CN116859670A

CN116859670A - Colored composition, colored cured film, method for producing same, color filter, display element, light-receiving element, and curable composition

Info

Publication number: CN116859670A
Application number: CN202311057156.9A
Authority: CN
Inventors: 福间聡司; 井川茂; 仓怜史
Original assignee: JSR Corp
Current assignee: Lishennoco Co ltd
Priority date: 2019-12-20
Filing date: 2020-12-18
Publication date: 2023-10-10
Also published as: JP2021102759A; TW202124595A; JP2023164445A; KR20230125149A; KR20210080243A; CN113009784A; TW202348741A

Abstract

The invention provides a coloring composition, a coloring hardening film and a manufacturing method thereof, a color filter, a display element, a light receiving element and a hardening composition. A coloring composition comprising: a colorant (A), a polymer (B), and a polymerizable compound (C), wherein at least one selected from the group consisting of the colorant (A), the polymer (B), and the polymerizable compound (C) has a partial structure represented by the formula (1) and is selected from the group consisting of the colorant (A), the polymer (B), and the polymer (C)At least one of the group consisting of the sexual compounds has a hydroxyl group. In the formula (1), R1 and R2 are each independently an alkyl group having 1 to 4 carbon atoms, L1 is a divalent organic group, and X1 is a divalent linking group having electron withdrawing property. n1 and n2 are each independently an integer of 0 to 2. "×" indicates a bond.

Description

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

The present invention is a divisional application of patent application of application number 202011500103.6, invention name "coloring composition, coloring cured film and its preparation method, color filter, display element, light receiving element and curing composition" filed on 12/18/2020.

Technical Field

The invention relates to a coloring composition, a coloring hardening film and a manufacturing method thereof, a color filter, a display element, a light receiving element and a hardening composition.

Background

As a method for producing a colored cured film of a color filter or the like, an inkjet method, an electrodeposition method, a printing method, a photolithography method, or the like is known. Among these, photolithography has been the mainstream in recent years. In the case of manufacturing a color filter by photolithography, for example, the following method can be adopted: a substrate is coated with a color curable composition to form a coating film, and then exposed to light through a photomask having a predetermined opening pattern, and developed to dissolve and remove the unexposed portion, thereby forming a pattern (for example, see patent document 1). After patterning, the following operations are typically performed: post-baking at 200-250 ℃ for about 30-60 minutes, thereby promoting the hardening of the coating film and improving the film hardness or solvent resistance of the film.

[ Prior Art literature ]

[ patent literature ]

[ patent document 1] Japanese patent laid-open No. 2-144502

Disclosure of Invention

[ problem to be solved by the invention ]

As a colorant contained in the colored cured film, it is considered that a dye can improve the hue or brightness of a display image when an image is displayed by the color purity of the dye itself or the vividness of the hue thereof, and that coarse particles derived from a pigment are reduced, thereby being effective for improving the contrast.

However, dyes generally have a problem of poor heat resistance. Therefore, it is difficult to heat a coating film formed using a coloring composition containing a dye at a post-baking temperature of 200 to 250 ℃. In addition, with the expansion of applications of display elements and the like, there has been studied a substrate as a substitute for a conventional glass substrate to a flexible plastic substrate. However, since the plastic substrate is generally low in heat resistance, there is a concern that elongation or shrinkage of the plastic substrate occurs when a coating film containing the coloring composition is formed on the plastic substrate and heated at a post-baking temperature of 200 to 250 ℃.

For this problem, it is considered to perform post baking at a temperature as low as possible. However, if post baking is performed at a low temperature, the film is not sufficiently cured, and there is a concern that problems such as a decrease in solvent resistance may occur. In addition, curable compositions having high sensitivity at low temperatures generally tend to have poor storage stability.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a coloring composition which is excellent in storage stability and low-temperature curability and which can give a cured film excellent in solvent resistance. Another object of the present invention is to provide a curable composition which is excellent in storage stability and low-temperature curability and which can give a cured film having excellent solvent resistance.

[ means of solving the problems ]

In order to solve the above problems, the present invention provides the following coloring composition, a coloring cured film, a color filter, a display element, a light receiving element, a method for producing the coloring cured film, and a curable composition.

[1] A coloring composition comprising: a colorant (A), a polymer (B), wherein the colorant (A) is excluded, and a polymerizable compound (C), wherein the colorant (A) and the polymer (B) are excluded, and wherein at least one selected from the group consisting of the colorant (A), the polymer (B) and the polymerizable compound (C) has a partial structure represented by the following formula (1), and at least one selected from the group consisting of the colorant (A), the polymer (B) and the polymerizable compound (C) has a hydroxyl group,

[ chemical 1]

(in the formula (1), R ¹ R is R ² Each independently represents an alkyl group having 1 to 4 carbon atoms; l (L) ¹ Is a divalent organic radical; x is X ¹ Is a divalent linking group having electron withdrawing property; n1 and n2 are each independently an integer of 0 to 2; "×" denotes a bond).

[2] A colored cured film formed using the colored composition according to [1 ].

[3] A color filter formed using the coloring composition according to the item [1 ].

[4] A display element comprising the colored hardened film according to [2 ].

[5] A light-receiving element comprising the colored hardened film according to [2 ].

[6] A method for producing a colored cured film, comprising: a step of forming a coating film by applying the coloring composition according to the above [1] on a substrate; and a step of removing the solvent from the coating film.

[7] A curable composition comprising: (B) A polymer (excluding a colorant), and (C) a polymerizable compound (excluding the colorant and the (B) polymer), wherein at least one selected from the group consisting of the (B) polymer and the (C) polymerizable compound in the curable composition has a partial structure represented by the following formula (1), and at least one selected from the group consisting of the (B) polymer and the (C) polymerizable compound has a hydroxyl group.

[ Effect of the invention ]

According to the coloring composition of the present invention, at least one selected from the group consisting of (a) a colorant, (B) a polymer and (C) a polymerizable compound has a partial structure represented by the above formula (1), and at least one selected from the group consisting of (a) a colorant, (B) a polymer and (C) a polymerizable compound has a hydroxyl group, whereby a colored cured film excellent in solvent resistance can be formed even in the case where post baking is performed at a low temperature. In addition, the coloring composition of the present invention has little change in viscosity with time and good storage stability. Therefore, the colored composition of the present invention is useful as a material for various color filters such as display elements and light-receiving elements.

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

Detailed Description

The following describes matters related to the embodiment in detail. In the present specification, the numerical range described in "to" is used to include the numerical values described before and after "to" as the lower limit value and the upper limit value. The term "constituent unit" is a unit mainly constituting a main chain structure, and means that at least two or more units are contained in the main chain structure.

