WO2021199786A1

WO2021199786A1 - Color material liquid dispersion, dispersing agent, curable coloring composition, color filter, and display device

Info

Publication number: WO2021199786A1
Application number: PCT/JP2021/006466
Authority: WO
Inventors: 健朗長井
Original assignee: 株式会社Ｄｎｐファインケミカル
Priority date: 2020-04-01
Filing date: 2021-02-19
Publication date: 2021-10-07
Also published as: JP2021161311A; CN115315483A; TW202204455A; KR20220162700A

Abstract

Provided is a color material liquid dispersion containing a color material, a dispersing agent, and a solvent, wherein the dispersing agent includes: a salt polymer obtained by forming a salt from at least some of the acidic groups that are of a polymer having the constituent unit represented by general formula (I) and are included in general formula (I); and at least one compound (B) selected from the group consisting of tertiary amines and basic heterocyclic compounds. (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

Color material dispersion, dispersant, color curable composition, color filter, display device

The present invention relates to a color material dispersion liquid, a dispersant, a color curable composition, a color filter, and a display device.

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

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

Here, the color filter is generally formed on 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 on the transparent substrate so as to partition each colored pattern. It has a formed light-shielding portion.

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

It is known that it is effective to use a dispersant as a method for improving the dispersibility of the finely divided pigment. For example, Patent Document 1 describes a block copolymer having two or more carboxyl groups as a block copolymer capable of giving a dispersion composition having excellent dispersion stability when used as a dispersant, and at least one of the carboxyl groups. It has an A block containing a structural unit derived from a vinyl monomer bonded to carbon atoms adjacent to each other on an aromatic ring, and a B block containing a structural unit derived from a (meth) acrylic acid alkyl ester. Block copolymers having a valence of 30 to 250 mgKOH / g are disclosed.

On the other hand, Patent Document 2 provides a coloring composition for a color filter, which has excellent dispersibility, contrast ratio, lightness, and heat resistance, and further has excellent developability against an alkaline aqueous solution and achieves high resolution. A coloring composition for a color filter containing a pigment, a basic dispersant, an acidic dispersant (X), a binder resin, and a solvent, wherein the acidic dispersant is a tricarboxylic acid anhydride and / or tetra. A dispersant having a main chain of polyester having a carboxyl group derived from carboxylic acid dianhydride and a side chain of a vinyl polymer having a specific structure. The basic dispersant is a graft co-weight having an amino group. A coloring composition for a color filter, which is a coalesced and / or block copolymer and has an amine value of 10 to 350 mgKOH / g, is described.

Japanese Unexamined Patent Publication No. 2016-204529 Japanese Unexamined Patent Publication No. 2016-191909

As described above, in recent color filters, the particle size of the pigment used has become finer due to the demand for high brightness and high contrast. Since the finely divided pigments tend to aggregate as the specific surface area increases, a dispersant having higher dispersion performance is required. Further, due to the demand for higher color gamut and thinner film, the demand for higher concentration of the coloring material in the color curable composition is increasing. As the ratio of the colorant in the color curable composition increases, the binder component decreases relatively. Among the binder components, the number of components related to the curability of the coating film, such as the polyfunctional monomer and the photoinitiator, is reduced, so that the crosslink density of the coating film is lowered due to insufficient curing, and the adhesion of the coating film to the substrate is lowered. Similarly, the proportion of the colorant that is difficult to dissolve in the solvent in the color curable composition increases, and the binder component that is easily soluble in the solvent decreases relatively, so that the solvent resolubility deteriorates. Therefore, in order to meet the demand for high concentration of the coloring material in the color curable composition, a technique for simultaneously solving the problems caused by the lack of these binder components is required. The substrate adhesion is an index of the adhesion of the formed colored coating film (cured product of the coloring curable composition) to the substrate, and if the substrate adhesion is poor, it is in the process after forming the colored coating film. The colored coating film peels off due to physical impact, causing a problem of display failure. Further, the solvent resolubility refers to the property that the solid content of the color-curable composition once dried is re-dissolved in the solvent. For example, if a color-curable composition adheres to the tip of a die lip during coating with a die coater, a solidified product is generated by drying, but the solidified product easily dissolves in the color-curable composition when coating is resumed. Otherwise, the solidified material on the die lip is partially peeled off and easily adheres to the colored layer of the color filter, for example, which causes foreign matter defects. In particular, when the concentration of the coloring material of the color curable composition is increased, the solvent resolubility tends to be insufficient, and there is a problem that the yield is lowered due to the generation of the above-mentioned foreign matter in the manufacturing process of the color filter.

The present invention has been made in view of the above circumstances, and is a color material dispersion capable of producing a color curable composition that simultaneously satisfies excellent dispersion stability, brightness, contrast, substrate adhesion, and solvent resolubility. It is an object of the present invention to provide a liquid and a dispersant. Another object of the present invention is to provide a color curable composition that simultaneously satisfies excellent dispersion stability, brightness, contrast, substrate adhesion, and solvent resolubility. Another object of the present invention is to provide a color filter and a display device formed by using the color curable composition.

The color material dispersion liquid according to the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent.
The dispersant contains at least a part of acidic groups contained in the general formula (I) of a polymer having a structural unit represented by the following general formula (I), a tertiary amino group-containing basic compound and basicity. It contains a salt-type polymer in which a salt is formed with one or more compounds (B) selected from the group consisting of heterocyclic compounds.

(In the 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 dispersant according to the present invention is a basic compound containing at least a part of acidic groups contained in the general formula (I) and a tertiary amino group-containing basic compound of the polymer having a structural unit represented by the general formula (I). A salt-type polymer obtained by forming a salt with one or more compounds (B) selected from the group consisting of a basic heterocyclic compound and a basic heterocyclic compound.

The color curable composition according to the present invention contains a coloring material, a dispersant according to the present invention, a polymerizable compound, an initiator, and a solvent.

The color filter according to the present invention is a color filter including at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a cured product of the colored curable composition according to the present invention. Is.

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

According to the present invention, there is provided a color material dispersion liquid and a dispersant capable of producing a color curable composition that simultaneously satisfies excellent dispersion stability, brightness, contrast, substrate adhesion, and solvent resolubility. can. Further, according to the present invention, it is possible to provide a color curable composition that simultaneously satisfies excellent dispersion stability, brightness, contrast, substrate adhesion, and solvent resolubility. Further, according to the present invention, it is possible to provide a color filter and a display device formed by using the color curable composition.

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

Hereinafter, the color material dispersion liquid, the dispersant, the color 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 invisible regions, and radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryloyl represents each of acryloyl and methacrylic, (meth) acrylic represents each of acrylic and methacrylic, and (meth) acrylate represents each of acrylate and methacrylate.
In the present specification, unless otherwise specified, the chromaticity coordinates x and y are in the XYZ color system of JIS Z8701: 1999 measured using a C light source.
Further, in the present specification, "-" indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

I. Color Material Dispersion Liquid The color material dispersion liquid according to the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent.
The dispersant contains at least a part of acidic groups contained in the general formula (I) of a polymer having a structural unit represented by the following general formula (I), a tertiary amino group-containing basic compound and basicity. It contains a salt-type polymer in which a salt is formed with one or more compounds (B) selected from the group consisting of heterocyclic compounds.

The coloring material dispersion liquid according to the present invention comprises a group consisting of at least a part of the acidic groups contained in the general formula (I), a tertiary amino group-containing basic compound and a basic heterocyclic compound as a dispersant. At least a salt-type polymer in which a salt is formed with one or more selected compounds (B) is used.
In the salt-type polymer used as a dispersant in the present invention, at least a part of the acidic group which is a coloring material adsorbing group is salt-formed with a specific basic compound, so that the polarity of the coloring material adsorbing group is increased. Since the color material adsorption property is enhanced, the dispersibility and dispersion stability of the color material are improved, and the contrast and brightness are improved. Further, it is presumed that the colorant adsorbability of the dispersant is increased, so that the colorant is appropriately coated with the dispersant, and the solvent resolubility is improved.
Further, in the salt-type polymer used as the dispersant in the present invention, the polarity of the dispersant is increased because at least a part of the acidic group which is the colorant adsorbing group is salt-formed with a specific basic compound. It is presumed that the adhesion to the base material is improved because the interaction with the surface of the base material is enhanced.

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

<Dispersant>
In the present invention, as the dispersant, at least a part of the acidic groups contained in the general formula (I) and the tertiary amino group-containing basicity of the polymer having the structural unit represented by the general formula (I). At least one salt-type polymer obtained by forming a salt with one or more compounds (B) selected from the group consisting of a compound and a basic heterocyclic compound is used.

[Polymer having a structural unit represented by the general formula (I)]
(Constituent unit represented by the general formula (I))
In the 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, 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 having a hydroxyl group. Examples thereof include hydrogen groups, aromatic hydrocarbon groups, -CONH- groups, -COO- groups, -NHCOO- groups, ether groups (-O- groups), thioether groups (-S- groups), and combinations thereof. .. In the present invention, the direction of bonding of the divalent linking group is arbitrary. That is, when -CONH- is contained 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, and conversely, -NH may be on the nitrogen atom side of the side chain. -CO may be on the nitrogen atom side of the side chain on the carbon atom side of the side chain.

Specific examples of the aliphatic hydrocarbon group include linear chains 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. Examples thereof include a branched alkylene group such as a alkylene group, a methylmethylene group, a methylethylene group, a 1-methylpentylene group and a 1,4-dimethylbutylene group, and a cyclic alkylene group such as a cyclopentylene group and a cyclohexylene group.
Examples of the number of carbon atoms of the aliphatic hydrocarbon group include 1 to 20, and from the viewpoint of dispersion stability, 1 to 16 is preferable, 1 to 12 is more preferable, and 2 to 8 is even more preferable.
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, and is preferably a -CONH- group and -COO. More preferably, it is 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.

The acidic groups represented by Q, for example, 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 can be mentioned.
The acidic groups represented by Q, among others, from the viewpoint of dispersion stability, carboxy group (-COOH), a sulfonic acid group _(SO 3 H), and a phosphoric acid group (-O-P (= O) (OH ) It is preferable that it is at least one selected from the group consisting of _2).
Examples of the phosphoric acid group-containing ethylenically unsaturated monomer include 2- (meth) acryloyloxyethyl acid phosphate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate and the like.
Examples of the sulfonic acid group-containing ethylenically unsaturated monomer include (meth) acryloyloxyethyl sulfonic acid and 2- (meth) acrylamide-2-methylpropanesulfonic acid.
As the acidic group represented by Q, a carboxy group is preferable from the viewpoint of brightness, and the structural unit represented by the general formula (I) includes the structural unit represented by the following general formula (II). Is preferable.

(In the 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 the general formula (II) may be the same as the 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, a structural unit derived from (meth) acrylic acid ester, and the like.
The general formula (II) includes a structural unit represented by the following general formula (II-1) and a structural unit represented by the following general formula (II-2) from the viewpoint of dispersibility and dispersion stability. At least one selected from the group consisting of is preferred.

(In the general formula (II-1), R ¹ represents a hydrogen atom or a methyl group, and represents
In the 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 the general formula (II-1) is a structural unit derived from (meth) acrylic acid.
In the structural unit represented by the general formula (II-2), R ² represents an aliphatic hydrocarbon group which may contain an oxygen atom.
The aliphatic hydrocarbon group in R ² may be the same as described above.
The aliphatic hydrocarbon group containing an oxygen atom in R ^2, or with a carbon atom in the aliphatic hydrocarbon group is replaced by an oxygen atom structure, hydrogen atoms in the aliphatic hydrocarbon group is an oxygen atom It has a structure substituted with a substituent containing. Examples of the aliphatic hydrocarbon group which may contain an oxygen atom include a structure in which a linking group such as -O-, -COO-, and -OCO- is contained in the carbon chain of the hydrocarbon group. Examples of the aliphatic hydrocarbon group containing an oxygen atom, and specific ^{^{examples, -R 20 - (O-R}} 21) s- ( wherein ^{each R 20} and ^{R 21} are independently an aliphatic hydrocarbon group, s represents a number of ^{1 ~ 80), - R 22} - (OCO-R 23) t- ( where ^{each R 22} and ^{R 23} independently represent an aliphatic hydrocarbon radical, t is a number of 1 to 40 Represents). The aliphatic hydrocarbon groups of R ²⁰ , R ²¹ , R ²² and R ²³ may be the same as those of the aliphatic hydrocarbon groups. From the viewpoint of dispersion stability, the R ²⁰ is preferably an alkylene group having 1 to 20 carbon atoms, the R ²¹ is preferably an alkylene group having 1 to 20 carbon atoms, s is 1 to 40, and further. The number is preferably 2 to 25, more preferably 2 to 10. Further, from the viewpoint of dispersion stability, the R ²² is preferably an alkylene group having 1 to 20 carbon atoms, the R ²³ is preferably an alkylene group having 1 to 20 carbon atoms, and t is 1 to 30. The number is preferably 1 to 20, more preferably 1 to 10.
The R ²⁰ and the R ²² are each independently preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an alkylene group having 2 to 8 carbon atoms.
The R ²¹ is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an ethylene group or a propylene group.
The R ²³ is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 3 to 7 carbon atoms.
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 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms. May be.

