JP2021102759A - Colored composition, colored cured film and method for producing the same, color filter, display element, light receiving-element, and curable composition - Google Patents

Abstract

To provide a colored composition that produces a cured film excelling in storage stability and low-temperature curability as well as in solvent resistance.SOLUTION: A colored composition has (A) a colorant, (B) a polymer (excluding the (A) colorant), and (C) a polymerizable compound (excluding the (A) colorant and (B) polymer). At least one selected from the group consisting of the (A) colorant, (B) polymer and (C) polymerizable compound has a partial structure represented by formula (1). At least one selected from the group consisting of the (A) colorant, (B) polymer and (C) polymerizable compound has a hydroxy group. In the formula (1), R1 and R2 independently represent a C1-4 alkyl group, L1 is a divalent organic group, X1 is an electron-withdrawing divalent linking group. n1 and n2 independently represent an integer of 0-2. * is a bond.SELECTED DRAWING: None

Description

The present invention relates to a colored composition, a colored cured film and a method for producing the same, a color filter, a display element, a light receiving element, and a curable composition.

As a method for producing a colored cured film such as a color filter, an inkjet method, an electrodeposition method, a printing method, a photolithography method and the like are known. Of these, the photolithography method has become the mainstream in recent years. When a color filter is produced by a photolithography method, for example, a color-curable composition is applied onto a substrate to form a coating film, and then exposure is performed through a photomask having a predetermined aperture pattern, and then development is performed. A method of forming a pattern by dissolving and removing an unexposed portion is adopted (see, for example, Patent Document 1). After the pattern is formed, the coating film is usually post-baked at a temperature of 200 to 250 ° C. for about 30 to 60 minutes to accelerate the curing of the coating film and improve the film hardness, the solvent resistance of the film, and the like.

Japanese Unexamined Patent Publication No. 2-144502

As a colorant contained in a colored cured film, a dye can enhance the hue and brightness of a displayed image when an image is displayed due to the color purity of the dye itself and the vividness of the hue, and is derived from the pigment. It is considered to be effective in improving the contrast by reducing the coarse particles.

However, dyes generally have a problem of being inferior in heat resistance. Therefore, it is difficult to heat the coating film formed by using the coloring composition containing the dye at a post-bake temperature of 200 to 250 ° C. Further, with the expansion of applications such as display elements, alternatives from conventional glass substrates to flexible plastic substrates are being considered as substrates. However, since a plastic substrate generally has low heat resistance, when a coating film made of a coloring composition is formed on the plastic substrate and heated at a post-bake temperature of 200 to 250 ° C., the plastic substrate may be stretched or shrunk. I am concerned.

To solve these problems, it is conceivable to perform post-baking at the lowest possible temperature. However, if post-baking is performed at a low temperature, the film is not sufficiently cured, which may cause a problem such as a decrease in solvent resistance. Further, a curable composition having high sensitivity at a low temperature generally tends to be inferior in storage stability.

The present invention has been made in view of the above problems, and one object of the present invention is to provide a coloring composition capable of obtaining a cured film having excellent storage stability and low temperature curability and excellent solvent resistance. And. Another object of the present invention is to provide a curable composition capable of obtaining a cured film having excellent storage stability and low temperature curability and excellent solvent resistance.

In order to solve the above problems, according to the present invention, the following colored composition, colored cured film, color filter, display element, light receiving element, method for producing colored cured film, and curable composition are provided.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して、炭素数１〜４のアルキル基である。Ｌ^１は、２価の有機基である。Ｘ^１は、電子求引性を有する２価の連結基である。ｎ１及びｎ２は、それぞれ独立して０〜２の整数である。「＊」は結合手であることを表す。）
［２］上記［１］の着色組成物を用いて形成された着色硬化膜。
［３］上記［１］の着色組成物を用いて形成されたカラーフィルタ。
［４］上記［２］の着色硬化膜を備える表示素子。
［５］上記［２］の着色硬化膜を備える受光素子。
［６］基板上に、上記［１］の着色組成物を塗布して塗膜を形成する工程と、前記塗膜から溶剤を除去する工程と、を含む、着色硬化膜の製造方法。
［７］（Ｂ）重合体（ただし、着色剤を除く。）と、（Ｃ）重合性化合物（ただし、前記着色剤及び前記（Ｂ）重合体を除く。）とを含有する硬化性組成物であって、前記（Ｂ）重合体及び前記（Ｃ）重合性化合物よりなる群から選択される少なくとも１種は、下記式（１）で表される部分構造を有し、前記（Ｂ）重合体及び前記（Ｃ）重合性化合物よりなる群から選択される少なくとも１種は、水酸基を有する、硬化性組成物。 [1] (A) Colorant, (B) Polymer (excluding (A) Colorant), (C) Polymerizable Compound (However, (A) Colorant and (B) At least one selected from the group consisting of the (A) colorant, the (B) polymer and the (C) polymerizable compound, which is a coloring composition containing (excluding the polymer). At least one selected from the group consisting of the above-mentioned (A) colorant, the above-mentioned (B) polymer and the above-mentioned (C) polymerizable compound having a partial structure represented by the following formula (1) has a hydroxyl group. Coloring composition having.

(In the formula (1), R ¹ and R ² are independently alkyl groups having 1 to 4 carbon atoms. L ¹ is a divalent organic group. X ¹ is electron attracting property. It is a divalent linking group having. N1 and n2 are independently integers of 0 to 2. “*” Indicates that it is a binder.)
[2] A colored cured film formed by using the coloring composition of the above [1].
[3] A color filter formed by using the coloring composition of the above [1].
[4] A display element provided with the colored cured film of the above [2].
[5] A light receiving element provided with the colored cured film of the above [2].
[6] A method for producing a colored cured film, which comprises a step of applying the coloring composition of the above [1] on a substrate to form a coating film, and a step of removing a solvent from the coating film.
[7] A curable composition containing a polymer (B) (excluding a colorant) and a polymerizable compound (C) (excluding the colorant and the polymer (B)). At least one selected from the group consisting of the polymer (B) and the polymerizable compound (C) has a partial structure represented by the following formula (1) and has the weight (B). At least one selected from the group consisting of coalescing and the above-mentioned (C) polymerizable compound is a curable composition having a hydroxyl group.

According to the coloring composition of the present invention, at least one selected from the group consisting of (A) colorant, (B) polymer and (C) polymerizable compound is a partial structure represented by the above formula (1). At least one selected from the group consisting of (A) colorant, (B) polymer and (C) polymerizable compound has a hydroxyl group, so that it can withstand post-baking at a low temperature. It is possible to form a colored cured film having excellent solvent properties. In addition, the coloring composition of the present invention has little change in viscosity with time and has good storage stability. Therefore, the coloring composition of the present invention is useful as a material for various color filters such as a display element and a light receiving element.

Further, according to the curable composition of the present invention, at least one selected from the group consisting of the polymer (B) and the polymerizable compound (C) has a partial structure represented by the above formula (1). Since at least one selected from the group consisting of (B) polymer and (C) polymerizable compound has a hydroxyl group, a cured film having excellent solvent resistance is formed even when post-baking is performed at a low temperature. can do. In addition, the curable composition of the present invention has little change in viscosity with time and has good storage stability. Therefore, the curable composition of the present invention is useful as a protective film material, a spacer material, and an insulating film material.

Hereinafter, matters related to the embodiment will be described in detail. In addition, in this specification, the numerical range described by using "~" means that the numerical value described before and after "~" is included as the lower limit value and the upper limit value. The "constituent unit" is a unit that mainly constitutes the main chain structure, and means a unit that is included in at least two or more in the main chain structure.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して、炭素数１〜４のアルキル基である。Ｌ^１は、２価の有機基である。Ｘ^１は、電子求引性を有する２価の連結基である。ｎ１及びｎ２は、それぞれ独立して０〜２の整数である。「＊」は結合手であることを表す。） [Coloring composition]
The coloring composition is a composition used for forming a coloring layer such as each color pixel used for a color filter, a black matrix, a black spacer, and the like. The coloring compositions of the present disclosure include (A) a colorant, (B) a polymer (excluding (A) colorant; the same applies hereinafter), and (C) a polymerizable compound (however, (A). ) Colorant and (B) polymer are excluded. The same shall apply hereinafter). In particular, the coloring compositions of the present disclosure include the following in the same or different molecules in at least one selected from the group consisting of (A) colorants, (B) polymers, and (C) polymerizable compounds: It contains a partial structure represented by the formula (1) and a hydroxyl group. That is, at least one selected from the group consisting of (A) colorant, (B) polymer and (C) polymerizable compound in the coloring composition of the present disclosure is a portion represented by the following formula (1). At least one selected from the group having a structure and consisting of (A) colorant, (B) polymer and (C) polymerizable compound has a hydroxyl group. The partial structure represented by the following formula (1) and the hydroxyl group may be present in the same molecule or may be present in different molecules.

(In the formula (1), R ¹ and R ² are independently alkyl groups having 1 to 4 carbon atoms. L ¹ is a divalent organic group. X ¹ is electron attracting property. It is a divalent linking group having. N1 and n2 are independently integers of 0 to 2. “*” Indicates that it is a binder.)

Here, in the coloring composition of the present disclosure, "in the same molecule or in a different molecule in at least one selected from the group consisting of (A) colorant, (B) polymer, and (C) polymerizable compound. , Including the partial structure represented by the formula (1) and the hydroxyl group "may be a mode in which the partial structure represented by the formula (1) and the hydroxyl group are present in the same type of component. Alternatively, the partial structure represented by the formula (1) and the hydroxyl group may be present in different components. For example, by having the colorant (A) having a partial structure represented by the formula (1) and a hydroxyl group, a coloring composition containing the partial structure represented by the formula (1) and a hydroxyl group may be obtained. Alternatively, the colorant (A) has a partial structure represented by the formula (1), and the polymer (B) has a hydroxyl group, so that the colorant contains the partial structure represented by the formula (1) and the hydroxyl group. It may be a composition.

In the coloring composition of the present disclosure, the content ratio of the partial structure represented by the above formula (1) is based on the total solid content of the coloring composition from the viewpoint of obtaining a colored cured film having high solvent resistance. , 0.5% by mass or more, more preferably 2% by mass or more, and further preferably 5% by mass or more. Further, the content ratio of the partial structure represented by the above formula (1) is preferably 50% by mass or less with respect to the total amount of the total solid content of the coloring composition from the viewpoint of improving the processability. , 35% by mass or less, and more preferably 20% by mass or less.

Further, in the coloring composition of the present disclosure, the content ratio of hydroxyl groups is 0.3% by mass or more with respect to the total solid content of the coloring composition from the viewpoint of obtaining a colored cured film having high solvent resistance. It is preferable, it is more preferably 1% by mass or more, and further preferably 3% by mass or more. Further, the content ratio of the hydroxyl group is preferably 35% by mass or less, and preferably 25% by mass or less, based on the total amount of the total solid content of the coloring composition from the viewpoint of improving the processability. , 15% by mass or less is more preferable.

In addition, in this specification, "solid content" means a component other than the solvent (E) contained in a coloring composition. Therefore, the "total solid content" refers to (A) colorant, (B) polymer and (C) polymerizable compound, (A) colorant, (B) polymer, (C) polymerizable compound and ( E) It means a component that is a combination of other components other than the solvent. For example, even liquid photopolymerizable compounds and additive components (surfactants, etc.) are included in the solid content.

(Compound having a partial structure represented by the above formula (1))
In the above formula (1), the alkyl groups having 1 to 4 carbon atoms of ^{R 1} and R ^{2 may be linear or branched.} From the viewpoint of allowing the reaction product of the partial structure represented by the above formula (1) and the hydroxyl group to be discharged out of the film, R ¹ and R ² are preferably alkyl groups having 1 to 4 carbon atoms. , More preferably a methyl group or an ethyl group.
n1 and n2 are preferably 0 or 1, and more preferably 0 in that the reaction efficiency with the hydroxyl group can be further increased.

X ¹ may be a divalent linking group having an electron attracting property, and is not particularly limited. Here, the "divalent linking group having an electron-attracting property" means a group obtained by removing a hydrogen atom from an arbitrary position of the electron-attracting group to form a new bond. In this case, it is considered that the electron attractability is exhibited in a bond different from the new bond. The electron-attracting group is a substituent having a Hammett substituent constant σp value of 0.15 or more, more preferably 0.2 or more. For Hammett substituent constants, see Journal of Medicinal Chemistry, 1973, Vol. 16, No. According to 11,1207-1216.

X ¹ is the reaction of the hydroxyl group from the viewpoint of advancing efficiently at a low temperature, a carbonyl group (-CO-), an amide group (-CONR ⁴ - ^* 1), an imido group (-CONR ⁴ CO-), an ester group ( From -CO-O- * ¹ ), sulfonyl group (-SO _2- ), sulfinyl group (-SO-), thiocarbonyl group (-CS-), and carboxylicimideyl group (-C (= NH)-) at least one member selected from the group consisting (wherein, R ⁴ is a monovalent hydrocarbon group having a hydrogen atom or 1 to 10 carbon atoms, "* ^1", the L ¹ in the formula (1) It is preferable that it represents a binding hand to be bonded). Of these, X ¹ is more preferably an amide group, a carbonyl group or an ester group, and even more preferably an amide group or a carbonyl group.
As the ^{divalent organic group of L 1} , -O-, -CO-, -COO-, are used between the carbon-carbon bonds of the alkanediyl group having 1 to 20 carbon atoms and the alkanediyl group having 1 to 20 carbon atoms. Examples thereof include groups having −NH−, −CONH− and the like.

The compound having a partial structure represented by the above formula (1) (hereinafter, also referred to as “specific compound”) is a low molecular weight compound having no repeating unit (hereinafter, also simply referred to as “low molecular weight compound”). It may be a polymer or a polymer. In the present specification, the "low molecular weight compound" is a compound having no molecular weight distribution and preferably having a molecular weight of 1,000 or less. The specific compound is preferably a polymer in that a colored film having excellent solvent resistance can be obtained. Specifically, the structural unit (a) having a partial structure represented by the above formula (1). It is preferably a polymer containing. When the specific compound is a polymer, the specific compound may be (A) a colorant or (B) a polymer. Further, as a specific compound, (A) a colorant and (B) a polymer may be contained in the coloring composition.

（式（１−２）中、Ｒ^３は、水素原子又は炭素数１〜４のアルキル基である。Ｒ^１、Ｒ^２、Ｌ^１、Ｘ^１、ｎ１及びｎ２は、それぞれ上記式（１）と同義である。） The structural unit (a) may have a partial structure represented by the above formula (1), and the other partial structures are not particularly limited. The structural unit (a) is a monomer having an ethylenically unsaturated group (hereinafter, "ethylene unsaturated single amount") in that the partial structure represented by the above formula (1) can be easily introduced into the side chain of the polymer. It is preferably a structural unit derived from (also referred to as "body"), and is derived from at least one selected from the group consisting of (meth) acrylic monomers, styrene monomers, and maleimide monomers. More preferably, it is a structural unit. Among these, the structural unit (a) is preferably a structural unit derived from a (meth) acrylic monomer, and is particularly preferably a structural unit represented by the following formula (1-2). In addition, in this specification, "(meth) acrylic" is a concept including acrylic and methacryl.

(In the formula (1-2), R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹ , R ² , L ¹ , X ¹ , n 1 and n 2 are the above formula (1), respectively. Is synonymous with.)

In the above formula (1-2), the description of the above formula (1) is applied to the description of specific examples and preferable examples of ^{R 1} , R ² , L ¹ , X ^{1, n1 and n2.}
R ³ is preferably a hydrogen atom or a methyl group. L ¹ preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms, in that a colored film having excellent solvent resistance can be obtained.