[ coloring composition ]

The coloring composition is a composition for forming a coloring layer such as each color pixel, black matrix, black spacer, and the like used in the color filter. The coloring composition of the present disclosure contains: the colorant (A), the polymer (B) (except for the colorant (A), the same applies hereinafter), and the polymerizable compound (C) (except for the colorant (A) and the polymer (B), the same applies hereinafter). In particular, the coloring composition of the present disclosure contains a hydroxyl group and a partial structure represented by the following formula (1) in the same molecule or in different molecules of at least one selected from the group consisting of (a) a colorant, (B) a polymer, and (C) a polymerizable compound. That is, in the coloring composition of the present disclosure, at least one selected from the group consisting of (a) a colorant, (B) a polymer, and (C) a polymerizable compound has a partial structure represented by the following formula (1), and at least one selected from the group consisting of (a) a colorant, (B) a polymer, and (C) a 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.

[ chemical 2]

(in the formula (1), R ¹ R is R ² Each independently represents an alkyl group having 1 to 4 carbon atoms; l (L) ¹ Is a divalent organic radical; x is X ¹ Is a divalent linking group having electron withdrawing property; n1 and n2 are each independently an integer of 0 to 2; "x" means a bond

Here, in the coloring composition of the present disclosure, "the partial structure represented by formula (1) and the hydroxyl group are contained in the same molecule or in different molecules of at least one selected from the group consisting of (a) a colorant, (B) a polymer, and (C) a polymerizable compound" may be in a form in which the partial structure represented by formula (1) and the hydroxyl group are present in the same kind of component, or may be in a form in which the partial structure represented by formula (1) and the hydroxyl group are present in different kinds of component. For example, by having the partial structure represented by the formula (1) and a hydroxyl group in the colorant (a), a coloring composition containing the partial structure represented by the formula (1) and a hydroxyl group can be produced. Alternatively, a coloring composition containing a hydroxyl group and a partial structure represented by the formula (1) can be produced by (a) a colorant having a partial structure represented by the formula (1) and (B) a polymer having a hydroxyl group.

In the coloring composition of the present disclosure, the content ratio of the partial structure represented by the formula (1) is preferably 0.5 mass% or more, more preferably 2 mass% or more, and even more preferably 5 mass% or more, relative to the total amount of all solid components of the coloring composition, from the viewpoint of obtaining a colored cured film having high solvent resistance. In order to improve the workability, the content of the partial structure represented by the formula (1) is preferably 50 mass% or less, more preferably 35 mass% or less, and even more preferably 20 mass% or less, based on the total amount of all solid components of the coloring composition.

In the coloring composition of the present disclosure, the content ratio of the hydroxyl groups is preferably 0.3 mass% or more, more preferably 1 mass% or more, and still more preferably 3 mass% or more, relative to the total amount of all solid components of the coloring composition, from the viewpoint of obtaining a colored cured film having high solvent resistance. In order to improve the workability, the content of hydroxyl groups is preferably 35 mass% or less, more preferably 25 mass% or less, and even more preferably 15 mass% or less, based on the total amount of all solid components of the coloring composition.

In the present specification, the term "solid component" refers to a component other than the solvent (E) contained in the coloring composition. Accordingly, the term "all solid components" refers to components obtained by adding (a) a colorant, (B) a polymer, and (C) a polymerizable compound to (a) a colorant, (B) a polymer, (C) a polymerizable compound, and (E) a solvent together. For example, even if the photopolymerizable compound or the additive component (surfactant or the like) is in a liquid state, these components are contained in a solid component.

(Compound having a partial Structure represented by the formula (1))

In the formula (1), R ¹ R is R ² The alkyl group having 1 to 4 carbon atoms may be linear or branched. From the viewpoint of discharging the reaction product of the partial structure represented by the formula (1) and the hydroxyl group out of the film, R ¹ R is R ² Preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.

In terms of further improving the reaction efficiency with hydroxyl groups, n1 and n2 are preferably 0 or 1, more preferably 0.

X ¹ The divalent linking group having electron withdrawing property is not particularly limited as long as it is a divalent linking group. The term "divalent linking group having electron withdrawing property" as used herein refers to a group in which a hydrogen atom is removed from an arbitrary position of an electron withdrawing group to form a new bond. In this case, it is considered that electron withdrawing property is exhibited in a bond different from the new bond. The electron withdrawing group is a substituent having a Hammett (Hammett) substituent constant σp of 0.15 or more, and more preferably 0.2 or more. The Hammett substituent constants are described in accordance with journal of pharmaceutical chemistry (Journal of Medicinal Chemistry) (1973, vol.16, no.11, 1207-1216).

X is from the viewpoint of allowing the reaction with hydroxyl groups to proceed efficiently at low temperature ¹ Preferably selected from carbonyl (-CO-), amido (-CONR) ⁴ -* ¹ ) Imide group (-CONR) ⁴ CO-, ester (-CO-O-) ¹ ) Sulfonyl (-SO) ₂ At least one selected from the group consisting of (-), sulfinyl (-SO-), thiocarbonyl (-CS-), and carbodiimide (-C (=NH) -) (wherein R ⁴ Is hydrogen atom or monovalent hydrocarbon group with 1-10 carbon atoms, " ¹ "means" L in the formula (1) ¹ Bonded bonds). Among these, X ¹ More preferably an amide group, a carbonyl group or an ester group, and still more preferably an amide group or a carbonyl group.

As L ¹ Examples of the divalent organic group of (2) include: an alkanediyl group having 1 to 20 carbon atoms, an-O-group between carbon and carbon bonds of the alkanediyl group having 1 to 20 carbon atoms-CO-, -COO-, -NH-; -CONH-, etc.

The compound having a partial structure represented by the above formula (1) (hereinafter, also referred to as "specific compound") may be a low-molecular-weight compound having no repeating unit (hereinafter, also referred to as "low-molecular-weight compound") or may be a polymer. In the present specification, the term "low molecular compound" refers to 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 terms of obtaining a colored film excellent in solvent resistance, and specifically, a polymer containing a constituent unit (a) having a partial structure represented by the formula (1) is preferable. In the case where the specific compound is a polymer, the specific compound may be (a) a colorant or (B) a polymer. In addition, the coloring composition may contain (A) a colorant and (B) a polymer as specific compounds.