In the structural unit represented by the general formula (II-2), R ³ represents a hydrocarbon group. Examples of the hydrocarbon group in R ³ include 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 described above.
The ^{number of carbon atoms of the hydrocarbon group of R 3} is 1 to 20, and from the viewpoint of dispersion stability, 1 to 16 is preferable, 2 to 12 is more preferable, and 2 to 6 is even more preferable.

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

In the polymer, the structural unit represented by the general formula (I) may consist of one type or may include two or more types of structural units.

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 preferably used. More preferably, it is at least one of a graft copolymer having a graft copolymer and a block copolymer having an A block containing the structural unit represented by the general formula (I).

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

(Constituent unit having a graft polymer chain)
The graft copolymer has a graft polymer chain on the side chain that functions as a solvent-affinity site.
As a guide, the polymer chain preferably has a solubility of 20 (g / 100 g solvent) or more at 23 ° C. with respect to the organic solvent used in combination.
The solubility of the polymer chain can be determined by the fact that the raw material into which the polymer chain is introduced when preparing the graft copolymer has the solubility. For example, when a polymerizable oligomer (macromonomer) containing a polymer chain and a group having an ethylenically unsaturated double bond at the end thereof is used to introduce the polymer chain into the graft copolymer, the polymerizable oligomer is described above. It suffices to have solubility. Further, after the copolymer is formed by the monomer containing a group having an ethylenically unsaturated double bond, a polymer chain containing a reactive group capable of reacting with the reactive group contained in the copolymer is used. When introducing a polymer chain, it is sufficient that the polymer chain containing the reactive group has the solubility.

The graft copolymer used in the present invention has a structural unit represented by the general formula (I) in the main chain, which functions as an adsorption site for a coloring material, and further has a side chain as a solvent-friendly site. It is preferable to have a structural unit represented by the following general formula (III), which has a functional polymer chain.

(In the 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 in A 1} is not particularly limited as long as the carbon atom derived from the ethylenically unsaturated double bond and the polymer chain can be linked. The divalent linking group may be the same as A in the general 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, and is preferably a -CONH- group or-. More preferably, it is 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.

It is preferable that the polymer chain contains at least one structural unit represented by the following general formula (IV) from the viewpoint of dispersibility and dispersion stability of the coloring material.

(In the 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 or may contain a hetero atom. .)

In general formula (IV), A ² is a divalent linking group. Examples of the divalent linking group in A ² include the same as the divalent linking group in A ¹ .
Among them, from the viewpoint of dispersibility and dispersion stability of the coloring material, A ² in the general formula (IV) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and is preferably -CONH-. More preferably, it is a group or a -COO- group.

In R ^4, the hydrocarbon group in a hydrocarbon group which may contain a hetero atom, for example, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, aryl group and aralkyl group or alkyl-substituted aryl group, These combinations such as and the like can be mentioned.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or n-. Examples thereof include nonyl group, n-lauryl group, n-stearyl group, cyclopentyl group, cyclohexyl group, boronyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group substituted adamantyl group and the like. The number of carbon atoms of the alkyl group is preferably 1 to 12, and more preferably 1 to 6.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, a propenyl group and the like. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the obtained polymer, it is preferable that the double bond is at the end of the alkenyl group. The alkenyl group preferably has 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xsilyl group and the like. The aryl group preferably has 6 to 24 carbon atoms, and more preferably 6 to 12 carbon atoms.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent. The carbon number of the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.
Further, a linear or branched alkyl group having 1 to 30 carbon atoms may be bonded to the aromatic ring such as the aryl group or the aralkyl group as a substituent.

As the hydrocarbon group for R ^4, among others, from the viewpoint of dispersibility and dispersion stability, an aryl group an alkyl group, carbon number alkyl groups may be substituted 6-12 1-18 carbon atoms and, It is preferable that the alkyl group is at least one selected from the group consisting of aralkyl groups having 7 to 14 carbon atoms which may be substituted, and is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or n-butyl. It is preferably one or more selected from the group consisting of a group, an n-nonyl group, an n-lauryl group, an n-stearyl group, a phenyl group in which an alkyl group may be substituted, and a benzyl group.

The hydrocarbon group containing a hetero atom in R ^4, or has a structure in which carbon atom is replaced with a heteroatom in the hydrocarbon radical, a hydrogen atom in the hydrocarbon group is replaced with a substituent group containing a hetero atom Has a hydrocarbon structure. Examples of the hetero atom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. Hydrocarbon groups that may contain heteroatoms include, for example, -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-,-in the carbon chain of the hydrocarbon group. S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O- , -O-NH- and the like, and examples thereof include a structure containing a linking group.
Further, the hydrocarbon group may have a substituent as long as it does not interfere with the dispersion performance of the graft copolymer, and examples of the substituent include a halogen atom, a hydroxyl group, a carboxy group and an alkoxy group. Examples thereof include a nitro group, a cyano group, an epoxy group, an isocyanate group and a thiol group.

As the hydrocarbon group which may contain a hetero atom in R ^4, may be a structure in which the polymerizable group is added alkenyl groups such as terminal through a linking group containing a hetero atom in the hydrocarbon group. For example, the structural unit represented by the general formula (IV) may have a structure in which a glycidyl (meth) acrylate is reacted with a structural unit derived from (meth) acrylic acid. ^{That is, the structure of -A 2-} R ⁴ in the general formula (IV) is represented by -COO-CH ₂ CH (OH) CH _2- OCO-CR = CH ₂ (where R is a hydrogen atom or a methyl group). It may be a structure that can be used. Further, the structural unit represented by the general formula (IV) may have a structure in which 2-isocyanatoalkyl (meth) acrylate is reacted with a structural unit derived from hydroxyalkyl (meth) acrylate. ^{That is, R 4} in the general formula (IV) is -R'-OCONH-R "-OCO-CR = CH ₂ (where R'and R" are independently alkylene groups, and R is a hydrogen atom or a methyl group. ) May be the structure.

Examples of the monomer for deriving the structural unit represented by the general formula (IV) include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and 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 having a structural unit derived from the above. However, it is not limited to these.

In the present invention, examples of the R ^4, among them, it is preferable to use those having excellent solubility in organic solvents to be described later, may be selected as appropriate in accordance with the organic solvent used in the colorant dispersion. Specifically, for example, when the organic solvent is an ether alcohol acetate-based, ether-based, ester-based, alcohol-based or other organic solvent generally used as an organic solvent for a coloring material dispersion, methyl is used. Group, ethyl group, isobutyl group, n-butyl group, 2-ethylhexyl group, benzyl group, cyclohexyl group, dicyclopentanyl group, hydroxyethyl group, phenoxyethyl group, adamantyl group, methoxypolyethylene glycol group, methoxypolypropylene glycol group , Polyethylene glycol group and the like are preferable.

In the polymer chain, the structural unit represented by the general formula (IV) may be used alone or in combination of two or more.
From the viewpoint of dispersibility and dispersion stability of the coloring material, the total ratio 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 ratio of the structural units represented by the general formula (IV) in the polymer chain is 40% by mass or more with respect to all the structural units of the polymer chain. It is preferably 70% by mass or more, and more preferably 70% by mass or more.

Further, the polymer chain of the macromonomer is composed of the structural unit represented by the following general formula (V) and the structural unit represented by the following general formula (V') among the structural units represented by the general formula (IV). It is preferable to include at least one structural unit selected from the above group from the viewpoint of improving the adhesion to the substrate and shortening the developing time.

In (Formula (V), R ^{11 'is} hydrogen atom or a methyl group, A ^2' is a divalent linking group, R ⁵ is an ethylene group or a propylene group, R ⁶ is a hydrogen atom, or a hydrocarbon group , M represents a number of 2 or more and 80 or less.
In the 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} is an alkylene group having 3 to 7 carbon atoms. The alkylene group R ⁹ 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, A 2 Formula (V) and a constitutional unit formula represented ^(V)', and A ^{2 "are} each independently a divalent linking group .A ² Examples of the divalent linking group in ^′ and A ^{2 ″} include those similar to the divalent linking group in ^{A 2 above.}
Among these, from the viewpoint of solubility in an organic solvent to be used in color filter applications, A ^{2 ',} and ^{A 2 "are} each independently a divalent linking group containing a -CONH- group or a -COO- group It is preferable, and it is more preferable that it is a -CONH- group or a -COO- group.

The m in the general formula (V) represents the number of repeating units of the ethylene oxide chain or the propylene oxide chain, and represents a number of 2 or more. Among them, 3 or more is preferable, and further, from the viewpoint of substrate adhesion. It is preferably 4 or more.
On the other hand, the upper limit of m is 80 or less, but it is preferably 50 or less from the viewpoint of solubility in an organic solvent used for color filter applications.

R ⁶ is a hydrogen atom or a hydrocarbon group ^{. Examples of the hydrocarbon group in 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 the like. Examples thereof include a combination thereof such as an aralkyl group and an alkyl-substituted aryl group.
Examples of the hydrocarbon group in R ⁶ include the same hydrocarbon groups as in R ⁴ .
As the hydrocarbon group for R ^6, among others, from the viewpoint of dispersion stability, an alkyl group having 1 to 18 carbon atoms, an aryl group of an alkyl group are carbon atoms 6 even to 12 substitutions, and, alkyl group It is preferably at least one selected from the group consisting of aralkyl groups having 7 to 14 carbon atoms which may be substituted, and is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or n. It is preferably one or more selected from the group consisting of a nonyl group, an n-lauryl group, an n-stearyl group, a phenyl group in which an alkyl group may be substituted, and a benzyl group.

In the general formula (V'), R ⁷ is an alkylene group having 1 to 10 carbon atoms, and among them, an alkylene group having 2 to 8 carbon atoms is preferable from the viewpoint of solvent resolubility.
R ⁸ is an alkylene group having 3 to 7 carbon atoms, and among them, an alkylene group having 3 to 5 carbon atoms and an alkylene group having 5 carbon atoms are preferable from the viewpoint of substrate adhesion.
R ⁹ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group in R ⁹ may be the same as the hydrocarbon group in ^{R 6.}

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. Among them, from the viewpoint of substrate adhesion, it is preferably 2 or more, and further 3 or more. Is preferable.
On the other hand, the upper limit of n is 40 or less, but it is preferably 20 or less from the viewpoint of solubility in an organic solvent used for color filter applications.

In the polymer chain, 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') may be used alone. It is good, but two or more kinds may be mixed.
From the viewpoint of improving the adhesion to the base material and shortening the developing time, the structural units represented by the general formula (V) and the following are used with respect to all the structural units of the polymer chain in the macromonomer of the graft copolymer. The total ratio of at least one structural unit selected from the group consisting of the structural units represented by the general formula (V') is preferably 5% by mass or more, and more preferably 10% by mass or more. , 15% by mass or more is more preferable. The total ratio 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 point of solvent resolubility. Therefore, it is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less with respect to all the constituent 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 is represented by 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 to be formed, other structural units may be included.
Examples of the other structural unit include a structural unit derived from an ethylenically unsaturated monomer that can be copolymerized with an ethylenically unsaturated monomer or the like that induces the structural unit represented by the general formula (IV).
Examples of the monomer for inducing other constituent units include styrenes such as styrene and 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 is based on the effect of the present invention with respect to all the structural units of the polymer chain. It is preferably 30% by mass or less, and more preferably 10% by mass or less.

Further, the mass average molecular weight Mw of the polymer chain is preferably 2000 or more, more preferably 3000 or more, and further preferably 4000 or more, from the viewpoint of dispersibility and dispersion stability of the coloring material. 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 specific surface area of the solvent-affinity portion of the dispersant is increased, so that the above-mentioned action can be improved.
The mass average molecular weight Mw of the polymer chain can be measured for the polymerizable oligomer or the polymer chain containing the reactive group in the same manner as the dispersant described later.

