pKa of 4.0 or less, foreign matter in the coating film is more likely to be produced than when an acidic group-containing compound having a pKa of 4.0 or less is used. Although the occurrence was slightly suppressed, the chromaticity change suppressing effect during heating was inferior, and the brightness was inferior (Comparative Examples 4, 14, and 21).
Further, as in Comparative Example 8, the phosphoric acid-based resin dispersant (b2-1) solution, the carboxylic acid-based resin dispersant (b4-1) solution, and the base used in Examples of Patent Document 2 A basic resin type dispersant having a phenylphosphonic acid and an amino group used in Examples of Patent Document 2, such as Comparative Examples 9 and 10, or using a combination of a resin type dispersant (b1-7) solution Even when the salt (b3-1) solution with the agent and the carboxylic acid resin type dispersant (b4-1) solution were used in combination, the effect of suppressing chromaticity change during heating was poor, and the brightness was poor. .

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

A coloring material, a dispersant, a nitrogen-containing basic compound with a pKa of 11.5 or more, an acidic group-containing compound with a pKa of 4.0 or less, and a solvent,
The nitrogen-containing basic compound having a pKa of 11.5 or more and the acidic group-containing compound having a pKa of 4.0 or less are added in an amount of 0.1 parts by mass to 30 parts by mass, respectively, based on 100 parts by mass of the coloring material. Contains 0 parts by mass,
A colorant dispersion liquid in which the dispersant contains a polymer having a structural unit represented by the following general formula (I) and having an amine value of less than 10 mgKOH/g before salt formation.

(In general formula (I), R 1 represents a hydrogen atom or a methyl group, A represents a direct bond or a divalent linking group, and Q is an acidic group.)
In a polymer having a structural unit represented by the general formula (I) and having an amine value of less than 10 mgKOH/g before salt formation, at least part of the acidic groups contained in the general formula (I); 2. The colorant dispersion according to claim 1, which forms a salt with a nitrogen-containing basic compound having a pKa of 11.5 or higher.
A polymer having a structural unit represented by the general formula (I) and having an amine value before salt formation of less than 10 mgKOH/g,
A graft copolymer having a structural unit represented by the general formula (I), and at least part of the acidic groups contained in the general formula (I) in the graft copolymer and a basic compound form a salt. a salt-type graft copolymer, and
A block copolymer having an A block containing a structural unit represented by the general formula (I), and at least part of the acidic groups contained in the general formula (I) in the block copolymer and a basic compound 3. The coloring material dispersion liquid according to claim 1, wherein is at least one salt type block copolymer forming a salt.
A polymer having a structural unit represented by the general formula (I) and having an amine value of less than 10 mgKOH/g before salt formation is represented by the general formula (I) as a structural unit represented by the following general formula ( 4. The colorant dispersion according to any one of claims 1 to 3, comprising a structural unit represented by II-1) and a structural unit represented by the following general formula (II-2).

(In general formula (II-1), R 1 represents a hydrogen atom or a methyl group,
In general formula (II-2), R 1 represents a hydrogen atom or a methyl group, R 2 represents an aliphatic hydrocarbon group which may contain an oxygen atom, and R 3 represents a hydrocarbon group. )
The dispersant is
A graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the following general formula (III), wherein the polymer chain in the general formula (III) is represented by the following general formula ( V) and a graft copolymer containing at least one structural unit selected from the group consisting of structural units represented by the following general formula (V'), and in the graft copolymer, A salt-type graft copolymer in which at least part of the acidic groups contained in the general formula (I) and a basic compound form a salt, and
It has an A block containing a structural unit represented by the general formula (I) and a B block containing a structural unit represented by the following general formula (IV), and the B block is represented by the following general formula (V) and a block copolymer containing at least one structural unit selected from the group consisting of structural units represented by the following general formula (V′), and the block copolymer in which the general formula (I ) a salt-type block copolymer in which at least part of the acidic groups contained in ) and a basic compound form a salt,
The colorant dispersion liquid according to any one of claims 1 to 4, comprising at least one of

(In general formula (III), R 1″ represents a hydrogen atom or a methyl group, A 1 represents a direct bond or a divalent linking group, and Polymer represents a polymer chain.)

(In general formula (IV), R 11 is a hydrogen atom or a methyl group, A 2 is a divalent linking group, R 4 is a hydrocarbon group which may have a substituent and which may contain a hetero atom. .)