The constituent unit (a) is not particularly limited as long as it has a partial structure represented by the above formula (1). In terms of ease of introducing the partial structure represented by the formula (1) into the side chain of the polymer, the constituent unit (a) is preferably a constituent unit derived from a monomer having an ethylenically unsaturated group (hereinafter also referred to as "ethylenically unsaturated monomer"), more preferably a constituent unit derived from at least one selected from the group consisting of a (meth) acrylic monomer, a styrene monomer, and a maleimide monomer. Among these, the constituent unit (a) is preferably a constituent unit derived from a (meth) acrylic monomer, and particularly preferably a constituent unit represented by the following formula (1-2). In the present specification, the term "(meth) acrylic acid" is a concept including acrylic acid and methacrylic acid.

[ chemical 3]

(in the formula (1-2), R ³ Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; r is R ¹ 、R ² 、L ¹ 、X ¹ N1 and n2 are each as defined for formula (1)

In the formula (1-2), R ¹ 、R ² 、L ¹ 、X ¹ The description of specific examples and preferred examples of n1 and n2 can be applied to the description of the above formula (1).

R ³ Preferably a hydrogen atom or a methyl group. L in terms of obtaining a colored film excellent in solvent resistance ¹ Preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms.

(hydroxyl 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-containing compound may be a low molecular compound or a polymer. The hydroxyl group-containing compound may be the same compound as the specific compound or may be a different compound. In the case where the hydroxyl group-containing compound is the same compound as the specific compound, the compound has the partial structure represented by the formula (1) and the hydroxyl group in one molecule. In this case, the partial structure represented by the formula (1) may contain a hydroxyl group, but it is preferable that the partial structure represented by the formula (1) and the hydroxyl group are present at different positions (i.e., in different constituent units).

Here, in the composition of the present disclosure including the partial structure represented by the formula (1) and a hydroxyl group, a group "OR" in the formula (1) is generated ¹ "and base" OR ² At least one of the "groups is reacted with a hydroxyl group by transesterification, whereby a crosslinked structure is thought to be formed and hardened in the molecule or between the molecules. The transesterification is a reversible reaction, and the progress of the transesterification is suppressed in a state where the equilibrium is maintained. Thus, it is considered that the coloring composition is not cured in a state where the balance is maintained before heating, but the mixed state of (a) the colorant, (B) the polymer, and (C) the polymerizable compound is stably maintained.

On the other hand, when the composition is applied and heated to generate a balance shift, the radical "OR" in the formula (1) is caused ¹ "and base" OR ² "transesterification of at least one of the hydroxyl groups. Transesterification of HO-R ¹ "OR" H-OR ² "is discharged to the outside of the system to cause equilibrium shift, whereby it is considered that a crosslinked structure is formed between the specific compound and the hydroxyl group-containing compound, and the composition hardens. In addition, the transesterification reaction may be performed at a low temperature of, for example, 180 ℃ or less, and result in film hardening. It is presumed that by utilizing such transesterification reaction, the coloring composition according to the present disclosure can achieve both storage stability and low-temperature curability.

[ chemical 4]

(formulation morphology of coloring composition)

The coloring composition of the present disclosure is not particularly limited as long as at least one selected from the group consisting of (a) a colorant, (B) a polymer, and (C) a polymerizable compound has a partial structure represented by the above formula (1), and at least one selected from the group consisting of (a) a colorant, (B) a polymer, and (C) a polymerizable compound has a hydroxyl group. That is, the specific compound may be any one of (a) a colorant, (B) a polymer and (C) a polymerizable compound, or two or more of these. Similarly, the hydroxyl group-containing compound may be any one of (a) a colorant, (B) a polymer, and (C) a polymerizable compound, or two or more of these. At least one of the (a) colorant, the (B) polymer, and the (C) polymerizable compound may contain a compound having a partial structure represented by the formula (1) and a hydroxyl group.

Specific examples of the composition of the coloring composition include the following formulation modes of [1] to [8 ].

[1] The colorant (A) contains a polymer having a partial structure represented by the formula (1) and a hydroxyl group, the polymer (B) contains a polymer having a hydroxyl group and not having a partial structure represented by the formula (1), and the polymerizable compound (C) contains a compound having a hydroxyl group and not having a partial structure represented by the formula (1).

[2] The polymer (B) is a polymer having a partial structure represented by the formula (1) and a hydroxyl group, and the polymerizable compound (C) is a compound having a hydroxyl group and not having a partial structure represented by the formula (1). Wherein the colorant (A) does not have a partial structure represented by the formula (1) and a hydroxyl group.

[3] The colorant (A) is a compound having a hydroxyl group and not having a partial structure represented by the formula (1), the polymer (B) is a polymer having a partial structure represented by the formula (1) and not having a hydroxyl group, and the polymerizable compound (C) is a compound having a hydroxyl group and not having a partial structure represented by the formula (1).

[4] A polymer having a partial structure represented by the formula (1) and not having a hydroxyl group is used as the polymer (B), and a compound having a hydroxyl group and not having a partial structure represented by the formula (1) is used as the polymerizable compound (C). Wherein the colorant (A) does not have a partial structure represented by the formula (1) and a hydroxyl group.

[5] The colorant (A) contains a polymer having a partial structure represented by the formula (1) and a hydroxyl group, the polymer (B) contains a polymer having a partial structure represented by the formula (1) and a hydroxyl group, and the polymerizable compound (C) contains a compound having a hydroxyl group and not having a partial structure represented by the formula (1).

[6] The colorant (A) contains a polymer having a partial structure represented by the formula (1) and a hydroxyl group, and the polymer (B) contains a polymer having a hydroxyl group and not having a partial structure represented by the formula (1). Wherein the polymerizable compound (C) does not have a partial structure represented by the formula (1) and a hydroxyl group.

[7] The colorant (A) is a polymer having a hydroxyl group and not having a partial structure represented by the formula (1), the polymer (B) is a polymer having a partial structure represented by the formula (1) and not having a hydroxyl group, and the polymerizable compound (C) is a compound having a hydroxyl group and not having a partial structure represented by the formula (1).

[8] A polymer having a hydroxyl group as the colorant (A), a polymer having a hydroxyl group as the polymer (B), and a compound having a partial structure represented by the formula (1) as the polymerizable compound (C). Wherein at least one of the (A) colorant and the (B) polymer may further have a partial structure represented by the formula (1).

Hereinafter, each component contained in the coloring composition of the present disclosure and, if necessary, the component will be described in detail.