Further, the polymer chain preferably has an acid value of 10 mgKOH / g or less, and more preferably 0 mgKOH / g or less from the viewpoint of dispersion stability. Here, the acid value can be measured for the polymerizable oligomer or the polymer chain containing the reactive group in the same manner as the acid value of the dispersant described later.
The polymer chain may contain the structural unit represented by the general formula (I) as long as the effect of the present invention is not impaired, but from the viewpoint of dispersion stability, all the structural units of the polymer chain may be contained. On the other hand, the total ratio of the constituent units containing an acidic group is preferably 5% by mass or less, and more preferably 0% by mass.

Further, the amine value of the polymer chain is preferably 10 mgKOH / g or less, 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 which is equivalent to the amount of hydrochloric acid required to neutralize 1 g of the solid content of the polymerizable oligomer or the polymer chain containing the reactive group. 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 effect of the present invention is not impaired. However, from the viewpoint of dispersion stability, the polymer chain contains a nitrogen atom with respect to all the structural units of the polymer chain. The total ratio of the constituent units is preferably 5% by mass or less, and more preferably 0% by mass.

In the graft copolymer, the content ratio 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 graft copolymer. It is more preferably 6% by mass or more and 45% by mass or less, and further preferably 9% by mass or more and 35% by mass or less. When the content ratio of the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity portion with the coloring material in the graft copolymer becomes appropriate, and Since the decrease in solubility in the organic solvent can be suppressed, the adsorptivity to the coloring material is improved, and excellent dispersibility, dispersion stability, and solvent resolubility can be obtained.
On the other hand, in the graft copolymer, the total content ratio of the structural unit containing the graft polymer chain and the structural unit represented by the general formula (III) is relative to all the structural units of the main chain of the graft copolymer. It is preferably 40% by mass or more and 97% by mass or less, more preferably 55% by mass or more and 94% by mass or less, and further preferably 65% by mass or more and 91% by mass or less. If the total content ratio of the structural unit containing the graft polymer chain in the graft copolymer and the structural unit represented by the general formula (III) is within the above range, the ratio of the solvent-affinitive portion in the graft copolymer. Is appropriate, a sufficient steric repulsion effect as a dispersant can be maintained, and the specific surface area of the solvent-affinitive portion of the dispersant is increased, so that the action on the effect can be improved.
The content ratio of the structural unit induces the structural unit represented by the general formula (I), the structural unit represented by the general formula (III), and the like when synthesizing the graft copolymer. It is calculated from the amount of monomer charged.

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 in which the effects of the present invention are not impaired. In addition to the above, it may have other structural units. As the other structural unit, an ethylenically unsaturated monomer, which 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, and the like. Constituent units can be introduced.
Other structural units copolymerized with the structural unit represented by the general formula (I) in the main chain include, for example, the structural unit represented by the general formula (IV) and the general formula (I). ), And the like, which contains an acidic group different from the structural unit represented by).
Examples of the monomer for inducing a structural unit containing an acidic group different from the structural unit represented by the general formula (I) include maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, and cinnamon bark. Acids and the like can be mentioned.
In the graft copolymer, the total content ratio of the other constituent units copolymerized in the main chain is preferably 40% by mass or less with respect to all the constituent units of 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 can produce the 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) and an ethylenically unsaturated binary at the polymer chain and its terminal are used. Examples thereof include a method in which a polymerizable oligomer (macromonomer) composed of a group having a heavy bond is contained as a copolymerization component and copolymerized to produce a graft copolymer.
If necessary, other monomers are also used, and a graft copolymer can be produced by using a known polymerization means.

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

Further, when a graft copolymer having a structural unit represented by the general formula (I) is produced, the monomer represented by the general formula (Ia) is additionally polymerized with another ethylenically unsaturated monomer. After the copolymer is formed, the polymer chain may be introduced using a polymer chain containing a reactive group that can react with the reactive group contained in the copolymer. 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 obtained. The polymer chain may be introduced by reacting with the containing polymer chain.
For example, a polymer chain having a glycidyl group in the side chain is reacted with a polymer chain having a carboxyl group at the end, or a polymer chain having an isocyanate group in the side chain is reacted with a polymer chain having a hydroxy group at the end. The polymer chain can be introduced.
In the polymerization, additives generally used for polymerization, such as a polymerization initiator, a dispersion stabilizer, and a chain transfer agent, may be used.

{Block copolymer}
The block copolymer used in the present invention has an A block containing a structural unit represented by the general formula (I), which functions as an adsorption site for a coloring material.
The block copolymer used in the present invention preferably further has a B block that functions 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, and thus the description thereof is omitted here.
In the A block, the structural unit represented by the general formula (I) may be composed of one type or may include two or more types of structural units.

The block A may have other structural units in addition to the structural unit represented by the general formula (I) as long as the effects of the present invention are not impaired. As the other structural unit, an ethylenically unsaturated monomer, which 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, and the like. Constituent units can be introduced.
Other structural units included in the A block within a range in which the effects of the present invention are not impaired include, for example, the structural unit represented by the general formula (IV) and the configuration represented by the general formula (I). Examples thereof include a structural unit containing an acidic group different from the unit.
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 in the graft copolymer. Since it is okay to have it, the explanation here is omitted.
The total content ratio of the other structural units contained in the A block is not particularly limited as long as the effect of the present invention is not impaired, but from the viewpoint of dispersibility and dispersion stability, all the structural units of the A block can be used. On the other hand, 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 ratio of the structural unit represented by the general formula (I) contained in the A block is 60% by mass or more with respect to all the structural units of the A block from the viewpoint of dispersibility and dispersion stability. Is preferable, 80% by mass or more is more preferable, and it 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 monomer that induces the structural unit represented by the general formula (I), depending on the solvent so as to have solvent affinity. It is preferable that the material is appropriately selected and used. As a guide, it is preferable to introduce the B block so that the solubility of the block copolymer at 23 ° C. is 20 (g / 100 g solvent) or more with respect to the solvent used in combination.

In the block copolymer used in the present invention, the B block that functions as a solvent affinity site has good solvent affinity, and the dispersibility and dispersion stability of the coloring material are good. ) Is preferably included at least one type of structural unit.
The structural unit contained in the B block and represented by the general formula (IV) may be the same as that described in the graft copolymer, and thus the description thereof is omitted here.

In the B block, the structural unit represented by the general formula (IV) may be one kind alone or a mixture of two or more kinds.
From the viewpoint of dispersibility and dispersion stability of the coloring material, the total ratio 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 ratio 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. It is preferably 70% by mass or more, and more preferably 70% by mass or more.

Further, the B block is a group consisting of a structural unit represented by the general formula (V) and a structural unit represented by the general formula (V') among the structural units represented by the general formula (IV). It is preferable to include at least one structural unit selected from the above from the viewpoint of improving the adhesion to the substrate and shortening the developing time.
As 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, the graft is used. Since it may be the same as that described for the polymer, the description thereof is omitted here.

In the B block, 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') may be used alone. It is good, but two or more kinds may be mixed.
At least 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') from the viewpoint of improving the adhesion to the substrate and shortening the developing time. The total ratio of one type of structural unit is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 15% by mass or more with respect to all the structural units of the B block. Even more preferable. The total ratio 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 point of solvent resolubility. Therefore, it is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less with respect to all the constituent units of the B block.

The B block includes 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'). In addition to the structural unit represented by the general formula (IV), other structural units may be included.
Examples of the other structural unit include a structural unit derived from an ethylenically unsaturated monomer that can be copolymerized with an ethylenically unsaturated monomer or the like that induces the structural unit represented by the general formula (IV).
Examples of the monomer for inducing other constituent units include styrenes such as styrene and α-methylstyrene, vinyl ethers such as phenyl vinyl ether, and the like.

From the viewpoint of the effect of the present invention, the total ratio of the other structural units in the B block is preferably 30% by mass or less, preferably 10% by mass or less, based on all the structural units of the B block. Is more preferable.

The mass average molecular weight Mw of the B block is preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, from the viewpoint of 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 specific surface area of the solvent-affinity portion of the dispersant is increased, so that the above-mentioned action can be improved.
The mass average molecular weight Mw of the B block only can be measured for the polymer of the B block only in the same manner as the dispersant described later.

Further, the acid value of the B block is preferably 10 mgKOH / g or less, and more preferably 0 mgKOH / g from the viewpoint of dispersion stability. Here, the acid value can be measured for the polymer containing only the B block in the same manner as the acid value of the dispersant described later.
The B block is at least one selected from the group consisting of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) as long as the effect of the present invention is not impaired. It may contain a structural unit containing an acidic group such as a structural unit of a seed, but from the viewpoint of dispersion stability, the total ratio of the structural unit containing an acidic group to all the structural units of the B block. Is preferably 5% by mass or less, and more preferably 0% by mass.

Further, the amine value of the B block is preferably 10 mgKOH / g or less, and 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 the polymer containing only the B block.
The B block may contain a nitrogen atom-containing constituent unit as long as the effect of the present invention is not impaired. However, from the viewpoint of dispersion stability, the B block contains nitrogen atoms with respect to all the constituent units of the B block. The total ratio of the constituent units is preferably 5% by mass or less, and more preferably 0% by mass.

Further, the B block may be selected so as to function as a solvent-affinity site, and the constituent unit may be one kind, or two or more kinds may be mixed. When the B block contains two or more kinds of structural units, two or more kinds of structural units may be randomly copolymerized in the B block.

The bonding order of the block copolymers may be any one that can stably disperse the coloring material, and is not particularly limited, but the block A block is bonded to one end of the block copolymer. However, it is preferable because it has excellent interaction with the coloring material and can effectively suppress the aggregation of the dispersants, and is an AB type block copolymer, an ABA type block copolymer, or a BAB type block copolymer. Of these, AB type block copolymers and BAB type block copolymers are preferable.

In the block copolymer, the total content ratio of 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 all the constituent units of the main chain of the block copolymer. More preferably, it is 9% by mass or more and 35% by mass or less. When the total content ratio of A blocks in the block copolymer is within the above range, the ratio of the affinity portion with the coloring material in the block copolymer becomes appropriate, and the decrease in solubility in the organic solvent is suppressed. Therefore, the adsorptivity to the coloring material is improved, and excellent dispersibility, dispersion stability and solvent resolubility can be obtained.
In the block copolymer, the content ratio 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 further preferably 9% by mass or more and 35% by mass or less. When the content ratio of the structural unit represented by the general formula (I) in the block copolymer is within the above range, the ratio of the affinity portion with the coloring material in the block copolymer becomes appropriate, and Since the decrease in solubility in organic solvents can be suppressed, the adsorptivity to coloring materials is improved, and excellent dispersibility, dispersion stability and solvent resolubility can be obtained.

On the other hand, in the block copolymer, the total content ratio of B blocks 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 all the constituent units of the main chain of the block copolymer. The following is more preferable, and 65% by mass or more and 91% by mass or less is further preferable. When the total content ratio of B blocks in the block copolymer is within the above range, the ratio of the solvent-affinitive portion in the block copolymer becomes appropriate, and a sufficient steric repulsion effect as a dispersant can be maintained. At the same time, the specific surface area of the solvent-affinitive portion of the dispersant is increased, so that the effect on the effect can be improved.
The content ratio of the structural unit induces the structural unit represented by the general formula (I), the structural unit represented by the general formula (IV), and the like when synthesizing a block copolymer. It is calculated from the amount of monomer charged.

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

{Characteristics of a polymer having a structural unit represented by the general formula (I)}
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, 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, from the viewpoint of solvent resolubility, it is preferably 50,000 or less, and more preferably 30,000 or less.
The ratio (Mw / Mn) of the mass average molecular weight Mw of the dispersant, which is the graft copolymer, to the number average molecular weight Mn is preferably 4.0 or less, preferably 3.5 or less, from the viewpoint of dispersion stability. It is more preferably less than or equal to, and more preferably 3.0 or less.
The ratio (Mw / Mn) of the mass average molecular weight Mw of the dispersant, which is the block copolymer, to the number average molecular weight Mn is preferably 1.8 or less, preferably 1.6 or less, from the viewpoint of dispersion stability. It is more preferably less than or equal to, and more preferably 1.4 or less.
In the present invention, the mass average molecular weight Mw and the number average molecular weight Mn are values measured by GPC (gel permeation chromatography). For the measurement, HLC-8120GPC manufactured by Tosoh was used, the elution solvent was N-methylpyrrolidone added with 0.01 mol / liter of lithium bromide, and the polystyrene standard for the calibration curve was Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (above, Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh), and the measurement columns were TSK-GEL ALPHA-M x 2 (manufactured by Tosoh). Is.