(Hydroxy group-containing compound)
The compound having a hydroxyl group (hereinafter, also referred to as “hydroxyl group-containing compound”) may be a compound having at least one hydroxyl group in one molecule. The hydroxyl group-containing compound may be a low molecular weight compound or a polymer. Further, the hydroxyl group-containing compound may be the same compound as the specific compound or a different compound. When the hydroxyl group-containing compound and the specific compound are the same compound, the compound has a partial structure represented by the above formula (1) and a hydroxyl group in one molecule. In this case, the partial structure represented by the above formula (1) may contain a hydroxyl group, but the partial structure represented by the above formula (1) and the hydroxyl group are different from each other (that is, in different structural units). It is preferably present in.

Here, in the composition of the present disclosure containing the partial structure represented by the above formula (1) and the hydroxyl group, at least one ^{of the group "OR 1} " and the group "OR ^{2" in the above formula (1) and the hydroxyl group} It is considered that a transesterification reaction with the above occurs, which forms a crosslinked structure intramolecularly or between molecules and cures. This transesterification reaction is a reversible reaction, and the progress of the transesterification reaction is suppressed in an equilibrium state. As a result, in the state where the equilibrium before heating is maintained, the coloring composition is not cured, and the mixed state of (A) colorant, (B) polymer and (C) polymerizable compound is stably maintained. It is thought that.

On the other hand, when the composition is applied and heated to cause equilibrium transfer, a transesterification reaction occurs between at least one ^{of the groups "OR 1} " and the group "OR ^{2" in the above formula (1) and a hydroxyl group.} The transesterified "HO-R ¹ " or "H-OR ² " is discharged out of the system and equilibrium transfer occurs, so that a crosslinked structure is formed between the specific compound and the hydroxyl group-containing compound, and the composition is cured. It is thought that. Further, this transesterification reaction can proceed at a low temperature of, for example, 180 ° C. or lower to cause film hardening. By utilizing such a transesterification reaction, it is presumed that, according to the coloring composition of the present disclosure, both storage stability and low-temperature curability can be achieved at the same time.

(Formulation mode of coloring composition)
The coloring composition of the present disclosure has a partial structure in which at least one selected from the group consisting of (A) colorant, (B) polymer and (C) polymerizable compound is represented by the above formula (1). However, as long as at least one selected from the group consisting of (A) colorant, (B) polymer and (C) polymerizable compound has a hydroxyl group, the blending mode is not particularly limited. That is, the specific compound may be any of (A) colorant, (B) polymer and (C) polymerizable compound, and may be two or more of these. Similarly, the hydroxyl group-containing compound may be any of (A) colorant, (B) polymer and (C) polymerizable compound, and may be two or more of these. Further, even if at least one of (A) a colorant, (B) a polymer and (C) a polymerizable compound contains a compound having a partial structure represented by the above formula (1) and a hydroxyl group. Good.

Specific aspects of the composition of the coloring composition include, for example, the following compounding modes [1] to [8].
[1] The colorant contains a polymer having a partial structure represented by the above formula (1) and a hydroxyl group, and the polymer (B) has a hydroxyl group and is represented by the above formula (1). An embodiment containing a polymer having no partial structure, and (C) a compound having a hydroxyl group as a polymerizable compound and not having a partial structure represented by the above formula (1).
[2] The polymer (B) contains a polymer having a partial structure represented by the above formula (1) and a hydroxyl group, and the (C) polymerizable compound has a hydroxyl group and is represented by the above formula (1). A mode containing a compound having no partial structure. However, the colorant (A) does not have the partial structure represented by the above formula (1) and the hydroxyl group.
[3] (A) Contains a compound having a hydroxyl group as a colorant and not having a partial structure represented by the above formula (1), and (B) a polymer having a partial structure represented by the above formula (1). An embodiment containing a polymer having a hydroxyl group and not having a hydroxyl group, and (C) a compound having a hydroxyl group as a polymerizable compound and not having a partial structure represented by the above formula (1).
[4] The polymer (B) contains a polymer having a partial structure represented by the above formula (1) and does not have a hydroxyl group, and the (C) polymerizable compound has a hydroxyl group and has the above formula (1). An embodiment containing a compound having no partial structure represented. However, the colorant (A) does not have the partial structure represented by the above formula (1) and the hydroxyl group.

[5] The (A) colorant contains a polymer having a partial structure represented by the above formula (1) and a hydroxyl group, and the (B) polymer contains a partial structure represented by the above formula (1) and a hydroxyl group. (C) An embodiment containing a polymer having a hydroxyl group as a polymerizable compound and not having a partial structure represented by the above formula (1).
[6] The (A) colorant contains a polymer having a partial structure represented by the above formula (1) and a hydroxyl group, and the (B) polymer has a hydroxyl group and is represented by the above formula (1). An embodiment containing a polymer having no partial structure. However, the polymerizable compound (C) does not have a partial structure represented by the above formula (1) and a hydroxyl group.
[7] (A) Contains a polymer having a hydroxyl group as a colorant and not having a partial structure represented by the above formula (1), and (B) a partial structure represented by the above formula (1) as a polymer. An embodiment containing a polymer having a hydroxyl group and having no hydroxyl group, and (C) a compound having a hydroxyl group as a polymerizable compound and not having a partial structure represented by the above formula (1).
[8] A partial structure represented by the formula (1) as (A) a polymer containing a hydroxyl group as a colorant, (B) containing a polymer having a hydroxyl group as a polymer, and (C) a polymerizable compound. Aspects containing a compound having. However, at least one of the (A) colorant and the (B) polymer may further have a partial structure represented by the above formula (1).
Hereinafter, each component contained in the coloring composition of the present disclosure and a component contained as necessary will be described in detail.

<(A) Colorant>
The color and type of the colorant (A) are appropriately selected according to the intended use. As the colorant (A), any of pigments, dyes, quantum dots and natural dyes can be used. The colorant (A) is preferably at least one of a pigment and a dye, and particularly preferably contains a dye, in that pixels having high brightness and color purity can be obtained. The pigments and dyes blended in the coloring composition are preferably organic substances. Examples of the colorant (A) include a specific compound, a hydroxyl group-containing compound, and other colorants having a partial structure represented by the above formula (1) and having no hydroxyl group.

(About specific compounds)
In one form of the coloring composition of the present disclosure, the colorant (A) comprises a specific compound. The specific compound (A) as a colorant may have a partial structure represented by the above formula (1) and is not particularly limited. When the specific compound is a polymer, the polymer having the partial structure represented by the above formula (1) can be relatively easily obtained by using a usual polymerization method, and as the colorant (A). The specific compound is preferably a polymer containing a structural unit (a) and a structural unit (b) having a dye structure (hereinafter, also referred to as “polymer (A1)”).

Here, the "dye structure" in the present specification is a partial structure derived from the dye and is a chromophore. The dye structure may have an electric charge. When the dye structure has an electric charge, the dye structure may be in the form of either an intramolecular salt or an intermolecular salt. As the dye structure, a structure derived from a known dye can be adopted, and the dye structure is not particularly limited. Specifically, for example, dipyrromethene pigment, diarylmethane pigment, triarylmethane pigment, xanthene pigment, aclysine pigment, anthraquinone pigment, azo pigment, quinoneimine pigment, polymethine pigment (oxonol pigment, merocyanine pigment, allylidene pigment, styryl pigment, cyanine). Dyes, squarylium dyes, croconium dyes, etc.), phthalocyanine dyes, subphthalocyanine dyes, and structures derived from dyes selected from these metal complex dyes can be mentioned. Among them, from the viewpoint of color characteristics, a structure derived from a pigment selected from the group consisting of triarylmethane pigments, xanthene pigments, anthraquinone pigments, azo pigments, quinoneimine pigments, polymethine pigments, subphthalocyanine pigments and phthalocyanine pigments is preferable. A structure derived from a pigment selected from the group consisting of a reelmethane pigment, a xanthene pigment, a quinoneimine pigment and a polymethine pigment is more preferable, and a dye selected from the group consisting of a triarylmethane pigment, a xanthene pigment, a quinoneimine pigment and a cyanine pigment. The derived structure is more preferred. For specific dyes that can form a dye structure, see "New Edition Dye Handbook" (Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and pigmentists), and "Dye Handbook" (Dye Handbook). It is described in Okawara et al.; Kodansha, 1986).

The dye structure may be composed of a cation portion or an anion portion, and examples thereof include a salt of a cationic chromophore and a counter anion, and a salt of an anionic chromophore and a counter cation. The counterion may be an organic ion or an inorganic ion. Here, the “cationic chromophore” as used herein refers to an atomic group having a positive charge. When the atomic group has a functional group having a positive charge and a functional group having a negative charge, and the total of these charges becomes a positive charge, it is included in the cationic chromophore. To do. The "anionic chromophore" refers to an atomic group having a negative charge. When the atomic group has a functional group having a positive charge and a functional group having a negative charge, and the total of these charges becomes a negative charge, it is included in the anionic chromophore. To do. Further, the dye structure may be an electrically neutral chromophore. The "electrically neutral color group" is an atomic group that does not correspond to either a cationic color group or an anionic color group, and has a functional group having a positive charge and a functional group having a negative charge. There is no or even if it has a functional group with a positive charge and a functional group with a negative charge, the total number of positive charges and the total number of negative charges are the same, and it is electrically neutral as a whole. An atomic group.

（式（ａ１）中、Ｒ^３は、水素原子又は炭素数１〜４のアルキル基である。Ｒ^１、Ｒ^２、Ｌ^１、Ｘ^１、ｎ１及びｎ２は、それぞれ上記式（１）と同義である。）

（式（ａ１−１）〜式（ａ１−９）中、Ｒは水素原子又は炭素数１〜４のアルキル基である。） The structural unit (a) is preferably derived from the compound represented by the following formula (a1) in that a polymer having a partial structure represented by the above formula (1) can be obtained relatively easily. It is a structural unit. Specific examples of the compound represented by the following formula (a1) include compounds represented by the following formulas (a1-1) to (a1-9).

(In the formula (a1), R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹ , R ² , L ¹ , X ¹ , n 1 and n 2 are synonymous with the above formula (1), respectively. Is.)

(In formulas (a1-1) to (a1-9), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

In the polymer (A1), the content ratio of the structural unit (a) is 5% by mass with respect to all the structural units of the polymer (A1) in that the solvent resistance of the cured film can be sufficiently increased. % Or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. Further, the content ratio of the structural unit (a) is 50 with respect to all the structural units of the polymer (A1) in that workability and good colorability at the time of preparing the coloring composition can be maintained. It is preferably 1% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less.

The structural unit (b) is preferably a structural unit derived from an ethylenically unsaturated monomer having a dye structure. The dye structure of the structural unit (b) is a structure derived from a dye selected from the group consisting of ionic dyes and non-ionic dyes in that pixels having high brightness and color purity can be obtained. preferable. Here, in the present specification, an ionic dye in which the chromophore has an acidic group is referred to as an "anionic dye". Anionic dyes are meant to include ionic dyes that form salts with acidic groups. Similarly, an ionic dye in which the chromophore has a basic group is called a "cationic dye". Cationic dye means to include an ionic dye forming a salt with a basic group. A "nonionic dye" is a dye other than a cationic dye and an anionic dye.

（式（ｂ１）中、Ｒは、水素原子又は炭素数１〜４のアルキル基である。Ｌ^２は、単結合又は２価の有機基であり、Ｙ^１は、イオン性染料又は非イオン性染料に由来する構造を有する１価の基である。） The structural unit (b) is a (meth) acrylic monomer, a styrene monomer, and a maleimide-based monomer among the ethylenically unsaturated monomers in that the dye structure can be easily introduced into the side chain of the polymer. It is preferably a structural unit derived from at least one selected from the group consisting of monomers. Among these, a structural unit derived from a (meth) acrylic monomer is preferable, and a structural unit represented by the following formula (b1) is particularly preferable.

(In the formula (b1), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. L ² is a single-bonded or divalent organic group, and Y ¹ is an ionic dye or a non-ionic dye. It is a monovalent group having a structure derived from a dye.)

In the above formula (b1), ^{as the divalent organic group of L 2} , the methylene group of the alkanediyl group having 1 to 20 carbon atoms and the methylene group of the alkanediyl group having 1 to 20 carbon atoms are −O−, −CO−, −. Examples thereof include groups substituted with COO-, -NH-, -CONH-, -S-, -O-CO-Ph-CO-O- (Ph is a phenylene group) and the like.

In Y ^1, as the structure derived from the non-ionic dyes such as triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes, quinoline dyes, nitro dyes , A structure derived from a known dye such as a quinoneimine dye, a phthalocyanine dye, or a squarylium dye. Of these, from the viewpoint of heat resistance, the structure derived from the nonionic dye may be a structure derived from the triarylmethane dye, the cyanine dye, the xanthene dye, the anthraquinone dye, the dipyrromethene dye, the squarylium dye or the phthalocyanine dye. preferable.

Specific examples of the structure derived from the ionic dye in Y ¹ include a structure composed of a cationic chromophore and a counter anion, and a structure composed of an anionic chromophore and a counter cation. In the above formula (b1), the bond between the dye structure of ^{Y 1 and L 2} is that of the cationic chromophore and the counter anion when the dye structure of ^{Y 1 is composed of a cationic chromophore and a counter anion.} One of them is formed by binding to ^{L 2} either directly or via a divalent linking group. When the dye structure of ^{Y 1} is composed of an anionic chromophore and a counter cation, the bond between the dye structure of ^{Y 1 and L 2 is directly formed by either the anionic chromophore or the counter cation.} Alternatively, it is formed by binding to ^{L 2} via a divalent linking group.

Examples of the cationic chromophore include triarylmethane chromophore, cyanine chromophore, xanthene chromophore, polymethine chromophore, azo chromophore, diarylmethane chromophore, quinoneimine chromophore, anthraquinone chromophore, phthalocyanine chromophore, and squarylium chromophore. A group, a quinophthalone chromophore, etc. can be mentioned. Of these, the cationic chromophore is preferably a triarylmethane chromophore, a cyanine chromophore, a xanthene chromophore, a polymethine chromophore, or an azo chromophore, and more preferably a triarylmethane chromophore or a cyanine chromophore. As a cationic chromophore, C.I .; published by The Society of Dyers and Colorists in the Color Index (CI; The Society of Dyers and Colorists). It is also possible to use the cation part of the dye classified as I. Basic.

In the structure composed of the cationic chromophore and the counter anion, the counter anion is not particularly limited, and examples thereof include the anion described in paragraph 0034 of JP2015-129263A. Among these, sulfonate anion, imide anion or carboxylate anion is preferable, imide anion is more preferable, and sulfonylimide anion is further preferable.

Examples of anionic chromophores include triarylmethane chromophore, polymethine chromophore, azo chromophore, diarylmethane chromophore, quinoneimine chromophore, anthraquinone chromophore, phthalocyanine chromophore, xanthene chromophore, squarylium chromophore, and quinophthalone chromophore. You can mention a group. Of these, the anionic chromophore is preferably a triarylmethane chromophore, an azo chromophore, a phthalocyanine chromophore or a xanthene chromophore, and a triaryl having at least one of _{−SO 3} − and −CO _{2 − substituents.} A methane chromophore, an azo chromophore, a phthalocyanine chromophore, or a xanthene chromophore is more preferred. As an anionic chromophore, C.I. Anionic portions of dyes classified as I. Acid can also be used.

In the structure composed of an anionic chromophore and a counter cation, examples of the counter cation include an ammonium cation, a phosphonium cation, a sulfonium cation, an iodonium cation, and a diazonium cation. Among these, the counter cation is preferably an ammonium cation or a phosphonium cation, and more preferably an ammonium cation.