Colorant (A)

(A) The coloring agent may be appropriately selected in color or kind according to the purpose. As the colorant (A), pigments, dyes, quantum dots and natural pigments can be used. In terms of obtaining a pixel having high brightness and color purity, the colorant (a) is preferably at least one of a pigment and a dye, and particularly preferably contains a dye. The pigment and dye to be formulated in the coloring composition are preferably organic substances. As the colorant (a), there may be mentioned: specific compounds, hydroxyl group-containing compounds, and other colorants that do not have the partial structure represented by the formula (1) and hydroxyl groups.

(for specific Compounds)

In one aspect of the coloring composition of the present disclosure, the (a) colorant comprises a specific compound. The specific compound as the colorant (a) is not particularly limited as long as it has a partial structure represented by the above formula (1). In the case where the specific compound is a polymer, the specific compound as the colorant (a) is preferably a polymer containing a constituent unit (a) and a constituent unit (b) having a pigment structure (hereinafter, also referred to as "polymer (A1)") in terms of relatively easily obtaining a polymer having a partial structure represented by the above formula (1) using a usual polymerization method.

In the present specification, the term "dye structure" refers to a partial structure derived from a dye and is a chromophore. Pigment structures may also have a charge. In the case where the dye structure has a charge, the dye structure may be in any of the forms of an intramolecular salt and an intermolecular salt. The pigment structure is not particularly limited, and may be a structure derived from a known pigment. Specifically, examples thereof include: derived from a pigment selected from the group consisting of dipyrromethene pigment, diarylmethane pigment, triarylmethane pigment, xanthene pigment, acridine pigment, anthraquinone pigment, azo pigment, quinone imine pigment, polymethine pigment (oxonol pigment, merocyanine pigment, arylene pigment, styryl pigment, cyanine pigment, squaraine pigment, kertinium pigment, etc.), phthalocyanine pigment, subphthalocyanine pigment, and metal complex pigments of these. Among them, from the viewpoint of color characteristics, the structure derived from a dye selected from the group consisting of triarylmethane dye, xanthene dye, anthraquinone dye, azo dye, quinonimine dye, polymethine dye, subphthalocyanine dye and phthalocyanine dye is preferable, the structure derived from a dye selected from the group consisting of triarylmethane dye, xanthene dye, quinonimine dye and polymethine dye is more preferable, and the structure derived from a dye selected from the group consisting of triarylmethane dye, xanthene dye, quinonimine dye and cyanine dye is more preferable. Specific pigments that can form a pigment structure are described in "New dye toilet seat" (written by the institute of organic synthetic chemistry; pill, 1970), dye Index (Color Index) (The Society of Dyers and colourists) and pigment handbook (written by Daihan Ota; lecture, 1986).

The pigment structure may contain a cationic portion or an anionic portion, and examples thereof include salts of a cationic chromophore and a counter anion, and salts of an anionic chromophore and a counter cation. The counter ion may be an organic ion or an inorganic ion. Here, in the present specification, the term "cationic chromophore" means an atomic group having a positive charge. The atomic group contains a functional group having a positive charge and a functional group having a negative charge, and when these charges are added together to form a positive charge as a whole, the atomic group is included in the cationic chromophore. The term "anionic chromophore" refers to an atomic group having a negative charge. The atomic group contains a functional group having a positive charge and a functional group having a negative charge, and when these charges are added together to form a negative charge as a whole, the atomic group is included in the anionic chromophore. In addition, the pigment structure may be a chromophore that is electrically neutral. The term "charge neutral chromophore" refers to an atomic group that corresponds to neither a cationic chromophore nor an anionic chromophore, and that does not contain a functional group having a positive charge and a functional group having a negative charge, or that has the same total number of positive charges as the total number of negative charges even if the functional group having a positive charge and the functional group having a negative charge are contained, and that is charge neutral as a whole.

In terms of relatively easily obtaining a polymer having a partial structure represented by the above formula (1), the constituent unit (a) is preferably a constituent unit derived from a compound represented by the following formula (a 1). Specific examples of the compound represented by the following formula (a 1) include compounds represented by the following formulas (a 1-1) to (a 1-9), respectively.

[ chemical 5]

(in the formula (a 1), R ³ Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; r is R ¹ 、R ² 、L ¹ 、X ¹ N1 and n2 are each as defined for formula (1)

[ chemical 6]

(in the formulae (a 1-1) to (a 1-9), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

In the polymer (A1), the content of the constituent unit (a) is preferably 5 mass% or more, more preferably 10 mass% or more, and still more preferably 15 mass% or more, relative to all constituent units of the polymer (A1), in terms of sufficiently improving the solvent resistance of the cured film. In addition, the content of the constituent unit (a) is preferably 50 mass% or less, more preferably 45 mass% or less, and still more preferably 40 mass% or less, relative to all constituent units of the polymer (A1), in terms of maintaining workability and good colorability in preparing the coloring composition.

The constituent unit (b) is preferably a constituent unit derived from an ethylenically unsaturated monomer having a pigment structure. In terms of obtaining a pixel having high brightness and color purity, the dye structure of the constituent unit (b) is preferably a structure derived from a dye selected from the group consisting of an ionic dye and a nonionic dye. In this specification, an ionic dye having an acidic group as a chromophore is referred to as an "anionic dye". Anionic dyes are meant to include ionic dyes that form salts with acidic groups. Likewise, an ionic dye having a chromophore with a basic group is referred to as a "cationic dye". Cationic dyes are meant to include ionic dyes that form salts with basic groups. The "nonionic dye" is a dye other than a cationic dye and an anionic dye.

In terms of ease of introducing the dye structure into the side chain of the polymer, the constituent unit (b) is preferably a constituent unit derived from at least one selected from the group consisting of (meth) acrylic monomers, styrene monomers, and maleimide monomers among ethylenically unsaturated monomers. Among these, the constituent unit derived from a (meth) acrylic monomer is preferable, and the constituent unit represented by the following formula (b 1) is particularly preferable.

[ chemical 7]

(in the formula (b 1), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; L ² Is a single bond or a divalent organic group, Y ¹ Is a monovalent radical having a structure derived from an ionic dye or a nonionic dye

In the formula (b 1), L is ² Examples of the divalent organic group of (2) include: an alkanediyl group having 1 to 20 carbon atoms alkylene-diyl methylene having 1 to 20 carbon atoms through-O-; -CO-, -COO-, -NH-, -CONH-, -S-, -O-CO-Ph-CO-O- (Ph is phenylene) and the like.

In Y ¹ Examples of the structure derived from a nonionic dye include known structures derived from triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes, quinoline dyes, nitro dyes, quinone imine dyes, phthalocyanine dyes, squaraine dyes, and the like. Of these, the structure derived from the nonionic dye is preferably derived from triarylmethane dye, cyanine dye, xanthene dye, anthraquinone dye from the viewpoint of heat resistanceStructure of the material, dipyrromethene dye, squarylium dye or phthalocyanine dye.