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, preferably 30 mgKOH / g or more, from the viewpoint of dispersion stability. More preferably, it is more preferably 40 mgKOH / g or more, and even more preferably 60 mgKOH / g or more.
On the other hand, the acid value of at least one of the graft copolymer and the block copolymer is preferably 250 mgKOH / g or less, and more preferably 180 mgKOH / g or less, from the viewpoint of solvent resolubility. , 160 mgKOH / g or less, and even more preferably 120 mgKOH / g or less.
The acid value of the dispersant represents the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid content of the copolymer, and is measured by the method described in JIS K 0070: 1992. Value.

[Salt polymer]
The salt-type polymer used as the dispersant in the present invention includes at least a 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 tertiary. It is a salt-type polymer in which one or more compounds (B) selected from the group consisting of an amino group-containing basic compound and a basic heterocyclic compound form a salt.

(Compound (B))
The compound (B) used as a modifier for forming a salt with at least a part of the acidic group contained in the general formula (I) comprises a tertiary amino group-containing basic compound and a basic heterocyclic compound. One or more selected from the group.
Compound (B) is a basic compound for forming a salt with an acidic group, and the acid dissociation constant (pKa) of the first stage of compound (B) is 7.5 or more, and is dispersible and dispersed. From the viewpoint of stability and solvent resolubility, it is preferably 8.5 or more, more preferably 9.5 or more, and even more preferably 10.5 or more. On the other hand, the upper limit of the acid dissociation constant is not particularly limited as long as the effect of the present invention is not impaired, but 30 or less can be mentioned. Here, pKa is a value of the acid dissociation constant in water at 25 ° C.
As a method for measuring the acid dissociation constant in the present invention, the alkaline titration method described on pages 215 to 217 of the second edition of the Experimental Chemistry Course published by Maruzen Co., Ltd. can be used.

Among the compound (B), the tertiary amino group-containing basic compound contains a tertiary amino group, and if it is a basic compound, it may further have another functional group. Examples of other functional groups include a hydroxyl group, a (meth) acryloyloxy group, a (meth) acrylamide group, an amide group, an ether group and the like.
Examples of the tertiary amino group-containing basic compound include dimethylbenzylamine (pKa: 9), triethylamine (pKa: 10.8), tributylamine (pKa: 10), and 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), N, N, N', N ", N" -pentamethyldiethylenetriamine (pKa: 8.8), 2- (dimethylamino) ethanol (pKa: 9.3), tetramethylethylenediamine (pKa:: 8.3), N, N, N', N', N "-pentamethyldipropylene triamine (pKa: 9.9), N, N-dimethylcyclohexylamine (pKa: 10.7), N- [3 -(Dimethylamino) propyl] acrylamide (pKa: 10.4), dimethylaminoethyl methacrylate (pKa: 8.2) and the like can be mentioned.
Examples of the basic heterocyclic compound include 1,8-diazabicyclo [5.4.0] undecene-7 (pKa: 12.5) and 1,5-diazabicyclo [4.3.0] nonen-. 5 (pKa: 12.7), 1,5,7-triazabicyclo [4.4.0] deca-5-ene (pKa: 14.7), 7-methyl-1,5,7-triaza Bicyclo [4.4.0] deca-5-ene (pKa: 14.4), 2-methylimidazole (pKa: 7.8), 1-isobutyl-2-methylimidazole (pKa: 7.8), and Examples thereof include triethylenediamine (pKa: 8.8).
In terms of dispersion stability, brightness, contrast, and solvent resolubility, among others, 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] Deca-5-ene (pKa: 14.7), and 7-Methyl-1 , 5,7-Triazabicyclo [4.4.0] Deca-5-ene (pKa: 14.4) It is preferable to use one or more selected from the group.
Further, since the curability of the coating film is improved and the chipping resistance of the resist coating film during alkaline development is improved, it is ethylenic like N- [3- (dimethylamino) propyl] acrylamide and dimethylaminoethyl methacrylate. Tertiary amino group-containing basic compounds and basic heterocyclic compounds having polymerizable functional groups such as unsaturated double bonds are also preferable.

From the viewpoint of dispersibility and dispersion stability, the compound (B) preferably has a molecular weight of 800 or less, more preferably 650 or less, further preferably 500 or less, and 350 or less. Is even more preferable. On the other hand, the compound (B) preferably has a molecular weight of 60 or more from the viewpoint of heat resistance.

In the salt-type polymer, the content of the compound (B) is salt-formed with the terminal acidic group of the structural unit represented by the general formula (I), and thus is represented by the general formula (I). The total amount of at least one selected from the compound (B) is preferably 0.01 molar equivalent or more, and is preferably 0.05 molar equivalent or more, with respect to the terminal acidic group of the represented structural unit. More preferably, it is more preferably 0.1 molar equivalent or more, and particularly preferably 0.2 molar equivalent or more. When it is at least the above lower limit value, the effect of improving the dispersibility of the coloring material, the contrast, the adhesion to the base material, and the brightness by salt formation can be easily obtained. Similarly, it is preferably 1 molar equivalent or less, more preferably 0.8 molar equivalent or less, further preferably 0.7 molar equivalent or less, and particularly preferably 0.6 molar equivalent or less. preferable. When it is not more than the above upper limit value, it can be considered that the alkali developability and the solvent resolubility are excellent.
At least one selected from the group consisting of compound (B) may be used alone or in combination of two or more. When two or more kinds are combined, the total content thereof is preferably within the above range.

The salt-type polymer is selected from the group consisting of the compound (B) in a solvent in which a polymer having a structural unit represented by the general formula (I) before salt formation is dissolved or dispersed. Examples thereof include a method of adding at least one kind, stirring, and heating if necessary.
It should be noted that the terminal acidic group of the structural unit represented by the general formula (I) of the polymer and at least one selected from the group consisting of the compound (B) form a salt, and The ratio can be confirmed by a known method such as NMR.

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

The dispersant according to the present invention is a basic compound containing at least a part of acidic groups contained in the general formula (I) and a tertiary amino group-containing basic compound of the polymer having a structural unit represented by the general formula (I). A salt-type polymer obtained by forming a salt with one or more compounds (B) selected from the group consisting of a basic heterocyclic compound and a basic heterocyclic compound.
In the colorant dispersion liquid according to the present invention, the dispersant includes at least a 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 3 It contains at least a salt-type polymer in which a salt is formed from one or more compounds (B) selected from the group consisting of a class amino group-containing basic compound and a basic heterocyclic compound, but the effect of the present invention is effective. Other dispersants may be included as long as they are not impaired. As the other dispersant, for example, a known dispersant can be appropriately selected and used.
In the dispersant used in the color material dispersion liquid according to the present invention, the content ratio of the salt-type copolymer is preferably 60% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more. It is even more preferably 90% by mass or more, and it may be 100% by mass.

In the color material dispersion liquid according to the present invention, at least the salt-type copolymer is used as the dispersant, and the content of the dispersant is the type of the color material used and the solid content in the coloring curable composition described later. It is appropriately selected according to the concentration and the like.
The content of the dispersant is preferably 3% by mass or more and 60% by mass or less with respect to the total solid content in the color material dispersion liquid, and 5% by mass or more and 45% by mass or less. Is more preferable. When it is at least the above lower limit value, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the color curable composition is excellent. Further, when it is not more than the above upper limit value, the development residue is good.
In the present invention, the solid content is all other than the above-mentioned solvent, and includes monomers dissolved in the solvent and the like.

<Color material>
In the present invention, the coloring material may be any as long as it can develop a desired color when the colored layer of the color filter is formed, and is not particularly limited. Salt-forming compounds and the like can be used alone or in combination of two or more. Among them, organic pigments are preferably used because they have high color development and high heat resistance. Examples of the organic pigment include compounds classified as Pigments in the color index (CI; published by The Society of Dyers and Colorists), specifically, the following color index (CI). .) 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: 1,128,129,133,134,136,138,138,142,147,148,150,151,152,153,154,155,156,157,158,159,160,161,162,163, 164, 165, 166, 167, 168, 173, 175, 185, 194, 211, 214, 215, 231 and C.I. I. Pigment Yellow 150 derivative pigment;
C. I.

Pigment Orange

1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 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 and 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 pigment include titanium oxide, barium sulfate, calcium carbonate, zinc flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, and oxidation. Examples include chrome green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

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

Examples of the dispersible dye include dyes that can be dispersed by imparting various substituents to the dye or by using the dye in combination with a solvent having low solubility.
Examples of the salt-forming compound of the dye include a compound in which the dye forms a salt with a counter ion, and examples thereof include a salt-forming compound of a basic dye and an acid and a salt-forming compound of an acidic dye and a base, which are soluble in a solvent. Also includes rake pigments insolubilized in a solvent using known rake formation (chloride formation) techniques.
In the present invention, the dispersibility and dispersion stability of the color material are improved by using a color material containing at least one selected from a dye and a salt-forming compound of the dye in combination with the dispersant of the present invention. Can be 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 guide, if the amount of the dye dissolved in 10 g of the solvent (or mixed solvent) is 10 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

Among them, the coloring materials are diketopyrrolopyrrole pigment, anthraquinone pigment, quinophthalone pigment, copper phthalocyanine pigment, zinc phthalocyanine pigment, aluminum phthalocyanine pigment, dioxazine pigment, azomethine dye, zinc phthalocyanine dye, triarylmethane dye, quinophthalone dye, coumarin. When at least one selected from the group consisting of dyes, phthalocyanine dyes, and salt-forming compounds of these dyes is contained, it is preferable to use the dispersant from the viewpoint that a high-brightness colored layer can be formed. The coloring materials include, 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 above group.

Examples of the diketopyrrolopyrrole pigment include C.I. I. Pigment Red 254, 255, 264, 272, 291 and the diketopyrrolopyrrole pigment represented by the following general formula (i), among which C.I. I. Pigment Red 254, 272, 291 and ^{at least one selected from diketopyrrolopyrrole pigments in which R 21} and R ²² are 4-bromophenyl groups in the following general formula (i) are preferable.

(In general formula (i), R ²¹ and R ²² are independently 4-chlorophenyl groups or 4-bromophenyl groups, respectively.)

Examples of the anthraquinone pigment include C.I. I. Pigment Red 177 and the like.
Examples of the quinophthalone pigment include C.I. I. Pigment Yellow 138, 231 and the like.
Examples of the copper phthalocyanine pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, C.I. I. Pigment Greens 7, 36, etc., among others, C.I. I. Pigment Blue 15: 6 is preferred.
Examples of the zinc phthalocyanine pigment include C.I. I. Pigment greens 58, 59 and the like.
Examples of the aluminum phthalocyanine pigment include C.I. I. Pigment greens 62, 63 and the like.
Examples of the dioxazine pigment 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 the quinophthalone dye include C.I. I. Disperse Yellow 54, 64, 67, 134, 149, 160, C.I. I. Solvent Yellow 114, 157 and the like can be mentioned, among which C.I. I. Disperse Yellow 54 is preferred.
Examples of the triarylmethane dye include C.I. I. Basic Red 9, C.I. I. Basic blue 1, 7, etc. can be mentioned.
Examples of the phthalocyanine dye include C.I. I. Basic Blue 140 and C.I. I. Examples thereof include zinc phthalocyanine dyes in which the central metal of Basic Blue 140 is replaced with zinc.
Further, the coloring material represented by the following general formula (1) is also preferably used in combination with the dispersant of the present invention from the viewpoint of brightness.

(In the general formula (1), 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 is at least saturated aliphatic hydrocarbon at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and a hetero atom may be contained in the carbon chain. B ^c- represents a c-valent polyacid anion. Represented. R ⁱ to R ^v each independently represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and represents R ⁱⁱ and R ⁱⁱ , and R ^iv and R. ^v may be bonded to form a ring structure. R ^vi and R ^vii may independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano. .Ar ¹ represents a group may be different even each R ^{i ~} R ^vii and Ar ¹ in. more representing a divalent aromatic group which may have a substituent the same.
a and c represent an integer of 2 or more, and b and d represent an integer 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. The plurality of e, f, and g may be the same or different from each other. )

As a description of each code of the color material represented by the general formula (1), the description of the code of the corresponding portion of the general formula (I) described in International Publication No. 2018/003706 can be referred to. Examples of the partial structure and other structures of the coloring material represented by the general formula (1) include the structures described in International Publication No. 2018/003706, International Publication No. 2012/144521, and the like.