In the polymer (A1), the content ratio of the structural unit (b) is 30% by mass or more with respect to all the structural units of the polymer (A1) from the viewpoint of obtaining a colorant exhibiting good colorability. It is preferable, it is more preferably 40% by mass or more, and further preferably 50% by mass or more. Further, the content ratio of the structural unit (b) is 99% by mass or less with respect to all the structural units of the polymer (A1) from the viewpoint of ensuring the developer solubility of the polymer (A1). It is more preferably 98% by mass or less, and even more preferably 95% by mass or less.

The polymer (A1) may have only the structural unit (a) and the structural unit (b), but from the viewpoint of improving solvent resistance, heat resistance, and dispersibility, the above formula (1) is used. It is preferable to further have a structural unit (c) having neither the represented partial structure nor the dye structure. The structural unit (c) is preferably a structural unit derived from an ethylenically unsaturated monomer, and is composed of a group consisting of a (meth) acrylic monomer, a styrene monomer, and a maleimide monomer. More preferably, it is a structural unit derived from at least one selected.

Specific examples of the monomer forming the structural unit (c) (hereinafter, also referred to as “other monomer”) include alkyl (meth) acrylate, alkenyl (meth) acrylate, and aryl (meth) acrylate. Hydroxyalkyl (meth) acrylate, primary amino group-containing alkyl (meth) acrylate, secondary amino group-containing alkyl (meth) acrylate, tertiary amino group-containing alkyl (meth) acrylate, and alicyclic hydrocarbon group (meth). ) Acrylate ester, aromatic vinyl compound, (meth) acrylic acid ester of polyhydric alcohol, N-substituted maleimide, vinyl ether, ethylenically unsaturated monomer having oxygen-containing saturated heterocycle, at the end of polymer molecular chain Examples thereof include macromonomers having a mono (meth) acryloyl group. The polymer (A1) may have only one type of the structural unit (c), or may have two or more types.

By using a monomer having a hydroxyl group (hereinafter, also referred to as “hydroxyl-containing monomer”) as the other monomer, the colorant (A) has a partial structure represented by the above formula (1). A polymer having a hydroxyl group and a dye structure (hereinafter, also referred to as “polymer (A1-1)”) can be obtained. By using such a polymer (A1-1) as the (A) colorant, a crosslinked structure is formed between the molecules of the polymer (A1-1), and the elution of the colorant from the cured film can be sufficiently suppressed. Is preferable. The polymer (A1-1) is both a specific compound and a hydroxyl group-containing compound. The hydroxyl group-containing monomer is preferably an ethylenically unsaturated monomer, and is at least one selected from the group consisting of a (meth) acrylic monomer, a styrene monomer, and a maleimide monomer. It is more preferably a seed, more preferably at least one selected from the group consisting of a (meth) acrylic monomer and a styrene-based monomer, and further preferably a (meth) acrylic monomer. Is particularly preferable.

Specific examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, and 6-hydroxyhexyl (meth). ) (Meta) acrylic acid hydroxyalkyl esters such as acrylates and 8-hydroxyoctyl (meth) acrylates; caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth) acrylates; diethylene glycol (meth) acrylates and polyethylene glycol (meth) acrylates. Oxyalkylene-modified monomers such as; Monomers containing primary and secondary hydroxyl groups such as glycerol mono (meth) acrylates;
(Meta) acrylic for side chain glycidyl groups such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, and glycidyl (meth) acrylate. Monomer to which an acid monomer such as acid is added, monomer to which a glycidyl group of a side chain such as glycidyl (meth) acrylate is added to an acid monomer such as (meth) acrylic acid, 3,4-epoxycyclohexylmethyl (meth) acrylate Etc., a monomer in which an acid monomer such as (meth) acrylic acid is added to an alicyclic epoxy group of the side chain, and a 3,4-epoxycyclohexylmethyl (meth) acrylate for an acid monomer such as (meth) acrylic acid. Add an acid monomer such as (meth) acrylic acid to the side chain oxetanyl group such as (3-ethyl-3-oxetanyl) methoxymethyl (meth) acrylate, which is a monomer to which an alicyclic epoxy group of the side chain is added. Secondary hydroxyl group-containing monomer such as a monomer obtained by adding a side chain oxetanyl group such as (3-ethyl-3-oxetanyl) methoxymethyl (meth) acrylate to an acid monomer such as (meth) acrylic acid;
Examples thereof include a tertiary hydroxyl group-containing monomer such as 2,2-dimethyl-2-hydroxyethyl (meth) acrylate. As the hydroxyl group-containing monomer, one type may be used alone, or two or more types may be used in combination.

The hydroxyl group-containing monomer used for the synthesis of the polymer (A1-1) is excellent in reactivity ^{with the group "OR 1} " and the group "OR ^{2" having the partial structure represented by the above formula (1).} Therefore, a monomer having a primary and / or secondary alcoholic hydroxyl group in the polymer side chain is preferable. Among them, the hydroxyl group-containing monomer is preferably at least one selected from the group consisting of a primary hydroxyl group-containing monomer, a primary hydroxyl group and a secondary hydroxyl group-containing monomer, and a secondary hydroxyl group-containing monomer. Examples of the primary hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth). ) Hydroxyalkyl esters of (meth) acrylic acids such as acrylates are particularly preferred. As the primary hydroxyl group and secondary hydroxyl group-containing monomer, glycerol mono (meth) acrylate is particularly preferable. Examples of the secondary hydroxyl group-containing monomer include a monomer obtained by adding an acid monomer such as (meth) acrylic acid to a glycidyl group of a side chain such as glycidyl (meth) acrylate, and a glycidyl with respect to an acid monomer such as (meth) acrylic acid. A monomer to which a glycidyl group of the side chain such as (meth) acrylate is added, and an acid monomer such as (meth) acrylic acid to the alicyclic epoxy group of the side chain such as 3,4-epoxycyclohexylmethyl (meth) acrylate. The added monomer, a monomer in which a side chain alicyclic epoxy group such as 3,4-epoxycyclohexylmethyl (meth) acrylate is added to an acid monomer such as (meth) acrylic acid, (3-ethyl-3-oxetanyl) ) For a monomer in which an acid monomer such as (meth) acrylic acid is added to a side chain oxetanyl group such as methoxymethyl (meth) acrylate, and for an acid monomer such as (meth) acrylic acid (3-ethyl-3-3). Monomers to which a side chain oxetanyl group is added, such as oxetanyl) methoxymethyl (meth) acrylate, are particularly preferable.

As a method for obtaining the polymer (A1-1), a method of polymerizing the above-mentioned hydroxyl group-containing monomer, specific group-containing monomer, and monomer having a dye structure as a raw material monomer (method [method]. In addition to 1a]), the following methods [2a] to [4a] can be mentioned.
Method [2a]: Epoxide group side by polymerizing an epoxy group-containing monomer (or carboxy group-containing monomer), a specific group-containing monomer, and a monomer having a dye structure as a raw material monomer. A method in which a polymer having a chain is obtained, and then the polymer is reacted with a carboxy group-containing compound (or an epoxy group-containing compound) to introduce a hydroxyl group (more specifically, a secondary hydroxyl group) into a side chain.
Method [3a]: Specific group-containing monomer and dye using a polymerization initiator having a hydroxyl group (for example, 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) propionamide) or the like). A method of polymerizing a raw material monomer containing a monomer having a structure.
Method [4a]: A chain transfer agent containing a hydroxyl group (for example, monoethanolamine thioglycolate, 2,3-dihydroxy-1,4-butanedithiol, etc.) is used to obtain a specific group-containing monomer and a dye structure. A method of polymerizing a raw material monomer containing a monomer having.
Of these, according to the method [1a] and the method [2a], a polymer having a hydroxyl group in the side chain can be obtained. Further, according to the method [3a] and the method [4a], a polymer having a hydroxyl group at the end of the main chain can be obtained. Here, in the present specification, "having a hydroxyl group at the end of the main chain" means that a bond is formed with respect to a structural unit of the main chain structure that does not form a bond with an adjacent structural unit. ..

In the method [2a], the epoxy group-containing monomer is preferably a (meth) acrylic monomer, for example, an oxylanyl group-containing (meth) acrylic monomer such as glycidyl (meth) acrylate; 3,4-epoxide. Alicyclic epoxy group-containing (meth) acrylic monomer such as cyclohexylmethyl (meth) acrylate; (3-ethyl-3-oxetanyl) Oxetanyl group-containing (meth) acrylic monomer such as methoxymethyl (meth) acrylate The body etc. can be mentioned. As the carboxy group-containing compound, a compound having a carboxy group and an ethylenically unsaturated bond is preferable, a (meth) acrylic compound is more preferable, and (meth) acrylic acid is particularly preferable. The polymer (A1-1) is preferably a polymer having a hydroxyl group in at least a side chain because the amount of hydroxyl groups contained in the polymer can be easily adjusted and a hydroxyl group-containing polymer can be obtained relatively easily. ..

In the polymer (A1-1), the content ratio of the structural unit having a hydroxyl group is 0, with respect to all the structural units of the polymer (A1-1), from the viewpoint of obtaining a colored cured film having high solvent resistance. It is preferably 5% by mass or more, more preferably 1% by mass or more, and further preferably 5% by mass or more. Further, the content ratio of the structural unit having a hydroxyl group is preferably 50% by mass or less, preferably 45% by mass, based on all the structural units of the polymer (A1-1) from the viewpoint of improving storage stability. It is more preferably% or less, and further preferably 40% by mass or less.

The method for obtaining the polymer (A1) is not particularly limited. The polymer (A1) can be produced by using the above-mentioned monomer, for example, by radical polymerization, anionic polymerization, cationic polymerization, living radical polymerization, living anionic polymerization, living cationic polymerization or the like. When the polymer (A1-1) is produced by the above method [2a], the reaction between the epoxy group-containing monomer and the carboxy group-containing compound can be carried out in a solution, for example, according to a known method.

(About hydroxyl group-containing compounds)
In one form of the coloring composition of the present disclosure, the colorant (A) comprises a hydroxyl group-containing compound. The hydroxyl group-containing compound as the (A) colorant may be a low molecular weight compound or a polymer. (A) When a low molecular weight compound having a hydroxyl group is used as the colorant, the low molecular weight compound can obtain a colored cured film having high brightness and color purity. 1) ”) is preferable. The hydroxyl group-containing dye (A2-1) may be either a nonionic dye or an ionic dye, and in the case of an ionic dye, it may be either an anionic dye or a cationic dye.

The number of hydroxyl groups contained in the hydroxyl group-containing dye (A2-1) is preferably 1 to 10 and more preferably 2 to 8 from the viewpoint of achieving both solvent resistance and storage stability.
Examples of the hydroxyl group-containing dye (A2-1) include the hydroxyl group-containing dyes described in Japanese Patent Application Laid-Open No. 2013-173850 and Pamphlet of International Publication No. 2014/192973. Further, it can be produced by a known method using the known dyes exemplified above as raw materials. As the hydroxyl group-containing dye (A2-1), one type may be used alone, or two or more types may be used.

(A) When a polymer having a hydroxyl group is used as the colorant, the polymer has a hydroxyl group and a dye structure in addition to the polymer (A1-1) and is represented by the above formula (1). Examples thereof include a polymer having no partial structure (hereinafter, also referred to as “hydroxyl-containing polymer (A2-2)”). The hydroxyl group-containing polymer (A2-2) may have a hydroxyl group and a dye structure, and the position of the hydroxyl group and the like are not particularly limited. That is, the hydroxyl group-containing polymer (A2-2) may have a hydroxyl group in the side chain, may have a hydroxyl group at the end of the main chain, or may have a hydroxyl group at both the side chain and the end of the main chain. Good. Examples of the method for obtaining the hydroxyl group-containing polymer (A2-2) include the method of polymerizing without using the specific group-containing monomer in the methods [1a] to [4a] described in the polymer (A1-1). Be done. When producing the hydroxyl group-containing polymer (A2-2), only one of these methods may be used, or two or more of these methods may be combined. The polymer (A2-2) is preferably a polymer having a hydroxyl group in at least a side chain because the amount of hydroxyl groups can be easily adjusted and a hydroxyl group-containing polymer can be obtained relatively easily.

In the polymer (A2-2), the content ratio of the structural unit having a hydroxyl group is 0, with respect to all the structural units of the polymer (A2-2), from the viewpoint of obtaining a colored cured film having high solvent resistance. It is preferably 5% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, and even more preferably 5% by mass or more. Further, the content ratio of the structural unit having a hydroxyl group is preferably 70% by mass or less, preferably 60% by mass, based on the total structural unit of the polymer (A2-2) from the viewpoint of obtaining good colorability. It is more preferably less than or equal to 50% by mass or less.

When the colorant (A) is a polymer, the weight average molecular weight (Mw) of the polymer measured by gel permeation chromatography (GPC) is preferably 1,000 to 100,000. Mw is preferably 3,000 or more. Further, Mw is preferably 50,000 or less. When Mw is 1,000 or more, the pattern shape is preferable, and when it is 100,000 or less, the resolution time does not become too long, which is preferable from the viewpoint of ensuring processability. When the colorant (A) is a polymer, the ratio (Mw / Mn) of Mw of the polymer to the number average molecular weight (Mn) is preferably 1.0 to 5.0, more preferably 1. It is 0 to 3.0.

(Other colorants)
The coloring composition may contain at least one of the specific compound and the hydroxyl group-containing compound as the colorant (A), but has both the partial structure represented by the above formula (1) and the hydroxyl group. A non-coloring agent (hereinafter, also referred to as “another colorant”) may be used in combination. Further, when at least one component selected from the group consisting of (B) polymer and (C) polymerizable compound contains a partial structure represented by the above formula (1) and a hydroxyl group, a coloring composition. (A) may contain only other colorants as the colorant.

The other colorants are not particularly limited, and colors and types can be appropriately selected depending on the intended use. As other colorants, any of pigments, dyes, quantum dots and natural dyes can be used. When the coloring composition of the present disclosure is used for forming each color pixel constituting a color filter, other colorants are selected from the group consisting of pigments and dyes in that pixels having high brightness and color purity can be obtained. At least one selected from the group consisting of organic pigments and organic dyes is more preferable.

As the organic pigment, a compound classified as a pigment in the color index (CI; published by The Society of Dyers and Colorists), that is, the following color index (CI) name is given. The following organic pigments can be preferably used.

C. I. Pigment Red 166, C.I. I. Pigment Red 177, C.I. I. Pigment Red 224, C.I. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. Pigment Red 264, C.I. I. Red pigments such as Pigment Red 279;
C. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Green pigments such as Pigment Green 59;
C. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 79, C.I. I. Pigment Blue 80, C.I. I. Blue pigments such as Pigment Blue 60;
C. I. Pigment Yellow 83, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 179, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 211, C.I. I. Pigment Yellow 215, C.I. I. Pigment Yellow 231 and other yellow pigments;
C. I. Pigment Orange 38 and other orange pigments; C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Purple pigments such as Pigment Violet 29; black pigments such as lactam-based black pigments and perylene-based black pigments.
Further, as the organic pigment, in addition to the above, a brominated diketopyrrolopyrrole pigment represented by the formula (Ic) of JP-A-2011-523433 can also be used.

Examples of the inorganic pigment include carbon black and titanium black. Other examples of the inorganic pigments include JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-237384, JP-A-2010-237569, JP-A-2011-006602, and JP-A-2011. The rake pigment described in JP-A-145346 and the like can be mentioned.

When a pigment is used, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof. Further, if desired, the particle surface of the pigment may be modified with a resin before use. Further, when using an organic pigment, the primary particles may be made finer by so-called salt milling. As the salt milling method, for example, the method described in JP-A-08-179111 can be adopted.

The dye is not particularly limited, and for example, in addition to the compounds classified as Dye in the above color index, known dyes can be used. Examples of such dyes include known dyes exemplified above. Among the above, from the viewpoint of heat resistance, triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes and phthalocyanine dyes are preferable.