In Y ¹ Specific examples of the structure derived from an ionic dye include a structure including a cationic chromophore and a counter anion, and a structure including an anionic chromophore and a counter cation. In the formula (b 1), in Y ¹ In the case where the dye structure is a structure including a cationic chromophore and a counter anion, Y ¹ Pigment structure and L ² The bond of (2) is formed by: either of the cationic chromophore and the counter anion is linked to L either directly or via a divalent linking group ² And (5) bonding. In addition, at Y ¹ In the case where the dye structure is a structure including an anionic chromophore and a counter cation, Y ¹ Pigment structure and L ² The bond of (2) is formed by: either of the anionic chromophore and the counter cation is linked to L either directly or via a divalent linking group ² And (5) bonding.

Examples of the cationic chromophore include: triarylmethane chromophores, cyanine chromophores, xanthene chromophores, polymethine chromophores, azo chromophores, diarylmethane chromophores, quinone imine chromophores, anthraquinone chromophores, phthalocyanine chromophores, squarylium chromophores, quinophthalone chromophores, and the like. Of these, the cationic chromophore is preferably a triarylmethane chromophore, a cyanine chromophore, a xanthene chromophore, a polymethine chromophore, or an azo chromophore, more preferably a triarylmethane chromophore or a cyanine chromophore. As the cationic chromophore, a cationic moiety of a dye classified as c.i. basic (c.i. basic) in the dye index (c.i.; published by the institute of dyers, uk) (The Society of Dyers and Colourists) can also be used.

The structure including the cationic chromophore and the counter anion is not particularly limited, and examples thereof include anions described in paragraph 0034 of Japanese patent application laid-open No. 2015-129263. Among these, a sulfonate anion, an imide anion, or a carboxylate anion is preferable, an imide anion is more preferable, and a sulfonyl imide anion is further preferable.

Examples of the anionic chromophore include: triarylmethane chromophores, polymethine chromophores, azo chromophores, diarylmethane chromophores, quinone imine chromophores, anthraquinone chromophores, phthalocyanine chromophores, xanthene chromophores, squarylium chromophores, quinophthalone chromophores, and the like. Of these, the anionic chromophore is preferably a triarylmethane chromophore, azo chromophore, phthalocyanine chromophore or xanthene chromophore, more preferably having-SO ₃ -and-CO ₂ -a triarylmethane chromophore, an azo chromophore, a phthalocyanine chromophore, or a xanthene chromophore of a substituent of at least one of them. As anionic chromophores, the anionic part of the dyes classified as c.i. acidic (c.i. acid) in the dye index can also be used.

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

In the polymer (A1), the content of the constituent unit (b) is preferably 30 mass% or more, more preferably 40 mass% or more, and still more preferably 50 mass% or more, with respect to all constituent units of the polymer (A1), from the viewpoint of obtaining a colorant exhibiting good colorability. In addition, from the viewpoint of ensuring the solubility of the polymer (A1) in the developer, the content ratio of the constituent unit (b) is preferably 99 mass% or less, more preferably 98 mass% or less, and still more preferably 95 mass% or less, with respect to all constituent units of the polymer (A1).

The polymer (A1) may have only the constituent unit (a) and the constituent unit (b), and it is preferable that the polymer further contains the constituent unit (c) having neither the partial structure represented by the formula (1) nor the pigment structure, in view of improving solvent resistance or heat resistance and dispersibility. The constituent unit (c) is preferably a constituent unit derived from an ethylenically unsaturated monomer, more preferably a constituent unit derived from at least one selected from the group consisting of a (meth) acrylic monomer, a styrene monomer, and a maleimide monomer.

Specific examples of the unit (hereinafter, also referred to as "other unit") forming the constituent unit (c) include, for example: alkyl (meth) acrylates, alkenyl (meth) acrylates, aryl (meth) acrylates, hydroxyalkyl (meth) acrylates, alkyl (meth) acrylates containing a primary amino group, alkyl (meth) acrylates containing a secondary amino group, alkyl (meth) acrylates containing a tertiary amino group, (meth) acrylates having an alicyclic hydrocarbon group, aromatic vinyl compounds, (meth) acrylates of polyhydric alcohols, N-substituted maleimides, vinyl ethers, ethylenically unsaturated monomers having an oxygen-containing saturated heterocycle, macromers having a mono (meth) acryloyl group at the end of the polymer molecular chain, and the like. The polymer (A1) may have only one kind of the constituent unit (c), or may have two or more kinds.

By using a monomer having a hydroxyl group (hereinafter, also referred to as "hydroxyl group-containing monomer") as another monomer, a polymer having a partial structure represented by the above formula (1) and a hydroxyl group and a pigment structure (hereinafter, also referred to as "polymer (A1-1)") can be obtained as the (a) colorant. By using such a polymer (A1-1) as the colorant (A), a crosslinked structure can be formed between the molecules of the polymer (A1-1), and elution of the colorant from the cured film can be sufficiently suppressed, which is preferable. Furthermore, the polymer (A1-1) is a specific compound or a hydroxyl group-containing compound. The hydroxyl group-containing monomer is preferably an ethylenically unsaturated monomer, more preferably at least one selected from the group consisting of a (meth) acrylic monomer, a styrene monomer, and a maleimide monomer, still more preferably at least one selected from the group consisting of a (meth) acrylic monomer and a styrene monomer, and particularly preferably a (meth) acrylic monomer.

Specific examples of the (meth) acrylic monomer having a hydroxyl group include: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate; caprolactone-modified monomers such as 2-hydroxyethyl (meth) acrylate; oxyalkylene modified monomers such as diethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate; monomers containing a primary hydroxyl group and a secondary hydroxyl group such as glycerol mono (meth) acrylate;

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, a monomer obtained by adding a glycidyl group of a side chain such as glycidyl (meth) acrylate to an acid monomer such as (meth) acrylic acid, a monomer obtained by adding an acid monomer such as (meth) acrylic acid to an alicyclic epoxy group of a side chain such as 3, 4-epoxycyclohexylmethyl (meth) acrylate, a monomer obtained by adding an acid monomer such as (meth) acrylic acid to a side chain such as (3-ethyl-3-oxetanyl) methoxymethyl (meth) acrylate, a monomer obtained by adding an acid monomer such as (meth) acrylic acid to a side chain such as (3-ethyl-3-oxethyl) methoxymethyl (meth) acrylate, a hydroxyl group-containing monomer such as a hydroxyl group;

And tertiary hydroxyl group-containing monomers such as 2, 2-dimethyl-2-hydroxyethyl (meth) acrylate. As the hydroxyl group-containing monomer, one species may be used alone, or two or more species may be used in combination.