As the coloring material used in the present invention, C.I. I. Pigment Red 177, 254, 291 and 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. Pigment Violet 23 and at least one selected from the group consisting of the coloring material represented by the general formula (1) are preferable.

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

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

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

In the color material dispersion liquid according to the present invention, the content of the color material is not particularly limited. The content of the coloring material is 5% by mass or more and 80% by mass or less, more preferably 8% by mass or more and 70% by mass or less, based on the total amount of solids in the coloring material dispersion liquid from the viewpoint of dispersibility and dispersion stability. It is preferable to mix in the ratio of.
In particular, when a coating film or a colored layer having a high color material concentration is formed, 30% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 75% by mass, based on the total amount of solid content in the color material dispersion liquid. It is preferable to mix in the following proportions.

<Solvent>
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the colorant dispersion and can dissolve or disperse them. The solvent can be used alone or in combination of two or more.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; and carbitol solvents such as methoxy ethoxy ethanol and ethoxyethoxy ethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester solvents such as ethyl lactate and cyclohexanol acetate; 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; aproton amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, 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 Can be 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 the solubility of other components. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, etc. In addition, one or more selected from the group consisting of 3-methoxybutyl acetate is preferable from the viewpoint of solubility of other components and application suitability.

The color material dispersion liquid according to the present invention preferably contains the above solvent in a range of 55% by mass or more and 95% by mass or less with respect to the total amount of the color material dispersion liquid containing the solvent. It is preferably in the range of 65% by mass or more and 90% by mass or less, and more preferably in the range of 70% by mass or more and 88% by mass or less. If the amount of solvent is too small, the viscosity tends to increase and the dispersibility tends to decrease. Further, if the amount of the solvent is too large, the density of the coloring material decreases, and it may be difficult to achieve the target chromaticity coordinates.

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

The color material dispersion liquid according to the present invention is used as a preliminary preparation for preparing a color curable composition described later. That is, the color material dispersion liquid is (mass of the color material component in the composition) / (solid content other than the color material component in the composition) that is preliminarily prepared in the step before preparing the color curable composition described later. A colorant dispersion with a high mass ratio. Specifically, the ratio (mass of color material component in composition) / (mass of solid content other than color material component in composition) is usually 1.0 or more. By mixing the color material dispersion liquid with each component described later, it is possible to prepare a color curable composition having excellent dispersibility.

<Manufacturing method of color material dispersion liquid>
In the present invention, the method for producing the color material dispersion liquid is not particularly limited as long as the color material is a method for obtaining the color material dispersion liquid dispersed in the solvent by the dispersant.
From the viewpoint of excellent dispersibility and dispersion stability of the color material, the method for producing the color material dispersion liquid according to the present invention includes a step of preparing the dispersant and a color material in a solvent in the presence of the dispersant. Examples include those having a step of dispersing the above.

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

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

<Use>
Since the color material dispersion liquid and the dispersant according to the present invention can produce a color curable composition that simultaneously satisfies excellent dispersion stability, brightness, contrast, substrate adhesion, and solvent resolubility. Above all, it can be suitably used for color filter applications.
Further, the colorant dispersion liquid and the dispersant according to the present invention can also be used for a colored resin composition that does not require a photosensitive component or a thermosetting colored resin composition.
The color material dispersion liquid and the dispersant according to the present invention are used in various applications in which excellent dispersion stability of fine color materials is required, and are used in inkjet inks, printing inks, writing tools, cosmetics, and the like. Is also used.

II. Color Curable Composition The color curable composition according to the present invention is characterized by containing a coloring material, the dispersant according to the present invention, a polymerizable compound, an initiator, and a solvent.
By using the dispersant according to the present invention, the color-curable composition of the present invention can simultaneously satisfy excellent dispersion stability, brightness, contrast, substrate adhesion, and solvent resolubility. ..

The color curable composition of the present invention contains at least a coloring material, a dispersant, a polymerizable compound, an initiator, and a solvent, and further other components are used as long as the effects of the present invention are not impaired. It may contain an ingredient. Hereinafter, each component contained in the color curable composition of the present invention will be described. However, the dispersant, the coloring material, and the solvent are the same as those described in the coloring material dispersion liquid according to the present invention. The description here will be omitted.

<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 thermopolymerizable compound can be used. As the thermopolymerizable compound, a compound having a thermopolymerizable functional group such as a carboxyl group, an amino group, an epoxy group, a hydroxyl group, a glycidyl group, an isocyanate group, and an alkoxyl group can be used in the molecule. Further, by using a compound having an ethylenically unsaturated group in combination with a thermal radical polymerization initiator, it can also be used as a thermally polymerizable compound. As the polymerizable compound, a photopolymerizable compound that can be polymerized with a photoinitiator, which will be described later, is preferable because a pattern can be easily formed by a photolithography method using an existing process.

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

One of these photopolymerizable compounds may be used alone, or two or more thereof may be used in combination. Further, when the color curable composition of the present invention is required to have excellent photocurability (high sensitivity), the photopolymerizable compound has three or more polymerizable double bonds (trifunctional). Is preferable, and poly (meth) acrylates of trivalent or higher-valent polyhydric alcohols and their dicarboxylic acid-modified products are preferable. Acrylate, succinic acid-modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate A succinic acid modified product, dipentaerythritol hexa (meth) acrylate and the like are preferable.

The content of the polymerizable compound in the color-curable composition is preferably 5% by mass or more and 60% by mass or less, preferably 10% by mass or more and 50% by mass or less, based on the total solid content of the color-curable composition. It is more preferable that the content is 20% by mass or more and 40% by mass or less. When the content of the polymerizable compound is at least the above lower limit value, curing failure can be suppressed, so that the exposed portion can be suppressed from being eluted during development, and the content of the polymerizable compound is at least the above upper limit value. Since development defects can be suppressed and heat shrinkage can be suppressed, minute wrinkles are less likely to occur on the entire surface of the colored layer.

<Initiator>
The initiator used in the color-curable composition of the present invention is not particularly limited, and one or a combination of two or more of the various conventionally known initiators can be used. Examples of the initiator include polymerization initiators such as thermal polymerization initiators and photopolymerization initiators, and specific examples thereof include those described in JP2013-029832A.

Examples of the photoinitiator 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 the photoinitiator include aromatic ketones such as benzophenone, 4,4'-bisdiethylaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, and ethyl benzoin. Benzoyls, biimidazoles such as 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazol and the like Halomethyloxaziazole compounds, halomethyl-S-triazine compounds such as 2- (4-butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1 , 2-Diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone- ,, 1-Hydroxy-cyclohexyl-phenylketone, benzyl, benzoyl benzoic acid, methyl benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, p-dimethylamino benzoate Isoamyl acid, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenylsulfide, 1-hydroxy- Cyclohexyl-phenylketone, 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-propanol, 1- (9,9-dibutyl-9H-fluoren-2-yl) -2-methyl-2- (4-morpholinyl)- 1-Propanon and the like can be mentioned.
Among them, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1- Butanone, 4,4'-bis (diethylamino) benzophenone, and diethylthioxanthone are preferably used. Furthermore, it is sensitive to combine an α-aminoacetophenone-based initiator such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one with a thioxanthone-based initiator such as diethylthioxanthone. It is preferable because it suppresses adjustment and water stains and improves development resistance.
When the α-aminoacetophenone-based initiator and the thioxanthone-based initiator are used, the total content thereof is preferably 5% by mass or more and 15% by mass or less with respect to the total solid content of the color-curable composition. When the amount of the initiator is 15% by mass or less, the sublimated product in the manufacturing process is reduced, which is preferable. When the amount of the initiator is 5% by mass or more, development resistance such as water stain is improved.

In the present invention, the photoinitiator preferably contains an oxime ester-based photoinitiator because the sensitivity can be improved. Further, by using the oxime ester-based photoinitiator, it is easy to suppress the variation in the line width in the plane when forming the fine line pattern. Further, by using the oxime ester-based photoinitiator, the residual film ratio tends to be improved and the effect of suppressing the occurrence of water stains tends to be enhanced.
The oxime ester-based photoinitiator preferably has an aromatic ring, and has a condensed ring containing an aromatic ring, from the viewpoint of reducing contamination of the colored curable composition and equipment contamination by decomposition products. It is more preferable to have a fused ring containing a benzene ring and a hetero ring.
Oxime ester-based photoinitiators include 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime), JP-A-2000-80068, JP-A-2001-233842, JP-A-2010-527339, JP-A-2010-527338, It can be appropriately selected from the oxime ester-based photoinitiators described in JP-A-2013-041153 and the like. Commercially available products include Irgacure OXE-01 having a diphenylsulfide skeleton, Adeka Arkuru's NCI-930, TR-PBG-345, TR-PBG-304 having a carbazole skeleton, Irgacure OXE-02 having a fluorene skeleton, and Adeka Arkuru's NCI. -831, TR-PBG-365, TR-PBG-3057 having a diphenylsulfide skeleton (all manufactured by Joshu Strong Electronics New Materials Co., Ltd.) and the like may be used. In particular, it is preferable to use an oxime ester-based photoinitiator having a diphenylsulfide skeleton or a fluorene skeleton from the viewpoint of brightness. Further, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.

Further, it is preferable to use an oxime ester-based photoinitiator in combination with a photoinitiator having a tertiary amine structure from the viewpoint of suppressing water stains and improving sensitivity. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure which is an oxygen quencher in the molecule, the radicals generated from the initiator are not easily deactivated by oxygen, and the sensitivity can be improved. be. Examples of commercially available photoinitiators having a tertiary amine structure include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (for example, Irgacure 907, manufactured by BASF). 2-Benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (eg, Irgacure 369, manufactured by BASF), 4,4'-bis (diethylamino) benzophenone (eg, Hycure ABP, etc.) (Made by Kawaguchi Yakuhin).
In addition, it is preferable to combine the oxime ester-based photoinitiator with the thioxanthone-based initiator from the viewpoints of adjusting the sensitivity, suppressing water stains, and improving the development resistance. It is preferable to combine an initiator in that the brightness and the residual film ratio are improved, the sensitivity can be 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 color curable composition is preferably 0.1% by mass or more and 15% by mass or less with respect to the total solid content of the color curable composition, and is 1% by mass or more and 10% by mass or less. Is more preferable. When the content of the initiator is at least the above lower limit value, curing proceeds sufficiently, and when the content of the initiator is at least the above upper limit value, side reactions can be suppressed and stability over time can be maintained. ..

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

(polymer)
As the polymer, when a photolithography step is used to form the colored layer, an alkali-soluble resin 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 step is used, an alkali-soluble resin different from the dispersant is not an essential component.
The photosensitive colored resin composition of the present invention preferably further contains an alkali-soluble resin different from the dispersant from the viewpoint that the alkali solubility can be easily adjusted.
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 referred to as having an acid value of 30 mgKOH / g or more as a guide.

As the alkali-soluble resin, a conventionally known alkali-soluble resin can be appropriately selected and used. For example, the alkali-soluble resin described in WO2016 / 104493 can be appropriately selected and used.
The preferable alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group, and specifically, an acrylic such as an acrylic copolymer having a carboxy group and a styrene-acrylic copolymer having a carboxy group. Examples thereof include based resins and epoxy (meth) acrylate resins having a carboxy group. Among these, those having a carboxy group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain are particularly preferable. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. Further, these acrylic copolymers, acrylic resins such as styrene-acrylic copolymers, and epoxy acrylate resins may be used by mixing two or more kinds.

The content of the alkali-soluble resin used in the color-curable composition is not particularly limited, but is preferably 1% by mass or more and 60% by mass or less, more preferably 5 with respect to the total solid content of the color-curable composition. It is in the range of mass% or more and 40 mass% or less. When the content of the alkali-soluble resin is at least the above lower limit, sufficient alkali developability can be easily obtained, and when the content of the alkali-soluble resin is at least the above upper limit, the film is roughened or the pattern is chipped during development. Is easy to suppress.
In the present invention, the solid content is all other than the solvent, and includes the monomer dissolved in the solvent and the like.