The dye may be composed of a cationic moiety and an anionic moiety. Examples of such a dye include a salt of a cationic chromophore and a counter anion, or a salt of an anionic chromophore and a counter cation. The above description applies to examples of cationic chromophores, anti-anions, anionic chromophores and anti-cations.

If desired, the coloring composition of the present disclosure may contain a dispersant together with the (A) colorant. Further, the coloring composition may contain a dispersion aid together with the dispersant. Known dispersants and dispersion aids can be used. Specifically, as the dispersant, for example, urethane dispersant, polyethyleneimine dispersant, polyoxyethylene alkyl ether dispersant, polyoxyethylene alkyl phenyl ether dispersant, polyethylene glycol diester dispersant, sorbitan fatty acid ester. System dispersants, polyester dispersants, acrylic dispersants and the like; examples of the dispersion aids include pigment derivatives and the like.

Specific examples of the dispersant include, as basic dispersants, for example, Solspars 11200, Solspers 13240, Solspers 13650, Solspers 13940, Solspers 16000, Solspers 17000, Solspers 18000, Solspers 20000, Solspers 24000SG, Solspers 24000GR, Solspers 28000, Solspers 31845. , Sol Spurs 32000, Sol Spurs 32500, Sol Spurs 32550, Sol Spurs 32600, Sol Spurs 33000, Sol Spurs 34750, Sol Spurs 35100, Sol Spurs 35200, Sol Spurs 37500, Sol Spurs 38500, Sol Spurs 39000, Sol Spurs 56000, Sol Spurs 71000, Sol Spurs 76400, Sol Spurs 76 9000, Sol Spurs J200 (all manufactured by Loubrizor), DISPERBYK-108, DISPERBYK-109, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-163 -166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-182, DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBYK-2000, DISPERBYK-2008, DISPERBYK-2009, DISPERBYK-2022, DISPERBYK-2022 , DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164, BYK-9077 (above, manufactured by Big Chemie), Azisper PB821, PB822, PB823, PB824, PB827 (above, manufactured by Ajinomoto Fine-Techno) and the like.

As the acidic dispersant, Solspars 3000, Solspers 21000, Solspers 26000, Solspers 36600, Solspers 41000, Solspers 41090, Solspers 43000, Solspers 44000, Solspers 46000, Solspers 47000, Solspers 55000 (all manufactured by Lubrizol), DISPERBYK-102. , DISPERBYK-111, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-2096, BYK-P104, BYK-P104S, BYK-P105, BYK-220S (all manufactured by Big Chemie) and the like. The dispersant may be used alone or in combination of two or more.

The content ratio of the colorant (A) can be appropriately selected depending on the intended use and the like. From the viewpoint of forming pixels having high brightness and excellent color purity and forming a black matrix having excellent light-shielding property, the content ratio of (A) the colorant is preferable with respect to the total solid content of the coloring composition. Is 5 to 70% by mass. The content ratio of the colorant (A) is more preferably 8% by mass or more, further preferably 10% by mass or more, and particularly preferably 12% by mass or more, based on the total solid content of the coloring composition. Is. The content ratio of the colorant (A) is more preferably 60% by mass or less, still more preferably 55% by mass or less, and particularly preferably 45% by mass, based on the total solid content of the coloring composition. % Or less.

The content ratio of the dye in the (A) colorant is preferably 5% by mass or more with respect to the total amount of the (A) colorant. In general, since dyes are inferior in heat resistance, it is difficult to heat the coating film at a post-bake temperature of 200 ° C. or higher when forming a cured film using a coloring composition containing a dye. On the other hand, the coloring composition of the present disclosure can form a cured film having excellent solvent resistance even when post-baking is performed at a temperature of less than 200 ° C., preferably 180 ° C. or lower. Therefore, the coloring composition of the present disclosure can increase the content ratio of the dye, and can be suitably used for producing various color filters. From the viewpoint of obtaining a colored cured film having high brightness and color purity, the content ratio of the dye is more preferably 10% by mass or more, further preferably 20% by mass or more, and further preferably 30% by mass with respect to the total amount of the (A) colorant. % Or more is particularly preferable.

<(B) Polymer>
The polymer (B) is contained in the coloring composition for the purpose of dispersing, dyeing or permeating the colorant (A) or as a binder resin. When an alkali-developed colored composition for forming a cured film is obtained, it is preferable that the polymer (B) is an alkali-soluble polymer. The polymer (B) is different from the polymer such as a dye resin which is a colorant in that it does not have a dye structure.

When the polymer (B) is an alkali-soluble polymer, the polymer (B) may be soluble in an alkaline solution, and is not particularly limited, but has a carboxy group, a phenolic hydroxyl group, or the like. It is preferably a polymer having the acidic functional group of. Among these, the polymer (B) is preferably a polymer having a carboxy group (hereinafter, also referred to as “carboxy group-containing polymer”). Examples of the carboxy group-containing polymer include an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter, also referred to as “unsaturated monomer (b1)”) and an unsaturated monomer (b1). ) And an ethylenically unsaturated monomer (hereinafter, also referred to as “unsaturated monomer (b2)”) that can be copolymerized with the copolymer.

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, mono oxalic acid [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth). Examples thereof include acrylate, p-vinylbenzoic acid, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid and the like. The carboxy group-containing polymer may have only one type of structural unit derived from the unsaturated monomer (b1), or may have two or more types in combination.

In the above-mentioned copolymer, the content ratio of the structural unit derived from the unsaturated monomer (b1) is that a colored cured film having excellent alkali developability can be obtained, and the entire composition of the polymer (B) is obtained. It is preferably 5% by mass or more, and more preferably 8% by mass or more with respect to the unit. Further, the content ratio of the structural unit derived from the unsaturated monomer (b1) is 30% by mass or less with respect to all the structural units of the above-mentioned copolymer in terms of improving the solubility in a solvent. It is preferably 20% by mass or less, and more preferably 20% by mass or less.

The unsaturated monomer (b2) can be appropriately selected depending on the intended use and the like, and is not particularly limited. (B) When synthesizing a polymer, an ethylenically unsaturated monomer having a partial structure represented by the above formula (1) as an unsaturated monomer (b2) (hereinafter, also referred to as a “specific group-containing monomer””. By using (referred to as), a specific compound can be obtained as the (B) polymer. Further, by using an ethylenically unsaturated monomer having a hydroxyl group as the unsaturated monomer (b2), a hydroxyl group-containing compound can be obtained as the polymer (B).

(About specific compounds)
In one form of the coloring composition of the present disclosure, the (B) polymer comprises a specific compound. (B) The specific compound as the polymer has the structural unit (a) in that it is easy to synthesize a polymer having a partial structure represented by the above formula (1) in the side chain (hereinafter, "heavy"). It is also preferable to be a coalescence (B1). The description of (A) colorant applies to examples and preferred examples of specific group-containing monomers used to have the structural unit (a).

In the polymer (B1), the content ratio of the structural unit (a) is 2% by mass with respect to all the structural units of the polymer (B1) in that the solvent resistance of the cured film can be sufficiently increased. % Or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. Further, the content ratio of the structural unit (a) is 80% by mass or less with respect to all the structural units of the polymer (B1) in that the storage stability of the coloring composition can be maintained. It is preferably 70% by mass or less, more preferably 60% by mass or less.

By using a hydroxyl group-containing monomer as the unsaturated monomer (b2) in the synthesis of the polymer (B1), the partial structure represented by the above formula (1) and the hydroxyl group can be used as the polymer (B). A polymer having a polymer (hereinafter, also referred to as “polymer (B1-1)”) can be obtained. By containing the polymer (B1-1) in the coloring composition, a crosslinked structure is formed between the polymers (B1-1), and a cured film having better solvent resistance can be obtained, which is preferable. Is. The polymer (B1-1) is both a specific compound and a hydroxyl group-containing compound. The description of (A) colorant applies to examples and preferred examples of hydroxyl group-containing monomers used in the synthesis of the polymer (B1).

As a method for obtaining the polymer (B1-1), in addition to a method of polymerizing a hydroxyl group-containing monomer and a specific group-containing monomer as a raw material monomer (method [1b]), the following method [2b] ] To [4b].
Method [2b]: A polymer having an epoxy group in the side chain is obtained by polymerizing using an epoxy group-containing monomer (or a carboxy group-containing monomer) and a specific group-containing monomer as a raw material monomer. Next, a method in which the polymer is reacted with a carboxy group-containing compound (or an epoxy group-containing compound) to introduce a hydroxyl group (more specifically, a secondary hydroxyl group) into the side chain.
Method [3b]: Contains a specific group-containing monomer using a polymerization initiator having a hydroxyl group (for example, 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) propionamide) or the like). A method of polymerizing a raw material monomer.
Method [4b]: A raw material monomer containing a specific group-containing monomer using a chain transfer agent containing a hydroxyl group (for example, monoethanolamine thioglycolate, 2,3-dihydroxy-1,4-butanedithiol, etc.). Method of polymerizing.
The description of the above method [2a] is applied to specific examples of the epoxy group-containing monomer and the carboxy group-containing compound used in the method [2b]. The polymer (B1-1) is preferably a polymer having a hydroxyl group in at least a side chain because the amount of hydroxyl groups contained in the polymer can be easily adjusted and a hydroxyl group-containing polymer can be obtained relatively easily. ..

Examples of the unsaturated monomer (b2) used in the synthesis of the polymer (B1) include N-alkylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like. -Substituted maleimide; aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;
Methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, allyl ( Meta) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, dicyclopentenyl (meth) ) Acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane, etc. (Meta) acrylic acid ester;
Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylvinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane. The polymer (B) may have only one type of structural unit derived from the unsaturated monomer (b2), or may have two or more types in combination.

(About hydroxyl group-containing compounds)
In one form of the coloring composition of the present disclosure, the polymer (B) contains a hydroxyl group-containing compound. (B) When a polymer having a hydroxyl group is used as the polymer, the polymer has a partial structure having a hydroxyl group and represented by the above formula (1) in addition to the above polymer (B1-1). Examples thereof include polymers that do not have (hereinafter, also referred to as “hydroxyl-containing polymer (B2)”). The hydroxyl group-containing polymer (B2) may have a hydroxyl group in the side chain, may have a hydroxyl group at the end of the main chain, or may have a hydroxyl group at both the side chain and the end of the main chain. Of these, the hydroxyl group-containing polymer (B2) is a polymer having a hydroxyl group in at least a side chain in that the amount of the hydroxyl group can be easily adjusted and the hydroxyl group-containing polymer can be obtained relatively easily. Is preferable. Examples of the method for obtaining the hydroxyl group-containing polymer (B2) include the method of polymerizing in the methods [1b] to [4b] described in the polymer (B1-1) without using the specific group-containing monomer. The description of (A) colorant applies to examples and preferred examples of hydroxyl group-containing monomers used in the synthesis of the polymer (B2). When producing the hydroxyl group-containing polymer (B2), only one of the methods [1b] to [4b] may be used, or two or more thereof may be combined.

In each of the polymer (B1-1) and the polymer (B2), the content ratio of the structural unit having a hydroxyl group is the polymer (B1-1) or the polymer from the viewpoint of obtaining a colored cured film having high solvent resistance. It is preferably 2% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more with respect to all the constituent units of (B2). Further, the content ratio of the structural unit having a hydroxyl group is 70% by mass or less with respect to the total structural unit of the polymer (B1-1) or the polymer (B2) from the viewpoint of improving the storage stability. It is more preferable, it is more preferably 65% by mass or less, and further preferably 60% by mass or less.

(Other polymers)
The coloring composition may contain at least one of the specific compound and the hydroxyl group-containing compound as the polymer (B), but has both the partial structure represented by the above formula (1) and the hydroxyl group. A non-polymer (hereinafter, also referred to as “another polymer”) may be used in combination. When a specific compound and a hydroxyl group-containing compound are contained as at least one selected from the group consisting of (A) colorant and (C) polymerizable compound, the coloring composition may be another (B) polymer. It may contain only the polymer.

The other polymer is not particularly limited and may be appropriately selected depending on the intended use. Specific examples of other polymers include, for example, JP-A-7-140654, JP-A-8-259876, JP-A-10-31308, JP-A-10-300922, and JP-A-11-174224. Examples thereof include copolymers disclosed in JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728 and the like. Examples of the polymer (B) include JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, and JP-A-11-140144. , JP-A-2008-181095, etc., a carboxy group-containing polymer having a polymerizable unsaturated bond (for example, a carbon-carbon double bond in a (meth) acryloyl group) in a side chain. It can also be used.

The polymer (B) can be produced by a known method such as radical polymerization, anionic polymerization, cationic polymerization, living radical polymerization, living anionic polymerization, living cationic polymerization and the like. Further, for example, the structure, Mw and Mw / Mn can be controlled by the method disclosed in JP-A-2003-222717, JP-A-2006-259680, Pamphlet No. 07/029871 and the like. As the polymer (B), one type can be used alone or two or more types can be mixed and used.

For the polymer (B), the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) with tetrahydrofuran as the elution solvent is preferably 1,000 to 100,000. Mw is preferably 3,000 or more. Further, Mw is preferably 50,000 or less. When Mw is 1,000 or more, the pattern shape can be improved, and when it is 100,000 or less, the resolution time does not become too long, which is preferable from the viewpoint of ensuring processability.
The ratio (Mw / Mn) of the Mw of the polymer (B) to the number average molecular weight (Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. Mn is a polystyrene-equivalent value measured by GPC using tetrahydrofuran as the elution solvent.

In the coloring composition, the content of the (B) polymer is usually 10 to 1,000 parts by mass with respect to 100 parts by mass of the (A) colorant. When the content of the polymer (B) is in the above range, it has appropriate alkali developability in the coating film forming process, sufficient storage stability as a product of the coloring composition, and the required film thickness as a color filter. Sufficient color density can be secured. The content of the polymer (B) is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more with respect to 100 parts by mass of the (A) colorant. The content of the polymer (B) is preferably 500 parts by mass or less, and more preferably 300 parts by mass or less, with respect to 100 parts by mass of the (A) colorant.

<(C) Polymerizable compound>
The polymerizable compound (C) is a compound having preferably two or more polymerizable groups, and is a low molecular weight compound that functions as a cross-linking agent. The (C) polymerizable compound is different from the (A) colorant in that it does not have a dye structure, and is different from the (B) polymer in that it does not have a molecular weight distribution. That is, compounds having a polymerizable group and a dye structure are classified as (A) colorants. A polymer having a polymerizable group and not having a dye structure is classified as (B) polymer. The molecular weight of the polymerizable compound (C) is preferably 1,000 or less, more preferably 800 or less.

Examples of the polymerizable group include an ethylenically unsaturated group, an oxylanyl group, an oxetanyl group, an N-alkoxymethylamino group and the like. Of these, the (C) polymerizable compound is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups, and is preferably two or more (. A compound having a meta) acryloyl group is particularly preferable. The number of polymerizable groups contained in one molecule of the (C) polymerizable compound is preferably 2 to 10, and more preferably 2 to 8.

(About hydroxyl group-containing compounds)
In one form of the coloring composition of the present disclosure, the (C) polymerizable compound contains a hydroxyl group-containing compound (hereinafter, also referred to as “hydroxyl-containing cross-linking agent (C1)”). By using the hydroxyl group-containing cross-linking agent (C1), ^{the reaction points with the groups "-OR 1} " and the group "-OR ² " in the above formula (1) can be introduced relatively easily, and in the coloring composition. It is preferable because the content of the hydroxyl group of the above can be easily adjusted.

From the viewpoint of achieving both solvent resistance and storage stability, the hydroxyl group-containing cross-linking agent (C1) preferably has 1 to 8 hydroxyl groups in one molecule, and preferably 1 to 6 hydroxyl groups. More preferably, the number is more preferably 1 to 4. Further, the hydroxyl group-containing cross-linking agent (C1) is particularly preferably a compound having two or more (meth) acryloyl groups in that it has high reactivity to heat and light.