A group "OR" corresponding to the partial structure represented by the formula (1) ¹ "and base" OR ² In terms of excellent reactivity, "the hydroxyl group-containing monomer used in the synthesis of the polymer (A1-1) is preferably a monomer having a primary alcoholic hydroxyl group and/or a secondary alcoholic hydroxyl group in the side chain of the polymer. 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 secondary hydroxyl group-containing monomer, and a secondary hydroxyl group-containing monomer. As the primary hydroxyl group-containing monomer, particularly preferred isHydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate. The primary hydroxyl group-and secondary hydroxyl group-containing monomer is particularly preferably glycerol mono (meth) acrylate. The secondary hydroxyl group-containing monomer is particularly preferably 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, a monomer obtained by adding a glycidyl group of a side chain such as glycidyl (meth) acrylate to an acid monomer such as (meth) acrylic acid, a monomer obtained by adding an acid monomer such as (meth) acrylic acid to an alicyclic epoxy group of a side chain such as 3, 4-epoxycyclohexylmethyl (meth) acrylate, a monomer obtained by adding an alicyclic epoxy group of a side chain such as 3, 4-epoxycyclohexylmethyl (meth) acrylate to an acid monomer such as (meth) acrylic acid, a monomer obtained by adding an acid monomer such as (meth) acrylic acid to a side chain such as (3-ethyl-3-oxetanyl) methoxymethyl (meth) acrylate, or a monomer obtained by adding an oxetanyl group of a side chain such as (3-ethyl-3-oxetanyl) methoxymethyl (meth) acrylate.

As a method for obtaining the polymer (A1-1), there can be mentioned the following methods [ 2a ] to [ 4a ] in addition to the method (method [ 1a ]) in which the hydroxyl group-containing monomer, the specific group-containing monomer, and the monomer having a pigment structure are used as raw material monomers and polymerized.

Method [ 2a ]: a method in which an epoxy group-containing monomer (or a carboxyl group-containing monomer), a specific group-containing monomer, and a monomer having a pigment structure are used in a raw material monomer and polymerized to obtain a polymer having an epoxy group in a side chain, and then the polymer is reacted with a carboxyl group-containing compound (or an epoxy group-containing compound) to introduce a hydroxyl group (more specifically, a secondary hydroxyl group) in the side chain.

Method [ 3a ]: a method of polymerizing a raw material monomer containing a monomer having a specific group and a monomer having a pigment structure using a polymerization initiator having a hydroxyl group (for example, 2' -azobis (2-methyl-N- (2-hydroxyethyl) propionamide) or the like).

Method [ 4a ]: a method of polymerizing a raw material monomer containing a monomer having a specific group and a monomer having a pigment structure, using a chain transfer agent having a hydroxyl group (for example, monoethanolamine thioglycolate, 2, 3-dihydroxy-1, 4-butanethiol, etc.).

Among these, according to the method [ 1a ] and the method [ 2a ], a polymer having a hydroxyl group in a side chain can be obtained. In addition, according to the method [ 3a ] and the method [ 4a ], a polymer having hydroxyl groups at the terminal of the main chain can be obtained. In the present specification, the term "having a hydroxyl group at the end of the main chain" means that a bond is formed to a constituent unit in the main chain structure that does not form a bond with an adjacent constituent unit.

In the method [ 2a ], the epoxy group-containing monomer is preferably a (meth) acrylic monomer, and examples thereof include: an oxetanyl group-containing (meth) acrylic monomer such as glycidyl (meth) acrylate; alicyclic epoxy group-containing (meth) acrylic monomers such as 3, 4-epoxycyclohexylmethyl (meth) acrylate; oxetanyl group-containing (meth) acrylic monomers such as (3-ethyl-3-oxetanyl) methoxymethyl (meth) acrylate. The carboxyl group-containing compound is preferably a compound having a carboxyl group and an ethylenic unsaturated bond, more preferably a (meth) acrylic compound, and particularly preferably (meth) acrylic acid. The polymer (A1-1) is preferably a polymer having hydroxyl groups at least in the side chains, in terms of easy adjustment of the amount of hydroxyl groups in the polymer and relatively easy obtainment of a hydroxyl group-containing polymer.

In the polymer (A1-1), the content of the constituent unit having a hydroxyl group is preferably 0.5 mass% or more, more preferably 1 mass% or more, and still more preferably 5 mass% or more, relative to all constituent units of the polymer (A1-1), from the viewpoint of obtaining a colored cured film having high solvent resistance. In addition, from the viewpoint of improving storage stability, the content of the constituent unit having a hydroxyl group is preferably 50 mass% or less, more preferably 45 mass% or less, and still more preferably 40 mass% or less, relative to all constituent units of the polymer (A1-1).

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

(for hydroxyl group-containing Compound)

In one aspect of the coloring composition of the present disclosure, the (a) colorant comprises a hydroxyl-containing compound. The hydroxyl group-containing compound used as the colorant (A) may be a low molecular compound or a polymer. In the case of using a low-molecular compound having a hydroxyl group as the colorant (a), the low-molecular compound is preferably a dye (hereinafter, also referred to as "hydroxyl group-containing dye (A2-1)") in terms of obtaining a colored cured film having high brightness and color purity. 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, may be either an anionic dye or a cationic dye.

The number of hydroxyl groups in the hydroxyl group-containing dye (A2-1) is preferably 1 to 10, more preferably 2 to 8, from the viewpoint of both solvent resistance and storage stability.

Examples of the hydroxyl group-containing dye (A2-1) include: a dye containing a hydroxyl group described in Japanese patent application laid-open No. 2013-173850, international publication No. 2014/192973, and the like. The above-described known dye can be produced by a known method using the known dye as a raw material. The hydroxyl group-containing dye (A2-1) may be used singly or in combination of two or more.