Further, the color curable composition according to the present invention contains, 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, and the like. It may contain a thermosetting polymer such as a melamine-urea cocondensate resin, a silicon resin, or a polysiloxane resin.

The polymer may be used alone or in combination of two or more.
The content of the polymer in the color-curable composition is not particularly limited, but is preferably 1% by mass or more and 60% by mass or less with respect to the total solid content of the color-curable composition, and is 5% by mass or more and 50% by mass. It is more preferably mass% or less. When the polymer content is at least the above lower limit value, the decrease in film strength can be suppressed, and when the polymer content is at least the above upper limit value, components other than the polymer can be sufficiently contained. ..

(Antioxidant)
It is preferable that the color-curable composition of the present invention further contains an antioxidant from the viewpoints of improving heat resistance, suppressing fading of the coloring material, and improving brightness. The antioxidant may be appropriately selected from conventionally known ones. Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like, and have heat resistance. From this point of view, it is preferable to use a hindered phenolic antioxidant. It may be a latent antioxidant as described in WO 2014/021023.

Examples of the hindered phenol-based antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF). 1,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris (4-hydroxy-3) , 5-Di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilyzer MDP-S, Sumitomo Chemical Co., Ltd.), 6,6'-thiobis (2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3,5-di-tert-butyl-4-hydroxybenzylphosphone Benzyl acid acid (trade name: Irgamod 195, manufactured by BASF) and the like can be mentioned. Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. ..

When the color curable composition of the present invention is contained in combination with the oxime ester-based photoinitiator and an antioxidant, the brightness is improved by a synergistic effect, and a fine line pattern is formed as designed for the mask line width. It is preferable because it improves the ability.

The amount of the antioxidant to be blended is preferably 0.1% by mass or more and 10.0% by mass or less, preferably 0.5% by mass, based on the total amount of solids in the color curable composition. More preferably, it is 5.0% by mass or less. If it is at least the above lower limit value, it is excellent in heat resistance and light resistance. On the other hand, if it is not more than the above upper limit value, the color-curable composition of the present invention can be a highly sensitive photosensitive resin composition.

When the antioxidant is used in combination with the oxime ester-based photoinitiator, the amount of the antioxidant is 1 part by mass with respect to 100 parts by mass of the total amount of the oxime ester-based photoinitiator. It is preferably 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and further preferably 5 parts by mass or more and 45 parts by mass or less. If it is within the above range, the effect of the above combination is excellent.

(Various additives)
The color-curable composition of the present invention may contain various additives.
Examples of the additive include a polymerization inhibitor, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, a defoaming agent, a silane coupling agent, an ultraviolet absorber, an adhesion accelerator and the like.
Specific examples of the surfactant and the plasticizer include those described in JP2013-029832A.

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

The content of the silane coupling agent is preferably 0.05% by mass or more and 10.0% by mass or less, preferably 0.1% by mass or less, based on the total amount of solids in the coloring curable composition. It is more preferably mass% or more and 5.0 mass% or less. When it is at least the above lower limit value and at least the above upper limit value, the substrate adhesion is excellent.

<Mixing ratio of each component in the color curable composition>
The total content of the coloring material is preferably 3% by mass or more and 65% by mass or less, more preferably 4% by mass or more and 60% by mass or less, based on the total solid content of the color curable composition. .. When it is at least the above lower limit value, the colored layer when the coloring curable composition is applied to a predetermined film thickness (usually 1.0 to 5.0 μm) has a sufficient color density. Further, if it is not more than the above upper limit value, it is possible to obtain a colored layer having excellent storage stability, sufficient hardness, and adhesion to a substrate. In particular, when a colored layer having a high concentration of the coloring material is formed, the content of the coloring material is 15% by mass or more and 75% by mass or less, more preferably 25% by mass, based on the total solid content of the coloring curable composition. It is preferable to blend in a proportion of 70% by mass or less.
The content of the dispersant is not particularly limited as long as it can uniformly disperse the coloring material, but is, for example, 1% by mass with respect to the total solid content of the color curable composition. It can be used at a ratio of 40% by mass or less. Further, it is preferably blended in a proportion of 2% by mass or more and 30% by mass or less, particularly preferably 3% by mass or more and 25% by mass or less, based on the total solid content of the color-curable composition. When it is at least the above lower limit value, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the color curable composition is excellent. Further, when it is not more than the above upper limit value, the alkali developability is good. In particular, when a colored layer having a high colorant concentration is formed, the content of the dispersant is 2% by mass or more and 25% by mass or less, more preferably 3% by mass, based on the total solid content of the coloring curable composition. It is preferable to mix in a proportion of 20% by mass or less.
Further, the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. It is usually preferably in the range of 55% by mass or more and 95% by mass or less, and above all, in the range of 65% by mass or more and 88% by mass or less with respect to the total amount of the coloring curable composition containing the solvent. Is more preferable. When the content of the solvent is within the above range, the coatability can be made excellent.

<Manufacturing method of color curable composition>
The method for producing the color-curable composition of the present invention is not particularly limited. Can be obtained by adding the components of the above and mixing using a known mixing means. Alternatively, a coloring material, the dispersant according to the present invention, a polyfunctional monomer, a photoinitiator, a solvent, an alkali-soluble resin if necessary, and other components are added, and a known mixing means is used. Can be obtained by mixing.

<Use>
Since the color-curable composition according to the present invention can simultaneously satisfy excellent dispersion stability, brightness, contrast, substrate adhesion, and solvent resolubility, it is particularly preferably used for color filter applications. be able to.
The color curable composition according to the present invention is used in various applications in which excellent dispersion stability of a fine coloring material is required, and is also used in inkjet inks and printing inks.

III. Color filter The color filter according to the present invention is a color filter including at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a colored curable composition according to the present invention. It 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.

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

The colored layer can be formed, for example, by the following method.
First, the above-mentioned color-curable composition of the present invention is applied onto a substrate described later by using a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, and a die coating method. To form a wet coating film. Of these, the spin coating method and the die coating method can be preferably used.
Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to this through a mask having a predetermined pattern, and an alkali-soluble resin, a polyfunctional monomer, or the like is photopolymerized and cured. Use as a coating film. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
In addition, heat treatment may be performed in order to accelerate the polymerization reaction after exposure. The heating conditions are appropriately selected depending on the blending ratio of each component in the color 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 developing solution to dissolve and remove the unexposed portion. As the developing solution, a solution in which an alkali is usually dissolved in water or a water-soluble solvent is used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. Moreover, a general method can be adopted as a developing method.
After the development treatment, the developing solution is usually washed and the cured coating film of the coloring curable composition is dried to form a colored layer. After the development treatment, a heat treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited and are appropriately selected depending on the intended use of the coating film.

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

<Board>
As the substrate, a transparent substrate, a silicon substrate, which will be described later, 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. Another color filter layer, a resin layer, a transistor such as a TFT, a circuit, or the like may be formed on these substrates.
The transparent substrate in the color filter of the present invention may be a substrate that is transparent to visible light, and is not particularly limited, and a transparent substrate used in a general color filter can be used. Specifically, a transparent rigid material having no flexibility such as quartz glass, non-alkali glass, or synthetic quartz plate, or a transparent flexible material having flexibility such as a transparent resin film, an optical resin plate, or a flexible glass. The material is mentioned.
The thickness of the transparent substrate is not particularly limited, but one of about 100 μm to 1 mm can be used depending on the use of the color filter of the present invention.
In addition to the substrate, the light-shielding portion, and the colored layer, the color filter of the present invention may have, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like.

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

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

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

As a method for forming the liquid crystal layer, a method generally used as a method for producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method. After forming the liquid crystal layer by the above method, the enclosed liquid crystal can be oriented by slowly cooling the liquid crystal cell to room temperature.

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

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

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
The acid values of the graft copolymer and the block copolymer were determined according to the measurement method described in the specification of the present invention described above.
The weight average molecular weight (Mw) and Mw / Mn of the graft copolymer and the block copolymer are standard polystyrene conversion values by GPC (gel permeation chromatography) according to the measurement method described in the above-mentioned specification of the present invention. Asked as.

(Synthesis Example 1: Production of Macromonomer m1)
A reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer is charged with 30.0 parts by mass of propylene glycol methyl ether acetate (PGMEA), and the temperature is 90 while stirring under a nitrogen stream. It was heated to ° C. Methyl methacrylate (MMA) 45.0 parts by mass, butyl methacrylate (BMA) 10.0 parts by mass, benzyl methacrylate (BzMA) 10.0 parts by mass, unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone (PCL-FM5) (Product name; Praxel FM5, manufactured by Daicel Co., Ltd., number of caprolactone chain repetitions = 5) 35.0 parts by mass, 7.0 parts by mass of mercaptopropionic acid, α, α'-azobisisobutyronitrile (AIBN) 1 The mixed solution of 9.0 parts by mass was added dropwise over 1.5 hours, and the reaction was further carried out 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, to 100.0 parts by mass of this white powder, 50.0 parts by mass of PGMEA, 7.4 parts by mass of glycidyl methacrylate (GMA), 0.30 parts by mass of N, N-dimethyldodecylamine and 0.2 parts of p-methoxyphenol. A part by mass was added, and the mixture was stirred at 110 ° C. for 24 hours while performing air bubbling. After cooling, the 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). It was 4500 and the molecular weight distribution (Mw / Mn) was 1.6.

(Synthesis Example 2: Production of Macromonomer m2)
In the production of the macromonomer m1 of Synthesis Example 1, 45.0 parts by mass of MMA, 10.0 parts by mass of BMA, 10.0 parts by mass of BzMA, and 35.0 parts by mass of unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone (PCL-FM5) were added. Instead of using, as shown in Table 1, MMA 60.0 parts by mass, BMA 10.0 parts by mass, methoxypolyethylene glycol monomethacrylate (manufactured by Nichiyu Co., Ltd., trade name; Blemmer PME-200, number of repeating ethyleneoxy groups = 4) (PME-200) Macromonomer m2 was produced in the same manner as in Synthesis Example 1 except that it was changed to 30.0 parts by mass. The obtained macromonomer m2 had a weight average molecular weight (Mw) of 6000 and a molecular weight distribution (Mw / Mn) of 1.7.

(Synthesis Example 3: Production of Graft Copolymer A)
A reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 100.0 parts by mass of PGMEA and heated to a temperature of 85 ° C. while stirring under a nitrogen stream. A mixed solution of 94.6 parts by mass of macromonomer m1 of Synthesis Example 1, 5.4 parts by mass of methacrylic acid (MAA), 1.3 parts by mass of n-dodecyl mercaptan, 50.0 parts by mass of PGMEA, and 1.0 part by mass of AIBN. The mixture was added dropwise over 1.5 hours, heated and stirred for 3 hours, and then 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, and the mixture was further aged at the same temperature for 1 hour. After cooling, the reaction solution was reprecipitated with 3000 parts by mass of hexane to obtain 99.0 parts by mass of the graft copolymer A. The obtained graft copolymer A had a weight average molecular weight (Mw) of 11200, Mw / Mn of 2.6, and an acid value of 35 mgKOH / g.

(Synthesis Examples 4 to 8: Production of Graft Copolymers B to F)
In Synthesis Example 1, instead of using 94.6 parts by mass and 5.4 parts by mass of MAA for the macromonomer m1, as shown in Table 1, the type of macromonomer and the structural unit represented by the general formula (I) are used. The type of monomer to be induced and at least one of the mass ratios of the macromonomer and the monomer for inducing the structural unit represented by the general formula (I) were changed, and the amount of n-dodecyl mercaptan was adjusted to adjust the molecular weight. Graft copolymers B to F were produced in the same manner as in Synthesis Example 1 except that they were arbitrarily changed. Table 1 shows the weight average molecular weight (Mw), Mw / Mn, and acid value of the obtained graft copolymers B to F.
In the table, 2-MOES represents 2-methacryloyloxyethyl succinic acid that induces a structural unit represented by the general formula (II-2). ATBS stands for 2-acrylamide-2-methylpropanesulfonic acid (manufactured by Toagosei, product name ATBS), and P-1M stands for 2-methacryloxyethyl acid phosphate (Kyoeisha Chemical Co., Ltd., product name Light Ester P). Represents -1M).