(In general formula (V), R 11′ is a hydrogen atom or a methyl group, A 2′ is a divalent linking group, R 5 is an ethylene group or a propylene group, and R 6 is a hydrogen atom or a hydrocarbon group. , m represents a number of 2 or more and 80 or less.
In general formula (V′), R 11″ is a hydrogen atom or a methyl group, A 2″ is a divalent linking group, R 6′ is a hydrogen atom or a hydrocarbon group, and k is 3 or more and 7 or less. An integer, n represents a number of 2 or more and 80 or less. )
Claim 1, wherein the polymer having structural units represented by the general formula (I) and having an amine value of less than 10 mgKOH/g before salt formation has an acid value of 20 to 250 mgKOH/g before salt formation. 6. The colorant dispersion liquid according to any one of 1 to 5.
Any one of claims 1 to 6, wherein the dispersant further comprises a polymer having a structural unit represented by the following general formula (VI) and having an amine value of 35 mgKOH/g or more before salt formation. The colorant dispersion liquid described in .

(In general formula (VI), R 31 is a hydrogen atom or a methyl group, A 3 is a divalent linking group, R 32 and R 33 are each independently a hydrogen atom, or a carbon atom that may contain a hetero atom. represents a hydrogen group, and R 32 and R 33 may combine with each other to form a ring structure.)
In a polymer having a structural unit represented by the general formula (VI) and having an amine value of 35 mgKOH/g or more before salt formation, the terminal nitrogen site of the structural unit represented by the general formula (VI) 8. The colorant dispersion according to claim 7, wherein at least a part thereof and the acidic group-containing compound having a pKa of 4.0 or less form a salt.
The nitrogen-containing basic compound having a pKa of 11.5 or more and the acidic group-containing compound having a pKa of 4.0 or less each have a transmittance of 90% or more in a wavelength range of 400 nm to 700 nm. Item 9. The colorant dispersion according to any one of Items 1 to 8.
Claims 1 to 1, wherein the acidic group-containing compound having a pKa of 4.0 or less is one or more compounds selected from the group consisting of compounds represented by the following general formulas (1) and (2): 10. The colorant dispersion liquid according to any one of 9.

(In the general formula (1), R a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or -O- R b represents 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 C 1 to 4 It represents a (meth)acryloyl group via an alkylene group.
In general formula (2), each of R c and R d may independently have a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a substituent. represents a phenyl group, a benzyl group, or —O—R e , where R e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group optionally having a substituent, or It represents a benzyl group or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms. However, at least one of Rc and Rd contains a carbon atom. )
a coloring material, a nitrogen-containing basic compound having a pKa of 11.5 or more, and an acidic group-containing compound having a pKa of 4.0 or less, wherein the nitrogen-containing basic compound having a pKa of 11.5 or more; A modified colorant containing an acidic group-containing compound having a pKa of 4.0 or less and 0.1 to 30.0 parts by mass of each of 100 parts by mass of the colorant.
The nitrogen-containing basic compound having a pKa of 11.5 or more and the acidic group-containing compound having a pKa of 4.0 or less each have a transmittance of 90% or more in a wavelength range of 400 nm to 700 nm. Item 12. The modified colorant according to item 11.
The acidic group-containing compound having a pKa of 4.0 or less is one or more compounds selected from the group consisting of compounds represented by the following general formulas (1) and (2), or 13. The modified colorant according to 12.

(In the general formula (1), R a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or -O- R b represents 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 C 1 to 4 It represents a (meth)acryloyl group via an alkylene group.
In general formula (2), each of R c and R d may independently have a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a substituent. represents a phenyl group, a benzyl group, or —O—R e , where R e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group optionally having a substituent, or It represents a benzyl group or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms. However, at least one of Rc and Rd contains a carbon atom. )
At least part of the nitrogen-containing basic compound having a pKa of 11.5 or more and at least part of the acidic group-containing compound having a pKa of 4.0 or less form a salt according to claims 11 to 13. The modified colorant according to any one of claims 1 to 3.
A colored curable composition containing the colorant dispersion according to any one of claims 1 to 10, a polymerizable compound, and an initiator.
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 colored curable composition according to claim 15.
A display device having the color filter according to claim 16.