When a polymer having a hydroxyl group is used as the colorant (a), examples of the polymer include a polymer having a hydroxyl group and a pigment structure and not having a partial structure represented by the formula (1) (hereinafter, also referred to as "hydroxyl group-containing polymer (A2-2)") in addition to the polymer (A1-1). The hydroxyl group-containing polymer (A2-2) is not particularly limited as long as it has a hydroxyl group and a pigment structure, and the position of the hydroxyl group and the like. That is, the hydroxyl group-containing polymer (A2-2) may have a hydroxyl group in a side chain, a hydroxyl group in a main chain terminal, or a hydroxyl group in both a side chain and a main chain terminal. As a method for obtaining the hydroxyl group-containing polymer (A2-2), there can be mentioned the method [ 1a ] to [ 4a ] described in the polymer (A1-1), a method of polymerizing without using a monomer having a specific group. In the production of the hydroxyl group-containing polymer (A2-2), only one of these methods may be used, or two or more of these methods may be used in combination. In terms of easy adjustment of the amount of hydroxyl groups and relatively easy obtainment of a hydroxyl group-containing polymer, the polymer (A2-2) is preferably a polymer having hydroxyl groups at least in side chains.

In the polymer (A2-2), the content of the constituent unit having a hydroxyl group is preferably 0.5 mass% or more, more preferably 1 mass% or more, still more preferably 3 mass% or more, and still more preferably 5 mass% or more, relative to all constituent units of the polymer (A2-2), from the viewpoint of obtaining a colored cured film having high solvent resistance. In addition, from the viewpoint of obtaining good colorability, the content of the constituent unit having a hydroxyl group is preferably 70 mass% or less, more preferably 60 mass% or less, and still more preferably 50 mass% or less, with respect to all the constituent units of the polymer (A2-2).

In the case where the colorant (a) is a polymer, the weight average molecular weight (Mw) of the polymer as measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) is preferably 1,000 ～ 100,000.Mw is preferably 3,000 or more. Further, mw is preferably 50,000 or less. If Mw is 1,000 or more, the pattern shape is good, and if Mw is 100,000 or less, the resolution time is not excessively long, which is preferable from the viewpoint of ensuring the workability. In the case where the colorant (a) is a polymer, the ratio (Mw/Mn) of Mw to number average molecular weight (Mn) of the polymer is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

(other colorants)

The coloring composition may contain only at least one of a specific compound and a hydroxyl group-containing compound as the (a) colorant, but a colorant (hereinafter, also referred to as "other colorant") that does not have any of the partial structure and hydroxyl group represented by the above formula (1) may be used as the (a) colorant. In addition, when at least one component selected from the group consisting of (B) a polymer and (C) a polymerizable compound contains a hydroxyl group and a partial structure represented by the formula (1), the coloring composition may contain only other coloring agents as the coloring agent (a).

The other coloring agent is not particularly limited, and may be appropriately selected in color or kind according to the application. As other colorants, pigments, dyes, quantum dots and natural pigments may be used. In the case where the coloring composition of the present disclosure is used to form each color pixel constituting a color filter, the other coloring agent is preferably at least one selected from the group consisting of pigments and dyes, more preferably at least one selected from the group consisting of organic pigments and organic dyes, in terms of obtaining a pixel having high brightness and color purity.

The organic pigment may be a compound classified as pigment (pigment) in the dye index (c.i.; published by the institute of dyers, uk) (The Society of Dyers and Colourists), that is, a compound to which the name of the dye index (c.i.) described below is attached, and the following organic pigment may be preferably used.

Red pigments such as c.i. Pigment Red 166, c.i. Pigment Red 177, c.i. Pigment Red 224, c.i. Pigment Red 242, c.i. Pigment Red 254, c.i. Pigment Red 264, c.i. Pigment Red 279;

green pigments such as c.i. Pigment Green (Pigment Green) 7, c.i. Pigment Green 36, c.i. Pigment Green 58, c.i. Pigment Green 59, and the like;

c.i. Pigment Blue (Pigment Blue) 15: 6. blue pigments such as c.i. pigment blue 16, c.i. pigment blue 79, c.i. pigment blue 80, c.i. pigment blue 60, etc.;

yellow pigments such as c.i. Pigment Yellow (Pigment Yellow) 83, c.i. Pigment Yellow 129, c.i. Pigment Yellow 138, c.i. Pigment Yellow 139, c.i. Pigment Yellow 150, c.i. Pigment Yellow 179, c.i. Pigment Yellow 180, c.i. Pigment Yellow 185, c.i. Pigment Yellow 211, c.i. Pigment Yellow 215, and c.i. Pigment Yellow 231;

orange Pigment such as Pigment Orange (Pigment Orange) 38; violet pigments such as c.i. Pigment Violet (Pigment Violet) 19, c.i. Pigment Violet 23, c.i. Pigment Violet 29, etc.; black pigments such as lactam-based black pigments and perylene-based black pigments.

In addition, as the organic pigment, in addition to the above pigment, a brominated diketopyrrolopyrrole pigment represented by formula (Ic) in japanese patent application laid-open No. 2011-523433 can be used.

Examples of the inorganic pigment include carbon black and titanium black. Examples of the inorganic pigment include lake pigments described in japanese patent application laid-open No. 2001-081348, japanese patent application laid-open No. 2010-026334, japanese patent application laid-open No. 2010-237384, japanese patent application laid-open No. 2010-237569, japanese patent application laid-open No. 2011-006602, japanese patent application laid-open No. 2011-145346, and the like.

When a pigment is used, the pigment may be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination of these methods. The pigment may be used by modifying the particle surface of the pigment with a resin as necessary. In addition, when an organic pigment is used, primary particles can be finely divided by a so-called salt mill (salt mill). As a method of salt milling, for example, a method described in Japanese patent application laid-open No. 08-179111 can be used.

The Dye is not particularly limited, and for example, a known Dye may be used in addition to a compound classified into dyes (Dye) in the Dye index. Examples of such dyes include known dyes described above. Among these, triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, and phthalocyanine dyes are preferable from the viewpoint of heat resistance.

The dye may comprise a cationic moiety and an anionic moiety. Examples of such dyes include: a salt of a cationic chromophore with a counter anion, or a salt of an anionic chromophore with a counter cation. The description applies to examples of cationic chromophores, counter anions, anionic chromophores and counter cations.

The coloring composition of the present disclosure may also be formulated with (a) a colorant and a dispersant, if desired. In addition, the coloring composition may contain a dispersant and a dispersing aid. As the dispersant and the dispersing aid, known ones can be used. Specifically, examples of the dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkylphenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, polyester dispersants, and acrylic dispersants; examples of the dispersion aid include pigment derivatives.