(Synthesis Example 9: Production of Block Copolymer G)
Reactor equipped with cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, digital thermometer, PGMEA 150.0 parts by mass, iodine 3.0 parts, 2,2'-azobis (4-methoxy-2) , 4-Dimethylvaleronitrile) (trade name: V-70, manufactured by Wako Pure Chemical Industries, Ltd.), MMA 26.3 parts by mass, BMA 17.5 parts by mass, methoxypolyethylene glycol monomethacrylate (manufactured by Nichiyu Co., Ltd., trade name; Blemmer) PME-200, number of repeating ethyleneoxy groups = 4) (PME-200) 43.9 parts by mass and 0.04 parts by mass of succinate imide were charged, and the mixture was stirred at 40 ° C. for 5 hours while stirring under a nitrogen stream. A block copolymer was produced.
Subsequently, 12.3 parts by mass of MAA was added, and the mixture was 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 G was obtained. The block copolymer G thus obtained had a weight average molecular weight (Mw) of 8100, Mw / Mn of 1.2, and an acid value of 80 mgKOH / g.

(Synthesis Example 10: Production of Block Copolymer H)
In Synthesis Example 9, instead of using 26.3 parts by mass of MMA, 17.5 parts by mass of BMA, and 43.9 parts by mass of methoxypolyethylene glycol monomethacrylate, the parts were changed to 70.2 parts by mass of MMA and 17.5 parts by mass of BMA. , Block copolymer H was produced in the same manner as in Synthesis Example 9. Table 2 shows the weight average molecular weight (Mw), Mw / Mn, and acid value of the obtained block copolymer H.

(Production Example 1: Production of salt-type graft copolymer A)
25.0 parts by mass of PGMEA, 25.52 parts by mass of graft copolymer A, and 0.48 of 1,8-diazabicyclo [5.4.0] Undecen-7 (manufactured by San-Apro, "DBU") of compound (B). A salt-type graft copolymer A solution was prepared by adding a mass portion (0.2 mol equivalent to the MAA constituent unit of the graft copolymer A) and stirring at room temperature for 6 hours. The obtained salt-type graft copolymer A solution was adjusted to have a solid content of 35% by PGMEA.

(Production Examples 2 to 8: Production of salt-type grafts or block copolymers B to H)
In Production Example 1, instead of the graft copolymer A, the graft copolymers B to F or the block copolymers G and H are used, and the amount of DBU is adjusted to the graft copolymers B to F or the block copolymer G and The salt-type graft copolymers B to F solutions and the salt-type graft copolymers B to F solutions and the same as in Production Example 1 except that they were used so as to have 0.2 molar equivalents with respect to the structural unit represented by the general formula (I) of H. Salt-type block copolymers G and H solutions were produced, respectively.

(Production Examples 9 to 11: Production of salt-type graft copolymers I to K)
In Production Example 1, the graft copolymer B was used instead of the graft copolymer A, and the amount of the compound (B) (molar equivalent to the MAA constituent unit of the graft copolymer) was changed as shown in Table 4. The salt-type graft copolymers I to K solutions were produced in the same manner as in Production Example 1 except for the above.

(Production Examples 12 to 30: Production of salt-type graft copolymers L to AD)
In Production Example 1, the graft copolymer B was used instead of the graft copolymer A, and the type of the compound (B) was changed as shown in Table 4 or Table 5, except that the same as in Production Example 1. , Salt-type graft copolymers L to AD solutions were produced, respectively.

(Preparation Example 1: Preparation of alkali-soluble resin α)
In a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 300 parts by mass of PGMEA was charged, the temperature was raised to 100 ° C. in a nitrogen atmosphere, and then 2-phenoxyethyl methacrylate. (PhEMA) 90 parts by mass, MMA 54 parts by mass, methacrylic acid (MAA) 36 parts by mass, perbutyl O (manufactured by Nichiyu Co., Ltd.) 6 parts by mass, chain transfer agent (n-dodecyl mercaptan) 2 parts by mass for 1.5 hours It was dropped continuously over. Then, the reaction was continued at 100 ° C., and 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of dropping of the main chain forming mixture to terminate the polymerization.
Next, while blowing air, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, the temperature was raised to 110 ° C., 0.8 parts by mass of triethylamine was added, and the temperature was 110 ° C. for 15 hours. The 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).

(Example 1)
(1) Production of Coloring Material Dispersion Liquid G-1 14.9 parts by mass of the salt-type graft copolymer A solution of Production Example 1 as the dispersant A, and C.I. I. Pigment Green 58 (PG58) 11.7 parts by mass, C.I. I. Put 1.3 parts by mass of Pigment Yellow 138 (PY138), 72.1 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm in a mayonnaise bottle, and use a paint shaker (made by Asada Iron Works Co., Ltd.) as a preliminary crush. ), Then take out zirconia beads having a particle size of 2.0 mm, add 200 parts by mass of zirconia beads having a particle size of 0.1 mm, and disperse for 4 hours with a paint shaker as the main crushing. , Color material dispersion liquid G-1 was obtained.

(2) Production of Color Curable Composition G-1 9.80 parts by mass of the coloring material dispersion G-1 obtained in (1) above, and the alkali-soluble resin α solution obtained in Preparation Example 1 were obtained. 36 parts by mass, 1.31 parts by mass of polyfunctional monomer (trade name: Aronix M-403, manufactured by Toa Synthetic Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -On (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Ltd.) 0.06 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (light) Initiator: Brand name Irgacure 369, manufactured by BASF Japan, 0.06 parts by mass, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (photoinitiator: Product name Irgacure OXE01, manufactured by BASF Japan Ltd., 0.03 parts by mass, fluorine-based surfactant (trade name: Megafuck R-08MH, manufactured by DIC Co., Ltd.), 0.07 parts by mass, PGMEA 8. 30 parts by mass was added to obtain a coloring curable composition G-1.

(Examples 2 to 30)
(1) Production of Coloring Material Dispersion Liquids G-2 to G-30 In (1) of Example 1, instead of the salt-type graft copolymer A solution, as shown in Tables 3 to 5, salt-type grafts are used. Color material dispersions G-2 to G-30 were produced in the same manner as in Example 1 except that the copolymers B to AD solutions were used.
(2) Production of Color Curable Compositions G-2 to G-30 In (2) of Example 1, instead of the color material dispersion liquid G-1, the above color material dispersion liquids G-2 to G-30, respectively. The colored curable compositions G-2 to G-30 were obtained in the same manner as in (2) of Example 1 except that the above was used.

(Comparative Examples 1 to 3)
(1) Production of Comparative Coloring Material Dispersion Liquids CG-1 to CG-3 In (1) of Example 1, instead of the dispersant A which is a salt-type graft copolymer, as shown in Table 5, the compound ( Comparative colorant dispersions CG-1 to CG-3 were obtained in the same manner as in Example 1 except that the graft copolymers B, E, or F which were not salt-formed in B) were used.
(2) Production of Comparative Color Curable Compositions CG-1 to CG-3 In (2) of Example 1, instead of the color material dispersion liquid G-1, the comparative color material dispersion liquids CG-1 to CG, respectively. Comparative color-curable compositions CG-1 to CG-3 were obtained in the same manner as in (2) of Example 1 except that -3 was used.

(Example 31)
(1) Production of Coloring Material Dispersion Liquid R-1 The salt-type graft copolymer A solution of Production Example 1 was used as the dispersant A in an amount of 14.9 parts by mass, and C.I. I. Pigment Red 177 (PR177) 3.9 parts by mass, C.I. I. 9.1 parts by mass of Pigment Red 291 (PR291), 72.1 parts by mass of PGMEA, 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 as a preliminary crush. ), Then take out zirconia beads having a particle size of 2.0 mm, add 200 parts by mass of zirconia beads having a particle size of 0.1 mm, and disperse for 4 hours with a paint shaker as the main crushing. , Color material dispersion liquid R-1 was obtained.

(2) Production of Color Curable Composition R-1 9.80 parts by mass of the coloring material dispersion R-1 obtained in (1) above, and the alkali-soluble resin α solution obtained in Preparation Example 1 were obtained. 36 parts by mass, 1.31 parts by mass of polyfunctional monomer (trade name: Aronix M-403, manufactured by Toa Synthetic Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -On (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Ltd.) 0.06 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (light) Initiator: 0.06 part by mass of trade name Irgacure 369, manufactured by BASF Japan, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (photoinitiator: Product name Irgacure OXE01, manufactured by BASF Japan Ltd., 0.03 parts by mass, fluorine-based surfactant (trade name: Megafuck R-08MH, manufactured by DIC Co., Ltd.), 0.07 parts by mass, PGMEA 8. 30 parts by mass was added to obtain a coloring curable composition R-1.

(Examples 32 to 60)
(1) Production of Coloring Material Dispersion Liquids R-2 to R-30 In (1) of Example 31, instead of the salt-type graft copolymer A solution, as shown in Tables 6 to 8, salt-type grafts Color material dispersions R-2 to R-30 were produced in the same manner as in Example 31 except that the copolymers B to AD solutions were used.
(2) Production of Color Curable Compositions R-2 to R-30 In (2) of Example 31, instead of the color material dispersion liquid R-1, the above color material dispersion liquids R-2 to R-30, respectively. The colored curable compositions R-2 to R-30 were obtained in the same manner as in (2) of Example 31 except that the above was used.

(Comparative Examples 4 to 6)
(1) Production of Comparative Color Material Dispersants CR-1 to CR-3 In (1) of Example 31, instead of the dispersant A which is a salt-type graft copolymer, as shown in Table 8, the compound ( Comparative color material dispersions CR-1 to CR-3 were obtained in the same manner as in Example 31 except that the graft copolymers B, E, or F which were not salt-formed in B) were used.
(2) Production of Comparative Color Curable Compositions CR-1 to CR-3 In (2) of Example 31, instead of the color material dispersion liquid R-1, the comparative color material dispersion liquids CR-1 to CR-3 were used. Comparative color-curable compositions CR-1 to CR-3 were obtained in the same manner as in (2) of Example 31 except that -3 was used.

(Example 61)
(1) Production of Coloring Material Dispersion Liquid B-1 14.9 parts by mass of the salt-type graft copolymer A solution of Production Example 1 as the dispersant A, and C.I. I. Pigment Blue 15: 6 (PB 15: 6) 10.4 parts by mass, C.I. I. Pigment Violet 23 (PV23) is 2.6 parts by mass, PGMEA is 72.1 parts by mass, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm are placed in a mayonnaise bottle. ), Then take out zirconia beads having a particle size of 2.0 mm, add 200 parts by mass of zirconia beads having a particle size of 0.1 mm, and disperse for 4 hours with a paint shaker as the main crushing. , Color material dispersion liquid B-1 was obtained.

(2) Production of Color Curable Composition B-1 6.78 parts by mass of the coloring material dispersion B-1 obtained in (1) above, and the alkali-soluble resin α solution obtained in Preparation Example 1 were used. 46 parts by mass, 1.36 parts by mass of polyfunctional monomer (trade name: Aronix M-403, manufactured by Toa Synthetic Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -On (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Ltd.) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (light) Initiator: Brand name Irgacure 369, manufactured by BASF Japan, 0.09 parts by mass, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (photoinitiator: Product name Irgacure OXE01, manufactured by BASF Japan Ltd., 0.04 parts by mass, fluorine-based surfactant (trade name: Megafuck R-08MH, manufactured by DIC Co., Ltd.), 0.07 parts by mass, PGMEA 10. 11 parts by mass was added to obtain a coloring curable composition B-1.

(Examples 62 to 90)
(1) Production of Color Material Dispersion Liquids B-2 to B-30 In (1) of Example 61, instead of the salt-type graft copolymer A solution, as shown in Tables 9 to 11, salt-type grafts are used. Color material dispersions B-2 to B-30 were produced in the same manner as in Example 61, except that the copolymers B to AD solutions were used.
(2) Production of Color Curable Compositions B-2 to B-30 In (2) of Example 61, instead of the color material dispersion liquid B-1, the above color material dispersion liquids B-2 to B-30, respectively. B-2 to B-30 were obtained in the same manner as in (2) of Example 61, except that

(Comparative Examples 7-9)
(1) Production of Comparative Coloring Material Dispersion Liquids CB-1 to CB-3 In (1) of Example 61, instead of the dispersant A which is a salt-type graft copolymer, as shown in Table 11, the compound ( Comparative colorant dispersions CB-1 to CB-3 were obtained in the same manner as in Example 61, except that the graft copolymers B, E, or F which were not salt-formed in B) were used.
(2) Production of Comparative Color Curable Compositions CB-1 to CB-3 In (2) of Example 61, the comparative color material dispersion liquids CB-1 to CB were used instead of the color material dispersion liquid B-1. Comparative color-curable compositions CB-1 to CB-3 were obtained in the same manner as in (2) of Example 61 except that -3 was used.