When the coloring composition of the present disclosure contains only the hydroxyl group-containing cross-linking agent (C1) as the hydroxyl group-containing compound, the hydroxyl group-containing cross-linking agent (C1) preferably has a hydroxyl value of 10 to 500 mgKOH / g. By setting the hydroxyl value of the hydroxyl group-containing cross-linking agent (C1) to a value within the above range, the effect of increasing the solvent resistance of the colored cured film obtained by using the coloring composition of the present disclosure and the preservation of the coloring composition. It is preferable in that the effect of stability can be well-balanced. From the viewpoint of solvent resistance, the hydroxyl value of the hydroxyl group-containing cross-linking agent (C1) is more preferably 25 mgKOH / g or more, still more preferably 50 mgKOH / g or more. From the viewpoint of storage stability, the hydroxyl value of the hydroxyl group-containing cross-linking agent (C1) is more preferably 400 mgKOH / g or less, still more preferably 300 mgKOH / g or less. In the present specification, the "hydroxyl value" represents the number of mg of KOH required to neutralize 1 g of the solid content of the hydroxyl group-containing cross-linking agent (C1).

The hydroxyl group-containing cross-linking agent (C1) is preferably a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, and specific examples thereof include pentaerythritol. Tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate , Dipentaerythritol polyacrylate and the like. Of these, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol polyacrylate are particularly preferable because the crosslink density between molecules or within the molecule can be increased and the curability of the film can be further improved by low-temperature firing. .. As the hydroxyl group-containing cross-linking agent (C1), one type may be used alone, or two or more types may be used in combination.

(Other polymerizable compounds)
The coloring composition may contain only the hydroxyl group-containing compound as the (C) polymerizable compound, but the polymerizable compound having neither the partial structure represented by the above formula (1) nor the hydroxyl group (hereinafter, (Also referred to as “other polymerizable compounds”) may be used in combination. Further, when the coloring composition of the present disclosure contains a specific compound and a hydroxyl group-containing compound as at least one selected from the group consisting of (A) colorant and (B) polymer, the coloring composition is (1). C) As the polymerizable compound, only other polymerizable compounds may be contained.

Specific examples of other polymerizable compounds include polyfunctional (meth) obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid as a compound having two or more (meth) acryloyl groups. ) Acrylate, caprolactone-modified polyfunctional (meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting (meth) acrylate having a hydroxyl group with polyfunctional isocyanate. , Polyfunctional (meth) acrylate having a carboxy group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride and the like can be mentioned.

Examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, a urea structure and the like. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and are a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of compounds having two or more N-alkoxymethylamino groups include N, N, N', N', N'', N''-hexa (alkoxymethyl) melamine, N, N, N'. , N'-tetra (alkoxymethyl) benzoguanamine, N, N, N', N'-tetra (alkoxymethyl) glycoluryl and the like.

Other polymerizable compounds include polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, and the like. Polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate with carboxy group, N, N, N', N', N'', N''-hexa (alkoxymethyl) melamine, N, N, N' , N'-tetra (alkoxymethyl) benzoguanamine is preferable, polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, polyfunctional urethane (meth) acrylate, Polyfunctional (meth) acrylates having a carboxy group are more preferred. As other polymerizable compounds, one type can be used alone or two or more types can be mixed and used.

The content of the (C) polymerizable compound in the coloring composition is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more with respect to 100 parts by mass of the (A) colorant. The content of the (C) polymerizable compound is preferably 1,000 parts by mass or less, and more preferably 500 parts by mass or less, with respect to 100 parts by mass of the (A) colorant. When the content ratio of the polymerizable compound (C) is within the above range, sufficient curability and sufficient alkali developability as a colored cured film can be ensured, and ground stains on the substrate or the light-shielding layer of the unexposed portion can be prevented. It is preferable in that the generation of film residue and the like can be sufficiently suppressed.

The coloring composition of the present disclosure may contain various components in addition to (A) a colorant, (B) a polymer and (C) a polymerizable compound, if necessary. Other components that may be contained in the coloring composition of the present disclosure will be described below.

<(D) Photopolymerization Initiator>
The (D) photopolymerization initiator is a compound that generates an active species capable of initiating the polymerization of the (C) polymerizable compound by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. Examples of such photopolymerization initiators include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acyloxime-based initiators, benzoin-based compounds, benzophenone-based compounds, α-diketone-based compounds, and polynuclear compounds. Examples thereof include quinone-based compounds, diazo-based compounds, imide sulfonate-based compounds, and onium salt-based compounds. Of these, the photopolymerization initiator (D) preferably contains an oxime-based initiator in that radicals can be sufficiently generated and film curing can be sufficiently promoted. As the oxime-based initiator, an O-acyloxygen-based initiator can be preferably used.

等が挙げられる。Ｏ−アシルオキシム系開始剤としては、ＮＣＩ−８３１、ＮＣＩ−９３０（以上、株式会社ＡＤＥＫＡ社製）、ＰＢＧ−３０５７（以上、常州強力電子新材料社製）、イルガキュアＯＸＥ０３（以上、ＢＡＳＦジャパン株式会社製）等の市販品を使用してもよい。 Specific examples of the O-acyloxime-based initiator include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), etanone, 1- [9-ethyl-. 6- (2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) ) -9H-Carbazole-3-yl]-, 1- (O-acetyloxime), etanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-) Dioxolanyl) methoxybenzoyl} -9H-carbazole-3-yl]-, 1- (O-acetyloxime), 1,2-propanedione, 3-cyclohexyl-1- [4- (phenylthio) phenyl]-, 1- (O-Acetyloxime) (compound represented by the following formula (D-1)), compound represented by the following formula (D-2)

And so on. Examples of O-acyloxime initiators include NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), PBG-3057 (above, manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), and Irgacure OXE03 (above, BASF Japan Ltd.). Commercially available products such as (manufactured by the company) may be used.

（式（ｄ−１０）中、Ｘ^１及びＸ^２は、それぞれ独立して単結合又は−ＣＯ−である。ただし、Ｘ^１及びＸ^２の少なくとも一方は−ＣＯ−である。Ｒ^１は炭素数２〜６のアルキル基であり、Ｒ^２は炭素数４〜１０のアルキル基である。Ｒ^４は、炭化水素環又は複素環を有する１価の有機基である。Ｒ^３及びＲ^５は、それぞれ独立して、炭素数１〜６のアルキル基又はフェニル基である。）

（式（ｄ−１１）及び式（ｄ−１２）中、Ｘ^３は、単結合又は炭素数１〜５のアルカンジイル基であり、Ｘ^４は、−Ｏ−、−Ｓ−又は−ＮＲ^１０−（ただし、Ｒ^１０は水素原子、炭素数１〜２０の１価の脂肪族炭化水素基である。）である。Ｘ^５及びＸ^６は、それぞれ独立して単結合又は−ＣＯ−であり、Ｒ^６及びＲ^７は、それぞれ独立して、水素原子又は置換若しくは無置換の１価の炭化水素基であり、Ｒ^８及びＲ^９は、それぞれ独立して、置換若しくは無置換の炭素数１〜２０の１価の炭化水素基、又は置換若しくは無置換の炭素数３〜２０の複素環基である。Ｒ^１１及びＲ^１２は、それぞれ独立して水素原子又は１価の置換基である。） As the O-acyloxime-based initiator, compounds represented by the following formulas (d-10), (d-11) and (d-12) can also be preferably used.

(In formula (d-10), X ¹ and X ² are independently single bonds or -CO-, respectively, where at least one of ^{X 1} and X ^{2 is -CO-. R 1} is carbon. The number 2 to 6 is an alkyl group, R ² is an alkyl group having 4 to 10 carbon atoms. R ⁴ is a monovalent organic group having a hydrocarbon ring or a heterocycle. R ³ and R ⁵ are monovalent organic groups. , Independently, an alkyl group or a phenyl group having 1 to 6 carbon atoms.)

(In formulas (d-11) and (d-12), X ³ is a single bond or an alkanediyl group having 1 to 5 carbon atoms, and X ⁴ is -O-, -S- or -NR ^10. -(However, R ¹⁰ is a hydrogen atom and a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms.) X ⁵ and X ⁶ are independently single bonds or -CO-, respectively. , R ⁶ and R ⁷ are independently hydrogen atoms or substituted or unsubstituted monovalent hydrocarbon groups, and R ⁸ and R ⁹ are independently substituted or unsubstituted carbon atoms 1. It is a monovalent hydrocarbon group of ~ 20 or a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms. R ¹¹ and R ¹² are independently hydrogen atoms or monovalent substituents, respectively. )

In the above formula (d-10), R ¹ is preferably an ethyl group or a propyl group. R ² may be linear or branched, but is preferably linear. R ⁴ is preferably a group in which a hydrocarbon ring or a heterocycle is bonded to a carbon atom of an oxime ester group via a divalent linking group. The divalent linking group is preferably at least one selected from the group consisting of an alkanediyl group having 1 to 4 carbon atoms, -S-, -O- and -CO-, and is preferably a methylene group, an ethylene group, or-. More preferably, it is S- or -O-. The hydrocarbon ring is preferably a cyclopentane ring or a cyclohexane ring, and the heterocycle is preferably a dioxolane ring or a pyrimidine ring.

In the above formulas (d-11) and (d-12), when R ⁶ , R ⁷ , R ⁸ or R ⁹ has a substituent, the substituents include a halogen atom, a nitro group, a hydroxyl group and a carboxy group. , Sulfonic acid group, amino group, cyano group and the like. Substituents of R ¹¹ and R ¹² include halogen atom, nitro group, hydroxyl group, carboxy group, sulfonic acid group, amino group and cyano group, and alkyl group, cycloalkyl group, cycloalkylalkyl group or alkylcycloalkyl group. Examples thereof include a group in which at least one hydrogen atom of the above is substituted with a halogen atom, a nitro group, a hydroxyl group, a carboxy group, a sulfonic acid group, an amino group or a cyano group.

The O-acyloxime-based initiator is composed of an acyloxime compound having a diphenyl sulfide skeleton, an acyloxime compound having a carbazole skeleton, and an acyloxime compound having a fluorene skeleton in that the contrast ratio of the cured film can be improved. At least one selected from the group can be preferably used. The O-acyloxime-based initiator is more preferably at least one selected from the group consisting of an acyloxime compound having a diphenylsulfide skeleton and an acyloxime compound having a fluorene skeleton.

The content ratio of the (D) photopolymerization initiator is preferably 0.01 part by mass or more, and more preferably 1 part by mass or more, based on 100 parts by mass of the (C) polymerizable compound. The content ratio of the (D) photopolymerization initiator is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, with respect to 100 parts by mass of the (C) polymerizable compound. When the content of the photopolymerization initiator (D) is in the above range, sufficient curing of the coating film with an appropriate exposure amount and sufficient alkali developability as a coloring composition can be ensured, and the unexposed portion is covered. It is possible to sufficiently suppress the occurrence of background stains on the substrate or the light-shielding layer and film residue. In addition, the decrease in brightness of the coating film due to yellowing of the polymerization initiator during post-baking can be sufficiently suppressed. (D) The photopolymerization initiator may be used alone or in combination of two or more.

<(E) Solvent>
The coloring composition of the present disclosure is prepared as a liquid composition by blending the solvent (E). As the solvent (E), each component (A), (B), (C) and other components constituting the coloring composition are dispersed or dissolved, and the solvent does not react with these components and has appropriate volatility. Those having can be preferably used.

Specific examples of the solvent (E) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono-. n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n -Butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. Poly) alkylene glycol monoalkyl ethers;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate; having a linear, branched or cyclic structure such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol and the like. Alcohols that may be used; keto alcohols such as diacetone alcohol;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate; ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3- Ketones such as heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl propionate ;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i butyrate Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; aromatic carbides such as toluene and xylene Hydrogens;
Examples thereof include amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, or lactams.

Of these, the solvent (E) includes propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol from the viewpoints of solubility, pigment dispersibility, coatability, and the like. Monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, acetate At least one selected from the group consisting of i-amyl, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butylate, and ethyl pyruvate is preferable. As the solvent (E), one type can be used alone or two or more types can be mixed and used.

The coloring composition of the present disclosure contains at least one solvent (hereinafter, also referred to as "specific alcohols") selected from the group consisting of primary alcohols and secondary alcohols in a predetermined amount or less. Therefore, it is preferable in that the storage stability of the coloring composition can be improved. The specific alcohols are preferably solvents having a boiling point of 150 ° C. or lower in order to realize low-temperature firing. Preferred examples of the specific alcohols include methanol, ethanol, propane-1-ol, butane-1-ol, and pentan-1-ol as primary alcohols; and propane-2-ol as secondary alcohols. Butane-2-ol, pentan-2-ol, and hexane-2-ol can be mentioned respectively. Of these, primary alcohols are preferable in that a coloring composition having excellent storage stability can be obtained.

In the coloring composition of the present disclosure, the crosslink formation at the time of film formation is due to a transesterification reaction, and the transesterification reaction is a reversible reaction. Therefore, by allowing specific alcohols to exist in the coloring composition. It is considered that the storage stability of the coloring composition could be improved by maintaining the equilibrium and suppressing the progress of the transesterification reaction.

In the coloring composition of the present disclosure, the content ratio of the specific alcohols is 10% by mass with respect to the total amount of the solvent (E) contained in the coloring composition from the viewpoint of maintaining the dispersibility of the coloring agent (A). The following is preferable, 8% by mass or less is more preferable, and 7% by mass or less is further preferable. Further, the content ratio of the specific alcohols is preferably more than 0% by mass, more preferably 0.01% by mass or more, still more preferably 0.5% by mass or more in order to obtain the effect of improving the storage stability. 1, 1% by mass or more is even more preferable. As the specific alcohols, one type can be used alone or two or more types can be used in combination.

<(F) Additive>
The coloring composition may contain various additives other than the above, if necessary. Examples of the additive include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and silicon-based surfactants; adhesion. Accelerators; antioxidants; UV absorbers; polyfunctional thiols; metal chelate compounds such as zirconium compounds, titanium compounds, aluminum compounds, and the like. These blending ratios can be appropriately set according to the type of each additive as long as the effects of the present disclosure are not impaired.

In the coloring composition of the present disclosure, the content ratio of the specific compound and the hydroxyl group-containing compound is the content of the partial structure represented by the above formula (1) and the content of the hydroxyl group, depending on the compounding form of the specific compound and the hydroxyl group-containing compound. The amounts can be appropriately set so as to be in a suitable range.

<Preparation of coloring composition>
The coloring composition of the present disclosure can be prepared by an appropriate method. Examples of the preparation method include methods disclosed in JP-A-2008-58642 and JP-A-2010-132874. (A) When both a dye and a pigment are used as the colorant, as disclosed in Japanese Patent Application Laid-Open No. 2010-132874, the dye solution is passed through the first filter and then passed through the first filter. A method of preparing the dye solution by mixing it with a separately prepared pigment dispersion or the like and passing the obtained coloring composition through a second filter can be adopted. Further, after dissolving the dye, the above-mentioned (B) polymer and (C) polymerizable compound, and other components used as necessary in a solvent, and passing the obtained solution through a first filter, the dye is passed through a first filter. A method of preparing the solution by mixing the solution that has passed through the first filter with a separately prepared pigment dispersion and passing the obtained coloring composition through the second filter may be adopted. Further, after passing the dye solution through the first filter, the dye solution that has passed through the first filter, the above-mentioned (B) polymer and (C) polymerizable compound, and other components to be used as necessary are passed. The resulting solution was mixed and dissolved, passed through a second filter, and the solution passed through the second filter was mixed with a separately prepared pigment dispersion, and the obtained coloring composition was used as a third filter. A method of preparing by passing may be adopted.