[Evaluation method]
<Evaluation of dispersibility stability of color material dispersion liquid>
The viscosities of the color material dispersions obtained in Examples and Comparative Examples were measured immediately after preparation and after storage at 25 ° C. for 30 days, and the viscosity change rate was calculated from the viscosities before and after storage to evaluate the viscosity stability. bottom. A vibrating viscometer was used to measure the viscosity, and the viscosity at 25.0 ± 0.5 ° C. was measured.
(Dispersion stability evaluation standard)
A: Viscosity change rate before and after storage is less than 10% B: Viscosity change rate before and after storage is 10% or more and less than 20% C: Viscosity change rate before and after storage is 20% or more and less than 40% D: Before and after storage Viscosity change rate is 40% or more E: Gelling during dispersion or storage However, this is the value when the coloring material is 13% by mass with respect to the total mass of the coloring material dispersion liquid including the solvent.
If the evaluation result is C, the dispersion stability is relatively good, if the evaluation result is B, the dispersion stability is good, and if the evaluation result is A, the colorant dispersion is excellent in dispersion stability. ing.

<Optical performance, contrast>
After post-baking the color-curable compositions obtained in Examples and Comparative Examples on a glass substrate (manufactured by NH Techno Glass Co., Ltd., “NA35”) using a spin coater, Green set y = 0. .520, Red is x = 0.655, Blue is y = 0.082. After coating with a film thickness that forms a colored layer, it is dried on a glass substrate at 80 ° C. for 3 minutes using a hot plate. A colored layer was formed on the surface. The 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.
Contrast, chromaticity (x, y), and brightness (Y) of the obtained colored substrate were measured using a contrast measuring device CT-1B manufactured by Tsubosaka Electric and a microspectroscopy measuring device OSP-SP200 manufactured by Olympus.
The brightness was calculated when Green was y = 0.520, Red was x = 0.655, and Blue was y = 0.082. The larger the value, the higher the brightness.
(Contrast evaluation standard)
A: Green and Blue exceed 7,000, Red exceeds 6000,
B: Green and Blue are 6000-7000, Red is 5000-6000
C: Green and Blue are 5000-6000, Red is 4000-5000
D: Green and Blue are 4000-5000, Red is 3000-4000
E: Green and Blue are less than 4000, Red is less than 3000. Green is y = 0.520, Red is x = 0.655, Blue is contrast when y = 0.082. If the evaluation result is C, contrast. Is relatively good, and if the evaluation result is B, the contrast is good, and if the evaluation result is A, the contrast is excellent.

<Evaluation of substrate adhesion>
The colored curable compositions obtained in Examples and Comparative Examples were placed on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") using a spin coater to a thickness of 2.0 μm after post-baking. After coating with a film thickness to form a colored layer, the colored layer was formed on the glass substrate by drying at 80 ° C. for 3 minutes using a hot plate. The colored layer was irradiated with ultraviolet rays of ^{60 mJ / cm 2} using an ultra-high pressure mercury lamp.
Next, the colored substrate was post-baked in a clean oven at 230 ° C. for 30 minutes to prepare a colored substrate. The obtained colored substrate was subjected to a cut of 100 squares by the same method as JIS K5400, a cellophane adhesive tape was attached, and then the colored substrate was instantly peeled off. The change in the state of the notch of 100 squares before and after the test with the cellophane adhesive tape was observed using an optical microscope.
(Base material adhesion evaluation criteria)
A: 100 squares confirmed after the test, no change in the state of the notch before and after the test B: 100 squares confirmed after the test, the width of the notch changes widely before and after the test C: 70 squares or more and 100 squares after the test Less than 30 squares are confirmed D: 30 squares or more and less than 70 squares are confirmed after the test E: Less than 30 squares are confirmed after the test. Alternatively, if the evaluation result is C, the substrate adhesion is relatively good, if the evaluation result is B, the substrate adhesion is good, and if the evaluation result is A, the substrate adhesion is relatively good. Excellent material adhesion

<Solvent resolubility>
The tip of a glass substrate having a width of 0.5 cm and a length of 10 cm was immersed in the colored curable composition obtained in Examples and Comparative Examples, and applied to a 1 cm long portion of the glass substrate. The pulled glass substrate was placed in a constant temperature and humidity chamber so that the glass surface was horizontal, and dried at a temperature of 23 ° C. and a humidity of 80% RH for 30 minutes. Next, the glass substrate to which the dried coating film was attached was immersed in PGMEA for 15 seconds. At this time, the redissolved state of the dry coating film was visually discriminated and evaluated.
(Solvent resolubility evaluation standard)
A: The dry coating was completely dissolved B: Fragments of the dry coating were formed in the solvent, and the fragments were eventually dissolved C: Fragments of the dry coating were formed in the solvent and the solution was colored D: In the solvent E: No flakes of dry coating were formed in the solvent and the solution was not colored. If the evaluation result is C, the solvent resolubility is relatively good. If the evaluation result is B, the solvent resolubility is good, and if the evaluation result is A, the solvent resolubility is excellent.

<Development time evaluation>
The colored curable compositions obtained in Examples and Comparative Examples were placed on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") using a spin coater to a thickness of 2.0 μm after post-baking. After coating with a film thickness to form 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 ultrahigh pressure mercury lamp via a photomask. Then, the glass substrate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer, and the colored layer was completely dissolved to form the colored layer. The time until the glass surface of the portion appeared was measured as the developing time.
(Evaluation criteria)
A: The time until the glass surface appeared was 15 seconds or less B: The time until the glass surface appeared was over 15 seconds and 30 seconds or less C: The time until the glass surface appeared was over 30 seconds and 45 seconds D: The time until the glass surface appeared was over 45 seconds and 60 seconds or less. E: The glass surface did not appear. If the evaluation result is C, the developability is relatively good and the evaluation result is B. If it is, the developability is good, and if the evaluation result is A, the developability is excellent.

The above evaluation was performed on the color material dispersion liquid and the color curable composition obtained in the examples obtained above and the comparative examples. The evaluation results are shown in Tables 3 to 11.

[Summary of results]
By comparing Examples and Comparative Examples, the dispersant was selected from the group consisting of at least a part of the acidic groups contained in the general formula (I), a tertiary amino group-containing basic compound and a basic heterocyclic compound. In Examples 1 to 90 using the salt-type polymer obtained by forming a salt with one or more of the compounds (B), excellent dispersion stability, brightness, contrast, substrate adhesion, and solvent resolubility. It has been clarified that a colored curable composition satisfying the above conditions can be obtained.
On the other hand, the comparative colored curable compositions of Comparative Examples 1 to 9 using the acidic group-containing polymer not salt-formed by the compound (B) have poor dispersion stability, and are also inferior in brightness and contrast. Yes, it was inferior in substrate adhesion and solvent resolubility.
Compared in the examples, when the acid value of the dispersant is in a predetermined range, the dispersion stability, brightness, contrast, and solution resolubility tend to be superior, and the acidic group of the dispersant is a sulfonic acid group. And carboxy groups, especially carboxy groups, tended to be better in dispersion stability, brightness, contrast and solvent resolubility. Further, when the molar equivalent of the acidic group of the dispersant and the compound (B) salt-forming is within a predetermined range, the dispersion stability, brightness, contrast, substrate adhesion, and solvent resolubility tend to be excellent. It was shown that the larger the pKa of the compound (B), the better the dispersion stability, the brightness, the contrast, and the solvent resolubility tend to be.
In the dispersant, the polymer having the structural unit represented by the general formula (I) is composed of the structural unit represented by the general formula (V) and the structural unit represented by the following general formula (V'). The inclusion of at least one structural unit selected from the group tended to further improve substrate adhesion.

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

Claims

A color material dispersion liquid containing a color material, a dispersant, and a solvent.
The dispersant is composed of at least a part of acidic groups contained in the general formula (I) of a polymer having a structural unit represented by the following general formula (I), a tertiary amine and a basic heterocyclic compound. A color material dispersion liquid containing a salt-type polymer in which one or more compounds (B) selected from the above group form a salt.

(In the 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 polymer having the structural unit represented by the general formula (I) is a graft copolymer having the structural unit represented by the general formula (I), and the configuration represented by the general formula (I). The color material dispersion liquid according to claim 1, which is at least one of block copolymers having an A block containing a unit.
In the structural unit represented by the general formula (I), Q is carboxy group (-COOH), a sulfonic acid (-SO 3 H), and a phosphoric acid group (-O-P (= O) (OH) The coloring material dispersion liquid according to claim 1 or 2, which is at least one acidic group selected from the group consisting of 2).
The color material dispersion liquid according to any one of claims 1 to 3, wherein the compound (B) has a molecular weight of 800 or less.
The dispersant according to any one of claims 1 to 4, wherein the polymer having the structural unit represented by the general formula (I) before salt formation has an acid value of 20 to 250 mgKOH / g. Color material dispersion liquid.
The color material dispersion liquid according to any one of claims 1 to 5, wherein the structural unit represented by the general formula (I) includes the structural unit represented by the following general formula (II).

(In the general formula (II), R 1 represents a hydrogen atom or a methyl group, and A represents a direct bond or a divalent linking group.)
The polymer having the structural unit represented by the general formula (I) 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), and the polymer chain in the general formula (III) is the following general formula (III). A graft copolymer containing at least one structural unit selected from the group consisting of the structural unit represented by V) and the structural unit represented by the following general formula (V'), 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). A block copolymer containing at least one structural unit selected from the group consisting of the structural units to be formed and the structural units represented by the following general formula (V').
The color material dispersion liquid according to any one of claims 1 to 6, which is at least one of the above.

(In the 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 (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 or may contain a hetero atom. .)

In (Formula (V), R 11 'is hydrogen atom or a methyl group, A 2' is a divalent linking group, R 5 is an ethylene group or a propylene group, R 6 is a hydrogen atom, or a hydrocarbon group , M represents a number of 2 or more and 80 or less.
In the 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. )
Selected from the group consisting of at least a part of the acidic groups contained in the general formula (I) of the polymer having a structural unit represented by the following general formula (I), a tertiary amine and a basic heterocyclic compound. A dispersant, which is a salt-type polymer in which one or more compounds (B) form a salt.

(In the general formula (I), R 1 represents a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, and Q is an acidic group.)
The polymer having the structural unit represented by the general formula (I) is a graft copolymer having the structural unit represented by the general formula (I), and the configuration represented by the general formula (I). The dispersant according to claim 8, which is at least one of a block copolymer having an A block containing a unit.
In the structural unit represented by the general formula (I), Q is carboxy group (-COOH), a sulfonic acid (-SO 3 H), and a phosphoric acid group (-O-P (= O) (OH) The dispersant according to claim 8 or 9, which is at least one acidic group selected from the group consisting of 2).
The dispersant according to any one of claims 8 to 10, wherein the compound (B) has a molecular weight of 800 or less.
The dispersant according to any one of claims 8 to 11, wherein the polymer having the structural unit represented by the general formula (I) before salt formation has an acid value of 20 to 250 mgKOH / g.
The dispersant according to any one of claims 8 to 12, wherein the structural unit represented by the general formula (I) includes a structural unit represented by the following general formula (II).

(In the general formula (II), R 1 represents a hydrogen atom or a methyl group, and A represents a direct bond or a divalent linking group.)
The polymer having the structural unit represented by the general formula (I) 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), and the polymer chain in the general formula (III) is the following general formula (III). A graft copolymer containing at least one structural unit selected from the group consisting of the structural unit represented by V) and the structural unit represented by the following general formula (V'), 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). 8 to 13 of claims 8 to 13 which are block copolymers containing at least one structural unit selected from the group consisting of the structural units to be formed and the structural units represented by the following general formula (V'). The dispersant according to any one of the above.

(In the 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 (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 or may contain a hetero atom. .)

In (Formula (V), R 11 'is hydrogen atom or a methyl group, A 2' is a divalent linking group, R 5 is an ethylene group or a propylene group, R 6 is a hydrogen atom, or a hydrocarbon group , M represents a number of 2 or more and 80 or less.
In the 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. )
A color curable composition containing the dispersant according to any one of claims 8 to 14, a coloring material, a polymerizable compound, an initiator, and a solvent.
A color filter comprising 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.