[Color filter and its manufacturing method]
The color filter of the present disclosure includes a colored layer formed by using the above-mentioned coloring composition.

As a method for manufacturing a color filter, first, a light-shielding layer (black matrix) is formed on the surface of a substrate so as to partition a portion forming a pixel, if necessary. Next, for example, a green coloring composition (liquid composition) is applied onto this substrate, and then drying under reduced pressure or prebaking is performed to evaporate the solvent to form a coating film (film forming step). Next, the coating film is exposed to a photomask (exposure step) and then developed with an alkaline developer (development step). At this time, in the case of the positive type, the exposed portion of the coating film is dissolved and removed, and in the case of the negative type, the unexposed portion of the coating film is dissolved and removed. Then, by performing post-baking (heating step), a pixel array in which green pixel patterns are arranged in a predetermined arrangement is formed.

Then, using each of the red or blue coloring compositions, each coloring composition is applied, dried, exposed, developed and post-baked in the same manner as described above, and the red pixel array and the blue pixel array are placed on the same substrate. Form sequentially. As a result, a color filter in which pixel arrays of the three primary colors of green, red, and blue are arranged on the substrate is obtained. However, the order in which the pixels of each color are formed is not limited to the above. The black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern by using a photolithography method. Further, a coloring composition in which a black colorant is dispersed can be used to form the pixels in the same manner as in the case of forming the pixels.

Examples of the substrate used for forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. If desired, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition and the like.

When applying the coloring composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a rotary coating method (spin coating method), a slit die coating method (slit coating method), or a bar coating method is adopted. be able to. Of these, the spin coating method and the slit die coating method are particularly preferable because a coating film having a uniform film thickness can be obtained. After coating, a coating film is formed on the substrate by drying under reduced pressure. The vacuum drying is usually carried out at room temperature for 1 to 15 minutes, preferably 1 to 10 minutes, and is usually carried out at a pressure reaching 50 to 200 Pa. The coating film may be formed by heat treatment (pre-baking) at a temperature lower than the post-baking temperature. The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm as the film thickness after drying.

Examples of the light source of radiation used for exposure include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps, argon ion lasers, and YAG lasers. , XeCl excimer laser, laser light source such as nitrogen laser, and the like. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably in the range of 190 to 450 nm, more preferably in the range of 300 to 450 nm. The exposure amount of radiation is generally preferably ^{10 to 10,000 J / m 2.} The exposure amount of radiation is more preferably 100 J / m ² or more, and further preferably 200 J / m ² or more. The radiation exposure is more preferably 5,000 J / m ² or less, and ^{even more preferably 2,000 J / m 2} or less.

Examples of the alkaline developer include sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1 , 5-Diazabicyclo- [4.3.0] -5-Nonene and other aqueous solutions are preferred. For example, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added in an appropriate amount to the alkaline developer. After alkaline development, it is usually washed with water. As the developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid filling) developing method and the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature.

Post-baking is performed by heating the patterned coating at 70-230 ° C. The post-bake temperature is, for example, 70 to 120 ° C, or 120 ° C to 180 ° C, 180 ° C to 240 ° C in consideration of curability, solvent resistance, improvement of adhesion to the substrate, suppression of color transfer, and substrate protection. Etc., the heating temperature can be set according to the application. At that time, ^{in order to sufficiently proceed the ester exchange reaction between at least one of the groups "OR 1} " and the group "OR ² " of the specific compound and the OH group of the hydroxyl group-containing compound, the coloring composition is used. It is advisable to set a temperature higher than the boiling point of the contained alcohols as the heating temperature at the time of post-baking. The heating time during post-baking can be appropriately set depending on the heating temperature, but is usually 5 to 120 minutes, preferably 30 to 100 minutes at a low temperature of, for example, 70 to 120 ° C. The film thickness of the colored cured film (that is, the pixel) formed on the substrate is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

A protective film is formed on the pixel pattern thus obtained, if necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to form a color filter. The spacer is usually formed by using a transparent photosensitive resin composition, but a spacer having a light-shielding property (black spacer) can also be used. In this case, a photosensitive coloring composition in which a black colorant is dispersed is used. The coloring composition of the present disclosure can also be suitably used for forming such a black spacer.

The coloring composition of the present disclosure can be suitably used for forming any colored cured film such as each color pixel used for a color filter, a black matrix, and a black spacer. The color filter thus formed has high brightness and color purity, and is particularly useful for a color liquid crystal display element, a solid-state image sensor, a color sensor, an organic EL display element, electronic paper, and the like.

[Display element]
The display element of the present disclosure includes the color filter of the present disclosure. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

The color liquid crystal display element provided with the color filter of the present disclosure may include a cold cathode fluorescent tube (CCFL: Cold Camera Fluorescent Lamp) and a backlight unit using a white LED as a light source. Examples of the white LED include a white LED that obtains white light by mixing colors by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by combining a blue LED, a red LED, and a green phosphor, and a blue LED. A white LED that obtains white light by mixing colors with a red light emitting phosphor and a green light emitting phosphor, a white LED that obtains white light by mixing a blue LED and a YAG-based phosphor, a blue LED, an orange light emitting phosphor, and a green light emitting fluorescence. Examples thereof include a white LED that obtains white light by mixing colors by combining bodies, and a white LED that obtains white light by mixing colors by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor.

The organic EL display element provided with the color filter of the present disclosure can have an appropriate structure, and examples thereof include the structure disclosed in Japanese Patent Application Laid-Open No. 11-307242. Further, as the electronic paper provided with the color filter of the present disclosure, for example, the structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169 can be mentioned.

[Light receiving element]
The light receiving element of the present disclosure includes a colored cured film formed by using the above-mentioned coloring composition. The light receiving element of the present disclosure may have an appropriate structure. For example, the above-mentioned colored cured film is used as a color filter constituting the solid-state image sensor, and is combined with a photodiode to form an image pickup device such as a solid-state image sensor. be able to. Further, by using the cured film of the present disclosure as an infrared light transmission filter and combining it with a photodiode, an infrared light detection pixel can be configured.

[Curable composition]
The curable composition of the present disclosure contains the above-mentioned (B) polymer and (C) polymerizable compound. In particular, the curable composition of the present disclosure has a partial structure in which at least one selected from the group consisting of (B) polymer and (C) polymerizable compound has a partial structure represented by the above formula (1). At least one selected from the group consisting of B) polymers and (C) polymerizable compounds has a hydroxyl group. The partial structure represented by the above formula (1) and the hydroxyl group may be present in the same molecule or may be present in different molecules.

The curable composition of the present disclosure is a composition used for forming a cured film. Examples of the cured film include color pixels used in display elements and light receiving elements, interlayer insulating films, flattening films, banks (partition walls) that define regions for forming light emitting layers, black matrices, spacers, protective films, and the like. Examples of the display element include a color liquid crystal display element, an organic EL element, electronic paper, and the like, and examples of the light receiving element include a CCD image sensor, a CMOS image sensor, and the like.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In addition, "part" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified. In this example, the weight average molecular weight (Mw) of the polymer was measured by GPC. The compounds used in this example and their abbreviations are shown below.

(Crosslinkable monomer)

(Other monomers)

(Dye monomer)
The dye monomer I is a compound having a structural formula in which the anion moiety of the raw material monomer of the dye polymer XIV described in paragraph 0434 of Japanese Patent No. 5377595, which has a known structure, is replaced with a bis (trifluoromethanesulfonyl) imide anion. Dye monomers II to XI are compounds represented by the following structural formulas.

(dye)

(Hydroxy group-containing dye)

(Photopolymerization initiator)

Ｃ−２Ａ：上記式（Ｃ−２）で表され、水酸基価が６０〜１００ｍｇＫＯＨ／ｇである化合物
Ｃ−２Ｂ：上記式（Ｃ−２）で表され、水酸基価が１００〜１４０ｍｇＫＯＨ／ｇである化合物 (Polymerizable compound)

C-2A: Compound represented by the above formula (C-2) and having a hydroxyl value of 60 to 100 mgKOH / g C-2B: Represented by the above formula (C-2) and having a hydroxyl value of 100 to 140 mgKOH / g A compound

1. 1. Synthesis of dye resin [Synthesis Example 1-1]
8.70 g of dye monomer I, 1.41 g of methacrylic acid (MA), -2-[[[[2-methyl-1-oxo-2-propenyl] oxy] ethyl malonic acid] in a reaction vessel equipped with a cooling tube. ] Amino] carbonyl] -1,3 diethyl ester (manufactured by Showa Denko, trade name "Karenzu MOI-DEM", hereinafter referred to as "compound (M-1)") 2.25 g, 2-hydroxyethyl methacrylate (HEMA) ) 1.97 g and 0.42 g of 2-ethylhexyl-3-mercaptopropionate (EHMP) were added and dissolved in 25.4 g of propylene glycol monomethyl ether acetate (PGMEA) and 59.2 g of n-butanol. The solution was heated to 75 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name "V-70", hereinafter simply referred to as "V-70") ) Was added, and stirring was continued for 3 hours. Then, 0.42 g of V-70 was further added, and stirring was continued for 3 hours. Then, after cooling the reaction solution to room temperature, 60 g of PGMEA was added to make a uniform solution, and this solution was added dropwise to 1.1 L of hexane. The resulting precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C. to obtain 15.30 g of a polymer (referred to as "polymer (A-1)"). The obtained polymer (A-1) was confirmed by GPC to have Mw of 19,000 and Mn of 9,800.

[Synthesis Example 1-2-1-10, 1-12-1-22 and Comparative Synthesis Example 1-1-1-4]
The same operations as in Synthesis Example 1-1 were carried out except that the types and amounts of the monomers used were changed as shown in Table 1 below, and the polymers (A-2) to (A-10) and (A-12) were carried out. )-(A-22) and polymers (AR-1)-(AR-4) were synthesized, respectively. In addition, in Table 1, "-" indicates that the corresponding component was not blended (the same applies to the following table).

[Synthesis Example 1-11]
In a reaction vessel equipped with a cooling tube, dye monomer I 8.70 g, MA 1.41 g, compound (M-1) 2.25 g, glycerol monomethacrylate (GLM) 1.97 g, thioglycolate monoethanolamine (TG-MEA) ) 0.42 g was added and dissolved in 25.4 g of PGMEA and 59.2 g of n-butanol. The solution was heated to 75 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] (manufactured by Wako Pure Chemical Industries, Ltd., water-soluble radical initiator, trade name "VA-086", 0.42 g (hereinafter, also simply referred to as “VA-086”) was added, and stirring was continued for 3 hours. Then, 0.42 g of VA-086 was further added, and stirring was continued for 3 hours. Then, after cooling the reaction solution to room temperature, 60 g of PGMEA was added to make a uniform solution, and this solution was added dropwise to 1.1 L of hexane. The resulting precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C. to obtain 15.30 g of a polymer (referred to as "polymer (A-11)"). The obtained polymer (A-11) was confirmed by GPC to have Mw of 19,300 and Mn of 10,000.

[Synthesis Example 1-23]
8.45 g of p- (vinylphenyl) trifluoromethanesulfonylimide acid triethylamine salt (referred to as "acidic monomer I"), 1.41 g of MA, and 2.25 g of compound (M-1) in a reaction vessel equipped with a cooling tube. , HEMA 1.97 g and pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) 0.42 g were added and dissolved in cyclohexanone (CHN) 25.40 g and n-butanol 59.20 g. The solution was heated to 75 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, 0.84 g of V-70 was added, and stirring was continued for another 4 hours. Then, after cooling the reaction solution to room temperature, 60 g of acetone was added to make a uniform solution, and this solution was added dropwise to 1.1 L of hexane. The resulting precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C. to obtain 15.01 g of an anionic group-containing polymer represented by the following structural formula (referred to as "polymer (A-23-1)"). .. The obtained polymer (A-23-1) was confirmed by GPC to have Mw of 11,100 and Mn of 6,900.

2.0 g of the polymer (A-23-1) synthesized above was dissolved in 40 mL of acetone. Next, as shown in the following scheme, with respect to the number of moles of the structural unit derived from the p- (vinylphenyl) trifluoromethanesulfonylimide acid triethylamine salt calculated from the copolymerization ratio of the polymer (A-23-1). The equivalent amount of C.I. I. Basic Red 12 (basic dye I) was added, and the mixture was stirred at room temperature for 1 hour. Then, 200 mL of ion-exchanged water was added to the residue obtained by concentrating the reaction solution under reduced pressure, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain 2.61 g of a polymer represented by the following structural formula (referred to as "polymer (A-23)").

[Synthesis Examples 1-24, 1-25]
Polymers (A-24) and (A-25) were synthesized in the same manner as in Synthesis Example 1-23, except that the type of basic dye used was changed as shown in Table 2 below.

[Synthesis Example 1-26]
8.45 g of methacryloylpropyltrimethylammonium chloride (basic monomer I), 1.41 g of MA, 2.25 g of compound (M-1), 1.97 g of HEMA, 0.42 g of PEMP and 25.0 g of CHN in a reaction vessel equipped with a cooling tube. It was dissolved in 60.0 g of n-butanol. The solution was heated to 75 ° C. with stirring under a nitrogen stream. While stirring at the same temperature, 0.80 g of V-70 was added, and stirring was continued for another 4 hours. Then, after cooling the reaction solution to room temperature, 60.0 g of acetone was added to make a uniform solution, and this solution was added dropwise to 1.10 L of hexane. The resulting precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C. to obtain 15.11 g of a cationic group-containing polymer represented by the following structural formula (referred to as "polymer (A-26-1)"). .. It was confirmed by GPC that the obtained polymer (A-26-1) had Mw of 10,500 and Mn of 7,000.

2.00 g of the polymer (A-26-1) synthesized above was dissolved in 40.0 mL of acetone. Next, as shown in the scheme below, the molar amount of C.I. I. Acid Blue 93 (acid dye I) was added, and the mixture was stirred at room temperature for 1 hour. Then, 200 mL of ion-exchanged water was added to the residue obtained by concentrating the reaction solution under reduced pressure, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain 2.62 g of a dye multimer (referred to as "polymer (A-26)") represented by the following structural formula. The obtained polymer (A-26) was confirmed by GPC to have Mw of 12,600 and Mn of 7,500.

[Synthesis Example 1-27]
By performing the same operation as in Synthesis Example 1-26 above, except that the cationic monomer is changed to dimethylaminoethyl methacrylate (this is referred to as "basic monomer II"), the cation represented by the following structural formula 15.02 g of a sex group-containing polymer (referred to as “polymer (A-27-1)”) was obtained. The obtained polymer (A-27-1) was confirmed by GPC to have Mw of 11,400 and Mn of 6,800. Subsequently, by using the polymer (A-27-1) and performing the same operation as in Synthesis Example 1-26, the polymer (A-27-1) and C.I. I. A dye multimer (referred to as "polymer (A-27)") with Acid Blue 93 (acid dye I) was obtained.

[Synthesis Example 1-28]
By performing the same operation as in Synthesis Example 1-26 above, except that the cationic monomer was changed to N, N-dimethylaminomethylstyrene (referred to as "basic monomer III"), the following structural formula was obtained. 15.07 g of the represented cationic group-containing polymer (referred to as "polymer (A-28-1)") was obtained. It was confirmed by GPC that the obtained polymer (A-28-1) had Mw of 11,300 and Mn of 7,100. Subsequently, by using the polymer (A-28-1) and performing the same operation as in Synthesis Example 1-26, the polymer (A-28-1) and C.I. I. A dye multimer (referred to as "polymer (A-28)") with Acid Blue 93 (acid dye I) was obtained.

[Synthesis Example 1-29]
By performing the same operation as in Synthesis Example 1-26 above, except that the cationic monomer is changed to N-vinylpyrrolidone (referred to as "basic monomer IV"), the cation represented by the following structural formula is performed. 15.03 g of a sex group-containing polymer (referred to as “polymer (A-29-1)”) was obtained. The obtained polymer (A-29-1) was confirmed by GPC to have Mw of 12,100 and Mn of 7,400. Subsequently, by using the polymer (A-29-1) and performing the same operation as in Synthesis Example 1-26, the polymer (A-29-1) and C.I. I. A dye multimer (referred to as "polymer (A-29)") with Acid Blue 93 (acid dye I) was obtained.

[Synthesis Example 1-30]
As an acid dye, C.I. I. By performing the same operation as in Synthesis Example 1-26 except that Acid Red 289 (acid dye II) was used, the polymer (A-26-1) and C.I. I. A dye multimer (referred to as "polymer (A-30)") with Acid Red 289 (acid dye II) was obtained.

In Table 2, the abbreviations of the compounds are as follows.
Acidic Monomer I: p- (Vinylphenyl) Trifluoromethanesulfonylimide Acid Triethylamine Salt Basic Monomer I: Methacryloylpropyltrimethylammonium Chloride Basic Monomer II: Dimethylaminoethyl Methacrylate Basic Monomer III: N, N-dimethylaminomethylstyrene Base Sex Monomer IV: N-vinylpyrrolidone

2. Synthesis of binder resin [Synthesis Example 2-1]
In a reaction vessel, 28.0 g of compound (M-1), 24.5 g of 2-hydroxyethyl methacrylate (HEMA), 7.0 g of N-cyclohexylmaleimide (CHMI), 3.5 g of styrene (ST), and methacrylic acid (MA). 7.0 g and 4.92 g of 2,2'-azobis (2,4-dimethylvaleronitrile) were weighed and dissolved in 40 g of propylene glycol monomethyl ether acetate and 90 g of n-butanol. The temperature of the reaction solution was raised to 75 ° C. while stirring under a nitrogen stream, and stirring was continued for 5 hours. After cooling the reaction solution to room temperature, 200 g of the polymer solution having a solid content concentration of 35% by mass was recovered. It was confirmed by GPC measurement that the obtained polymer (referred to as "polymer (B-1)") had Mw of 16,000 and Mn of 7,000.

[Synthesis Examples 2-2-2-7, 2-9-2-17 and Comparative Synthesis Examples 2-1-2-5]
The same operations as in Synthesis Example 2-1 were carried out except that the types and amounts of the monomers used were changed as shown in Table 3 below, and the polymers (B-2) to (B-7) and (B-9) were carried out. )-(B-17) and polymers (BR-1)-(BR-5) were synthesized, respectively.

[Synthesis Example 2-8]
In the reaction vessel, 28.0 g of compound (M-1), 24.5 g of glycerin monomethacrylate (GLM), 7.0 g of N-cyclohexylmaleimide (CHMI), 3.5 g of styrene (ST), and 7. of methacrylic acid (MA). 4.60 g of 0 g, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] (manufactured by Wako Pure Chemical Industries, Ltd., water-soluble radical initiator, trade name "VA-086") It was weighed and dissolved in 40 g of propylene glycol monomethyl ether acetate and 90 g of n-butanol. The temperature of the reaction solution was raised to 75 ° C. while stirring under a nitrogen stream, and stirring was continued for 5 hours. After cooling the reaction solution to room temperature, 200 g of the polymer solution having a solid content concentration of 35% by mass was recovered. It was confirmed by GPC measurement that the obtained polymer (referred to as "polymer (B-8)") had Mw of 15,200 and Mn of 6,800.

[Synthesis Example 2-18]
In the reaction vessel, add 32.0 g of glycidyl methacrylate (GMA), 10.9 g of styrene (ST), 27.1 g of butyl methacrylate (BMA), and 7.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile). It was weighed and dissolved in 130 g of propylene glycol monomethyl ether acetate. The temperature of the reaction solution was raised to 75 ° C. while stirring under a nitrogen stream, and stirring was continued for 3 hours. Then, the temperature of the reaction solution was raised to 100 ° C. and polymerized for another 1 hour to obtain 200 g of the polymer solution. Got After cooling the polymer solution to room temperature, the mixture was switched to an air stream, 16.5 g of acrylic acid (AA) and 2.2 g of tetrabutylammonium bromide (TBAB) were added thereto, and a heating reaction was carried out at 105 ° C. for 10 hours. .. Then, 22.6 g of tetrahydrophthalic anhydride and 33 g of propylene glycol monomethyl ether acetate were added, and the mixture was reacted at 105 ° C. for 3 hours. After cooling the reaction solution to room temperature, 270 g of the polymer solution having a solid content concentration of 40% by mass was recovered. The obtained polymer (referred to as "polymer (B-18)") had Mw of 11,700 and Mn of 6,700.

[Synthesis Example 2-19]
7. In the reaction vessel, 19.4 g of compound (M-1), 26.4 g of methacrylic acid (MA), 24.2 g of butyl methacrylate (BMA), and 2,2'-azobis (2,4-dimethylvaleronitrile). 0 g was weighed and dissolved in 100 g of propylene glycol monomethyl ether acetate and 30 g of n-butanol. The temperature of the reaction solution was raised to 75 ° C. while stirring under a nitrogen stream, and stirring was continued for 3 hours. was gotten. After cooling to room temperature, switch to an air stream, add 27.0 g of methyl methacrylate [(3,4-epoxycyclohexane) -1-yl] and 1.9 g of tetrabutylammonium bromide (TBAB), and add 105 ° C. The heating reaction was carried out for 10 hours. After cooling the reaction solution to room temperature, 240 g of a polymer solution having a solid content concentration of 40% by mass was recovered. The obtained polymer (referred to as "polymer (B-19)") had Mw of 11,900 and Mn of 6,600.

[Synthesis Example 2-20]
A flask equipped with a cooling tube and a stirrer was charged with 3 parts by mass of 2,2'-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate. In this flask, 12 parts by mass of N-cyclohexylmaleimide (CHMI), 10 parts by mass of styrene, 20 parts by mass of methacrylic acid (MA), 15 parts by mass of 2-hydroxyethyl methacrylate (HEMA), and 29 parts by mass of 2-ethylhexyl methacrylate (EHMA). , 14 parts by mass of benzyl methacrylate (BzMA), and 5 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd.) were charged and substituted with nitrogen. Then, the reaction solution was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 3 hours for polymerization. Then, the temperature of the reaction solution is raised to 100 ° C., and the mixture is further polymerized for 1 hour to obtain a binder resin solution containing 33.3% by mass of a binder resin (referred to as "polymer (BA-1)"). Obtained. The polymer (BA-1) had Mw of 9,700 and Mn of 5,700.

[Synthesis Example 2-21]
A polymer (B-20) having Mw of 16,000 and Mn of 7,000 was synthesized by performing the same operation as in Synthesis Example 2-1 above except that ethanol was used instead of n-butanol.

3. 3. Synthesis of hydroxyl group-containing dye [Synthesis Example 3-1]
Using dye A1, 1 equivalent of succinic anhydride was stirred in a pyridine solvent in the presence of a catalytic amount of dimethylaminopyridine at room temperature, and then the solvent was distilled off, washed with water, dehydrated and then the solvent was distilled off, and the terminal carboxylic acid I got a body. Then, 1 equivalent of tris (hydroxymethyl) aminomethane was stirred in a dichloromethane solvent with 1.2 equivalents of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride at room temperature, and then washed with water. After dehydration, the solvent was distilled off to obtain dye A3.

[Synthesis Example 3-2]
The target dye A4 was obtained in the same manner as in Synthesis Example 3-1 above, except that a dye in which the anion of the dye A2 was changed to an iodine anion was used instead of the dye A1.
[Synthesis Example 3-3]
The target dye C was obtained in the same manner as in Synthesis Example 3-1 above, except that the dye described in paragraph 0003 of JP-A-2004-506775 was used instead of the dye A1.
[Synthesis Example 3-4]
The target dye E was obtained in the same manner as in Synthesis Example 3-1 above, except that the compound [2] described in Chinese patent CN102786459 was used instead of the dye A1.
The dye A1 was synthesized by a known method, and the dye D was synthesized by a known method with reference to Japanese Patent No. 2812624.

4. Preparation of colorant dispersion [Preparation Example 4-1]
As a colorant, C.I. I. 13 parts by mass of Pigment Green 58, 11.8 parts by mass of BYK-LPN21116 (manufactured by Big Chemie, solid content concentration 40.0% by mass) as a dispersant, and a polymer (BA-1) as a binder resin. A mixed solution consisting of 13.0 parts by mass of the solution (solid content concentration 33.3% by mass) and 55.0 parts by mass of propylene glycol methyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether as a solvent was prepared by a bead mill for 12 hours. A colorant dispersion (MB-G-1) was prepared by mixing and dispersing.

[Preparation Example 4-2]
The type of colorant is C.I. I. Preparation was carried out in the same manner as in Preparation Example 4-1 above except that the pigment was changed to Pigment Green 59 to obtain a colorant dispersion liquid (MB-G-2).
[Preparation Example 4-3]
The type of colorant is C.I. I. Preparation was carried out in the same manner as in Preparation Example 4-1 above except that the pigment green was changed to Pigment Green 7, to obtain a colorant dispersion liquid (MB-G-3).

[Preparation Example 4-4]
The type of colorant is C.I. I. The same preparation as in Preparation Example 4-1 was carried out except that the pigment was changed to Pigment Yellow 138 to obtain a colorant dispersion liquid (MB-Y-1).
[Preparation Example 4-5]
The type of colorant is C.I. I. The same preparation as in Preparation Example 4-1 was carried out except that the pigment was changed to Pigment Yellow 139 to obtain a colorant dispersion liquid (MB-Y-2).
[Preparation Example 4-6]
The type of colorant is C.I. I. Preparation was carried out in the same manner as in Preparation Example 4-1 above except that the pigment was changed to Pigment Yellow 185 to obtain a colorant dispersion liquid (MB-Y-3).

[Preparation Example 4-7]
The type of colorant is C.I. I. Preparation was carried out in the same manner as in Preparation Example 4-1 above except that the pigment was changed to Pigment Red 177 to obtain a colorant dispersion liquid (MB-R-1).
[Preparation Example 4-8]
The type of colorant is C.I. I. The same preparation as in Preparation Example 4-1 was carried out except that the pigment blue was changed to 15: 6, and a colorant dispersion liquid (MB-B-1) was obtained.

[Preparation Example 4-9]
As a colorant, C.I. I. Pigment Blue 607 parts by mass, C.I. I. Pigment Violet 296 parts by mass was used, but the same preparation as in Preparation Example 4-1 was carried out to prepare a colorant dispersion liquid (MB-Bk-1).
[Preparation Example 4-10]
A colorant dispersion (MB-Bk-2) was obtained in the same manner as in Preparation Example 4-1 above, except that the type of colorant was changed to a lactam pigment (Irgaphor Black S0100 CF manufactured by BASF). It was.
[Preparation Example 4-11]
A colorant dispersion (MB-Bk-3) was obtained in the same manner as in Preparation Example 4-1 above, except that the type of colorant was changed to a perylene pigment (Lumogen Black FK4280 manufactured by BASF). ..
[Preparation Example 4-12]
Preparation was carried out in the same manner as in Preparation Example 4-1 above except that the type of colorant was changed to carbon black (TPX1227R manufactured by Cabot Corporation) to obtain a colorant dispersion liquid (MB-Bk-4).

5. Preparation and evaluation of coloring composition [1]
[Example 1-1]
(1) Preparation of coloring composition 5.7 parts by mass of the polymer (A-1) obtained in the above synthesis example 1-1, 0.7 parts by mass of Varifast Orange 32 (manufactured by Orient Chemical Industry Co., Ltd.), a colorant dispersion liquid ( MB-Y-2) 11.7 parts by mass, polymer (BA-1) as a binder resin in a polymer solution (solid content concentration 33.3% by mass) 5.6 parts by mass, (C) as a polymerizable compound , Dipentaerythritol penta / hexaacrylate 3.2 parts by mass, (D) 1.0 part by mass of oxime-based initiator (D-1) as photopolymerization initiator, Megafuck F-554 (DIC) as fluorine-based surfactant (Manufactured by Co., Ltd.) 0.03 parts by mass was mixed, and methoxybutyl acetate in an amount corresponding to 10% by mass of the total amount of solvent was added so that the solid content concentration of the final composition was 15.0% by mass. An amount of n-butanol corresponding to 5% by mass of the solvent amount is added, an amount of diacetone alcohol corresponding to 20% by mass% of the total solvent amount is added, and an amount corresponding to the remaining solvent amount is propylene glycol monomethyl ether acetate. Was added to prepare a coloring composition (G1-1).

(2) Evaluation The coloring composition (G1-1) was evaluated according to the following (i) and (ii).
(I) Evaluation of Solvent Resistance The coloring composition (G1-1) _{is applied to a soda glass substrate on which a SiO 2} film for preventing sodium ion elution is formed on the surface using a spin coater, and then at room temperature. Drying under reduced pressure was performed to form a coating film having a thickness of 2.5 μm.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of ^{600 J / m 2 via a photomask.} Then, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. ^{was discharged to the substrate at a developing pressure of 1 kgf / cm 2} (nozzle diameter 1 mm) to perform shower development for 60 seconds. Then, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 150 ° C. for 30 minutes to form a strip-shaped pattern on the substrate. For this strip-shaped pattern, a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used to determine the chromaticity coordinate values (x, y) and stimulus values (Y) in the CIE color system with a C light source and a two-degree field of view. It was measured.
Next, for the strip-shaped pattern after immersing in a mixed solvent of diethylene glycol methyl ethyl ether / ethylene glycol monobutyl ether = 50/50 (mass ratio) for 5 minutes, a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used to C. The chromaticity coordinate values (x, y) and stimulus values (Y) in the CIE color system were measured with a light source and a two-degree field of view. The color change before and after immersion, that is, ΔE * ab was calculated. The evaluation criteria are as follows.
(Evaluation criteria)
⊚: ΔE * ab value is 3.0 or less ◯: ΔE * ab value is greater than 3.0 and 7.0 or less Δ: ΔE * ab value is greater than 7.0 and 15.0 or less ×: ΔE * As a result of the evaluation that the value of ab was larger than 15.0, the solvent resistance was "⊚" in Example 1-1.

(Ii) Evaluation of storage stability The viscosity Vo immediately after preparing the coloring composition (G1-1) was measured using an E-type viscometer (manufactured by Tokyo Keiki). Next, the coloring composition (G1-1) was filled in a light-shielding glass container, allowed to stand at 25 ° C. for 14 days in a sealed state, and then the viscosity was measured again using an E-type viscometer (manufactured by Tokyo Keiki). .. The rate of increase ΔV [%] (= ((Va-Vo) / Vo) × 100) of the viscosity Va after storage for 14 days with respect to the viscosity Vo immediately after preparation was calculated, and the storage stability was evaluated by the rate of increase ΔV. The evaluation criteria are as follows.
(Evaluation criteria)
◯: Increase rate ΔV is less than 5% Δ: Increase rate ΔV is 5% or more and less than 10% ×: Increase rate ΔV is 10% or more As a result of evaluation, the storage stability was “◯” in Example 1-1. ..

[Examples 1-2 to 1-30 and Comparative Examples 1-1 to 1-4]
In Example 1-1, except that the types of the colorant and other components were changed by the C light source so that the chromaticity coordinate values (x, y) in the CIE color system show the values in Table 4 below. Coloring compositions (G1-2) to (G1-30) and (G1-1R) to (G1-4R) were prepared in the same manner as in Example 1-1, respectively. The obtained coloring compositions (G1-2) to (G1-30) and (G1-1R) to (G1-4R) were evaluated for solvent resistance and storage stability in the same manner as in Example 1-1. It was. The results are shown in Table 4 below.

In Table 4, the abbreviations of the compounds are as follows (the same applies to Tables 5 to 9 below).
Q-1: Varifast Orange 3209
C-1: Dipentaerythritol penta / hexaacrylate (manufactured by Toagosei Co., Ltd., trade name Aronix M-402)
D-1: Oxime-based initiator (compound represented by the above formula (D-1))
E1: Methoxybutyl acetate E2: Propylene glycol monomethyl ether acetate E3: n-butanol E4: Diacetone alcohol E5: Cyclohexanone F-1: Megafuck F-554 (manufactured by DIC Corporation)

6. Preparation and evaluation of coloring composition [2]
[Example 2-1]
(1) Preparation of coloring composition 28.5 parts by mass of the colorant dispersion solution (MB-G-1), 29.1 parts by mass of the colorant dispersion solution (MB-Y-1), and a polymer (B-) as a binder resin. 2.7 parts by mass of 3) in a polymer solution (solid content concentration 35% by mass), 4.2 parts by mass of dipentaerythritol penta / hexaacrylate as (C) polymerizable compound, and (D) as a photopolymerization initiator. 0.5 parts by mass of the oxime-based initiator (D-1) and 0.03 parts by mass of Megafuck F-554 (manufactured by DIC Co., Ltd.) as the fluorine-based surfactant are mixed, and the solid content concentration of the final composition is 15. Add methoxybutyl acetate in an amount corresponding to 10% by mass of the total solvent amount to 0.0% by mass, add n-butanol in an amount corresponding to 5% by mass of the total solvent amount, and further add the remaining solvent amount. A corresponding amount of propylene glycol monomethyl ether acetate was added to prepare a coloring composition (G2-1).
(2) Evaluation The colored composition (G2-1) was evaluated for solvent resistance and storage stability in the same manner as in Example 1-1. The results are shown in Table 5 below.

[Examples 2-2 to 2-27 and Comparative Examples 2-1 to 2-5]
In Example 2-1 except that the types of the colorant and other components were changed by the C light source so that the chromaticity coordinate values (x, y) in the CIE color system show the values in Table 5 below. Coloring compositions (G2-2) to (G2-27) and (G2-1R) to (G2-5R) were prepared in the same manner as in Example 2-1. The obtained colored composition was evaluated for solvent resistance and storage stability in the same manner as in Example 1-1. The results are shown in Table 5 below.

[Examples 2-28 to 2-31 and Comparative Examples 2-6 to 2-9]
The coloring composition (G2-4) and the coloring composition (G2-3R) were the same as in Example 1-1 except that the temperature in the clean oven at the time of post-baking was changed as shown in Table 6 below. The solvent resistance was evaluated. The results are shown in Table 6 below.
[Example 2-32]
In Example 2-1 except that the types of the colorant and other components were changed by the C light source so that the chromaticity coordinate values (x, y) in the CIE color system show the values in Table 6 below. A coloring composition (G2-4A) was prepared in the same manner as in Example 2-1. The solvent resistance of the obtained coloring composition (G2-4A) was evaluated in the same manner as in Example 1-1 except that the temperature in the clean oven at the time of post-baking was changed to 85 ° C. The results are shown in Table 6 below.

7. Preparation and evaluation of coloring composition [3]
[Example 3-1]
(1) Preparation of coloring composition 3.4 parts by mass of dye A1, 0.7 parts by mass of Varifast Orange 3209 (manufactured by Orient Chemical Industries), 11.7 parts by mass of colorant dispersion (MB-Y-2), 7.9 parts by mass of the polymer (B-13) as the binder resin in the polymer solution (solid content concentration 35% by mass), 3.2 parts by mass of dipentaerythritol penta / hexaacrylate as the (C) polymerizable compound, (D) 1.0 part by mass of an oxime-based initiator (D-1) as a photopolymerization initiator and 0.03 part by mass of Megafuck F-554 (manufactured by DIC Co., Ltd.) as a fluorine-based surfactant are mixed. To make the solid content concentration of the final composition 15.0% by mass, an amount of methoxybutyl acetate corresponding to 10% by mass of the total solvent amount was added, and an amount of n-butanol corresponding to 5% by mass of the total solvent amount was added. To prepare a coloring composition (G3-1) by adding an amount of diacetone alcohol corresponding to 20% by mass of the total amount of the solvent, and further adding an amount of propylene glycol monomethyl ether acetate corresponding to the remaining amount of the solvent. did.
(2) Evaluation The colored composition (G3-1) was evaluated for solvent resistance and storage stability in the same manner as in Example 1-1. The results are shown in Table 7 below.

[Examples 3-2-3-13 and Comparative Examples 3-1-3-5]
In Example 3-1 except that the types of the colorant and other components were changed by the C light source so that the chromaticity coordinate values (x, y) in the CIE color system were changed as shown in Table 7 below. Coloring compositions (G3-2) to (G3-13) and (G3-1R) to (G3-5R) were prepared in the same manner as in -1. The obtained coloring compositions (G3-2) to (G3-13) and (G3-1R) to (G3-5R) were evaluated for solvent resistance and storage stability in the same manner as in Example 1-1. went. The results are shown in Table 7 below.

8. Preparation and evaluation of coloring composition [4]
[Example 4-1]
(1) Preparation of coloring composition 30.9 parts by mass of dye IX, 24.2 parts by mass of colorant dispersion (MB-Y-1), and polymer solution (solid) of polymer (B-12) as a binder resin. 6.5 parts by mass (35% by mass), (C) 3.9 parts by mass of dipentaerythritol penta / hexaacrylate having a hydroxyl value of 100 to 140 mgKOH / g as a polymerizable compound, (D) photopolymerization initiator 0.8 parts by mass of the oxime-based initiator (D-1) and 0.03 parts by mass of Megafuck F-554 (manufactured by DIC Co., Ltd.) as the fluorine-based surfactant were mixed as the solid content concentration of the final composition. To 15.0% by mass, add methoxybutyl acetate in an amount corresponding to 10% by mass of the total solvent amount, add n-butanol corresponding to 5% by mass in the total solvent amount, and add 40% by mass of the total solvent amount. A coloring composition (G4-1) was prepared by adding cyclohexanone in an amount corresponding to% by mass and further adding propylene glycol monomethyl ether acetate in an amount corresponding to the amount of the remaining solvent.
(2) Evaluation The colored composition (G4-1) was evaluated for solvent resistance and storage stability in the same manner as in Example 1-1. The results are shown in Table 8 below.

[Examples 4-2 to 4-11]
In Example 4-1 except that the types of the colorant and other components were changed by the C light source so that the chromaticity coordinate values (x, y) in the CIE color system were changed as shown in Table 8 below. Coloring compositions (G4-2) to (G4-11) were prepared in the same manner as in -1. The obtained coloring compositions (G4-2) to (G4-11) were evaluated for solvent resistance and storage stability in the same manner as in Example 1-1. The results are shown in Table 8 below.

In Table 8, the abbreviations of the compounds are as follows.
C-2A: Dipentaerythritol penta / hexaacrylate (hydroxyl value: 60 to 100 mgKOH / g)
C-2B: Dipentaerythritol penta / hexaacrylate (hydroxyl value: 100 to 140 mgKOH / g)

9. Preparation and evaluation of coloring composition [5]
[Example 5-1]
(1) Preparation of coloring composition 16 parts by mass of the colorant dispersion solution (MB-Bk-1), 1.4 parts by mass of the colorant dispersion solution (MB-Bk-4), the polymer (B-1) as a binder resin. 25.2 parts by mass in a polymer solution (solid content concentration 35% by mass), (C) 3.9 parts by mass of dipentaerythritol penta / hexaacrylate as a polymerizable compound, and (D) an oxime-based photopolymerization initiator. 1.9 parts by mass of the initiator (D-1) and 0.2 parts by mass of Megafuck RS-72-K (manufactured by DIC Co., Ltd.) as a fluorine-based surfactant are mixed, and the solid content concentration of the final composition is 30. Add methoxybutyl acetate in an amount equivalent to 10% by mass of the total solvent amount to 0.0% by mass, add n-butanol corresponding to 5% by mass in the total solvent amount, and add the remaining solvent amount. A corresponding amount of propylene glycol monomethyl ether acetate was added to prepare a coloring composition (Bk5-1).

(2) Evaluation The solvent resistance of the coloring composition (Bk5-1) was evaluated according to the following (i). Moreover, the storage stability was evaluated in the same manner as in Example 1-1. The results are shown in Table 9 below.
(I) Evaluation of Solvent Resistance The coloring composition (Bk5-1) _{is applied to a soda glass substrate on which a SiO 2} film for preventing sodium ion elution is formed on the surface using a spin coater, and then at room temperature. Drying under reduced pressure was performed to form a coating film having a thickness of 10 μm.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of ^{600 J / m 2 via a photomask.} Then, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. ^{was discharged to the substrate at a developing pressure of 1 kgf / cm 2} (nozzle diameter 1 mm) to perform shower development for 60 seconds. Then, the substrate is washed with ultrapure water, air-dried, and then post-baked in a clean oven at 85 ° C. for 60 minutes to form a line having a width of 3 to 50 μm (in 1 μm increments) and a length of 1 mm. Formed a pattern.
Next, the formed line pattern was immersed in a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 50/50 (mass ratio) for 5 minutes, and the line pattern was observed with an optical microscope after immersion. .. The solvent resistance was evaluated by the line width that was the smallest among the residual patterns after immersion.
(Evaluation criteria)
⊚: Minimum line width is 5 μm or less ○: Minimum line width is 6 μm or more and 10 μm or less Δ: Minimum line width is 11 μm or more and 30 μm or less ×: Minimum line width is 31 μm or more As a result of evaluation, the solvent resistance of Example 5-1 is It was "○".

[Examples 5-2 to 5-6 and Comparative Examples 5-1 to 5-6]
In Example 5-1, the coloring composition was the same as in Example 5-1 except that the types and parts by mass of the colorant and other components, and the solvent and solid content concentrations were changed as shown in Table 9 below. (Bk5-2) to (Bk5-6) and (Bk5-1R) to (Bk5-6R) were prepared, respectively. The coating films (Bk5-2) to (Bk5-4), (Bk5-6), (Bk5-2R) to (Bk5-4R) and (Bk5-6R) obtained in the solvent resistance evaluation were used. The solvent resistance and storage stability were evaluated in the same manner as in Example 5-1 except that the film thickness was changed to 1 μm. The results are shown in Table 9 below.

In Table 9, the abbreviations of the compounds are as follows.
E6: Ethanol F-2: Megafuck RS-72-K (manufactured by DIC Corporation)

From the above results, the (A) colorant, (B) polymer and (C) polymerizable compound contain the partial structure represented by the above formula (1) and the hydroxyl group in the same molecule or in different molecules. It has been clarified that the curable composition has excellent storage stability with little change in viscosity with time, and can produce a cured film having excellent solvent resistance even when the post-baking temperature is lowered.

Claims (25)

The (A) colorant, the (B) polymer (excluding the (A) colorant), and the (C) polymerizable compound (however, the (A) colorant and the (B) polymer are used. A coloring composition containing (excluding) and
At least one selected from the group consisting of the (A) colorant, the (B) polymer and the (C) polymerizable compound has a partial structure represented by the following formula (1).
A coloring composition in which at least one selected from the group consisting of the (A) colorant, the (B) polymer and the (C) polymerizable compound has a hydroxyl group.

(In the formula (1), R ¹ and R ² are independently alkyl groups having 1 to 4 carbon atoms. L ¹ is a divalent organic group. X ¹ is electron attracting property. It is a divalent linking group having. N1 and n2 are independently integers of 0 to 2. “*” Indicates that it is a binder.) The first aspect of the present invention, wherein at least one of the (A) colorant and the (B) polymer contains a polymer containing a structural unit (a) having a partial structure represented by the above formula (1). Coloring composition. 2. The structural unit (a) is a structural unit derived from at least one selected from the group consisting of (meth) acrylic monomers, styrene-based monomers, and maleimide-based monomers. The coloring composition according to. The coloring composition according to claim 2 or 3, wherein the structural unit (a) is a structural unit represented by the following formula (1-2).

(In the formula (1-2), R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹ , R ² , L ¹ , X ¹ , n 1 and n 2 are the above formula (1), respectively. Is synonymous with.) The method according to any one of claims 2 to 4, wherein the colorant (A) contains a polymer (A1) containing the structural unit (a) and the structural unit (b) having a dye structure. Coloring composition. The coloring composition according to claim 5, wherein the structural unit (b) has a structure composed of a cationic chromophore and a counter anion or a structure composed of an anionic chromophore and a counter cation as the dye structure. The coloring composition according to claim 5 or 6, wherein the polymer (A1) further has a structural unit having a hydroxyl group. The coloring composition according to claim 7, wherein the structural unit having a hydroxyl group is a structural unit derived from a monomer having an ethylenically unsaturated group. The coloring composition according to any one of claims 2 to 8, which contains the alkali-soluble polymer having the structural unit (a) as the polymer (B). The coloring composition according to claim 9, wherein the alkali-soluble polymer further has a structural unit having a hydroxyl group. The coloring composition according to claim 10, wherein the structural unit having a hydroxyl group is a structural unit derived from a monomer having an ethylenically unsaturated group. The coloring composition according to any one of claims 9 to 11, which contains a coloring agent having a hydroxyl group as the (A) coloring agent. The coloring composition according to any one of claims 1 to 12, wherein the polymer (B) contains a polymer containing a structural unit having a hydroxyl group. The coloring composition according to claim 13, wherein the structural unit having a hydroxyl group is a structural unit derived from a monomer having an ethylenically unsaturated group. The coloring composition according to any one of claims 1 to 14, which contains a compound having a hydroxyl group and two or more polymerizable groups as the (C) polymerizable compound. The X ¹ has at least one electron-attracting group selected from the group consisting of a carbonyl group, an amide group, an imide group, an ester group, a sulfonyl group, a sulfinyl group, a thiocarbonyl group, and a carboxylicimideyl group. The coloring composition according to any one of claims 1 to 15, which is a group. The coloring composition according to any one of claims 1 to 16, wherein the content of alcohol is more than 0% by mass and 10% by mass or less with respect to the total amount of the solvent contained in the coloring composition. .. The colorant (A) contains a dye and contains a dye.
The coloring composition according to any one of claims 1 to 17, wherein the content ratio of the dye is 5% by mass or more with respect to the total amount of the colorant (A). A colored cured film formed by using the coloring composition according to any one of claims 1 to 18. A color filter formed by using the coloring composition according to any one of claims 1 to 18. A display element including the colored cured film according to claim 19. A light receiving element comprising the colored cured film according to claim 19. A step of applying the coloring composition according to any one of claims 1 to 18 on a substrate to form a coating film, and a step of forming a coating film.
The step of removing the solvent contained in the coating film and
A method for producing a colored cured film, including. The step of exposing the coating film and
The step of developing the exposed coating film and
23. The method for producing a colored cured film according to claim 23. A curable composition containing a polymer (B) (excluding a colorant) and a polymerizable compound (C) (excluding the colorant and the polymer (B)). ,
At least one selected from the group consisting of the polymer (B) and the polymerizable compound (C) has a partial structure represented by the following formula (1).
At least one selected from the group consisting of the polymer (B) and the polymerizable compound (C) is a curable composition having a hydroxyl group.

(In the formula (1), R ¹ and R ² are independently alkyl groups having 1 to 4 carbon atoms. L ¹ is a divalent organic group. X ¹ is electron attracting property. It is a divalent linking group having. N1 and n2 are independently integers of 0 to 2. “*” Indicates that it is a binder.)