Specific examples of the dispersant include, for example: a cable or wire (Solsperse) 11200, cable or wire (Solsperse) 13240, cable or wire (Solsperse) 13650, cable or wire (Solsperse) 13940, cable or wire (Solsperse) 16000, cable or wire (Solsperse) 17000, cable or wire (Solsperse) 18000, cable or wire (Solsperse) 20000, cable or wire (Solsperse) 24000SG, cable or wire (Solsperse) 24000GR, cable or wire (Solsperse) 28000, cable or wire (Solsperse) 31845, cable or wire (Solsperse) 32000, cable or wire (Solsperse) 32500, cable or wire (Solsperse) 32550, cable or wire (Solsperse) 32600, cable or wire (Solsperse) 33000, cable or wire (Solsperse) 34750, cable or wire (Solsperse) 3500, cable or wire (Solsperse) 300, cable or wire (Solsperse) 300, lu Borun (manufactured by Lubrizol) company), diospasbik (DISPRBYK) -108, diospasbik (DISPRBYK) -109, diospasbik (DISPRBYK) -112, diospasbik (DISPRBYK) -116, diospasbik (DISPYBYK) -130, diospasbik (DISPYBK) -161, diospasbik (DISPYBYK) -162, diospasbik (DISPYBYK) -163, diospasbik (DISPYBYK) -164, diospasbik (DISPYBYK) -13, diospasbik (DISPYBYK), diospasbik (DISPYK) -166, diospasbik (DISPYBYK) -167, diospasbik (DISPYBYK) -168, diospasbik (DISPYBYK) -182, diospasbik (DISPYBYK) -183, diospasbik (DISPYBYK) -184, diospasbik (DISPYBYK) -185, diospasbik (DISPYBYK) -2000, diospasbik (DISPYBYK) -2008, diospasbik (DISPYBYK) -2009, diospasbik (DISPYBYK) -2022, diospasbik (DISPYBYK) -2050, diospasbik (DISPYBYBYK) -2150, diospasbik (DISPYBYK) -2155, diospasbik (DISPBYK) -2163, diospasbik (PB) 2164, diospasbik (DISPBYK) -77 (DISPYK) -2000, manufactured by chemical company (BYBYK) Ji Sipa, and the like, and manufactured by Chebyvarious technologies such as Chebyk-80, UK, utility, UK, god, utility, and the like.

Examples of the acidic dispersant include: soxhlet (Solsperse) 3000, soxhlet (Solsperse) 21000, soxhlet (Solsperse) 26000, soxhlet (Solsperse) 36600, soxhlet (Solsperse) 41000, soxhlet (Solsperse) 41090, soxhlet (Solsperse) 43000, soxhlet (Solsperse) 44000, soxhlet (Solsperse) 46000, soxhlet (Solsperse) 47000, soxhlet (Solsperse) 55000 (above, lu Borun (Lubrizol) corporation), diersban (dierbyk) -102, dierpban (dierbyk) -111, diespban (dierbyk) -170, dierpban (dierbyk) -171, dierpban (dierbyk) -174, dierpban (dierbk) -6, dierbk) -104, BYK (BYK) -104, BYK) -220, BYK (BYK) -220, and the like. The dispersant may be used singly or in combination of two or more.

(A) The content ratio of the colorant may be appropriately selected depending on the application and the like. The content ratio of the colorant (a) is preferably 5 to 70% by mass based on the total amount of all solid components of the coloring composition, from the viewpoint of forming a pixel having high brightness and excellent color purity, or from the viewpoint of forming a black matrix having excellent light shielding property. (A) The content ratio of the colorant is more preferably 8 mass% or more, still more preferably 10 mass% or more, and particularly preferably 12 mass% or more, relative to the total amount of all solid components of the coloring composition. The content of the colorant (a) is more preferably 60 mass% or less, still more preferably 55 mass% or less, and particularly preferably 45 mass% or less, based on the total amount of all solid components of the coloring composition.

(A) The content of the dye in the colorant is preferably 5 mass% or more with respect to the total amount of the colorant (a). In general, since the heat resistance of a dye is poor, when a cured film is formed using a coloring composition containing a dye, it is difficult to heat a coating film at a post-baking temperature of 200 ℃ or higher. In contrast, 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 ℃, preferably 180 ℃ or less. Therefore, the coloring composition of the present disclosure can increase the content ratio of the dye, and can be suitably used for the production of various color filters. The content ratio of the dye is more preferably 10 mass% or more, still more preferably 20 mass% or more, and particularly preferably 30 mass% or more, relative to the total amount of the colorant (a) in terms of obtaining a colored cured film having high brightness and color purity.

(B) Polymer

(B) The polymer is contained in the coloring composition for the purpose of dispersing, dyeing or impregnating the colorant of (a), or as a binder resin. In the case of obtaining the coloring composition for forming an alkali-developable cured film, the polymer (B) is preferably an alkali-soluble polymer. The polymer (B) is different from the polymer such as the dye resin as the colorant (a) in that it does not have a pigment structure.

In the case where the polymer (B) is an alkali-soluble polymer, the polymer (B) is not particularly limited as long as it is soluble in an alkaline solution, and is preferably a polymer having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Of these, (B) polymers are preferably polymers having carboxyl groups (hereinafter, also referred to as "carboxyl group-containing polymers"). Examples of the carboxyl group-containing polymer include: a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, also referred to as "unsaturated monomer (b 1)") and an ethylenically unsaturated monomer copolymerizable with the unsaturated monomer (b 1) (hereinafter, also referred to as "unsaturated monomer (b 2)").

Examples of the unsaturated monomer (b 1) include: (meth) acrylic acid, maleic anhydride, succinic acid mono [ 2- (meth) acryloyloxyethyl ] ester, ω -carboxypolycaprolactone mono (meth) acrylate, p-vinylbenzoic acid, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, and the like. The carboxyl group-containing polymer may have only one kind of constituent unit derived from the unsaturated monomer (b 1), or may have two or more kinds in combination.

In the copolymer, the content of the constituent unit derived from the unsaturated monomer (B1) is preferably 5 mass% or more, more preferably 8 mass% or more, relative to all constituent units of the polymer (B), in terms of obtaining a colored cured film excellent in alkali developability. In addition, in terms of improving the solubility with a solvent, the content of the constituent unit derived from the unsaturated monomer (b 1) is preferably 30 mass% or less, more preferably 20 mass% or less, relative to all constituent units of the copolymer.

The unsaturated monomer (b 2) may be appropriately selected depending on the application and the like, and is not particularly limited. In the synthesis of the polymer (B), a specific compound can be obtained as the polymer (B) by using an ethylenically unsaturated monomer having a partial structure represented by the above formula (1) (hereinafter, also referred to as "specific group-containing monomer") as the unsaturated monomer (B2). In addition, by using an ethylenically unsaturated monomer having a hydroxyl group as the unsaturated monomer (B2), a compound containing a hydroxyl group can be obtained as the (B) polymer.

(for specific Compounds)

In one aspect of the coloring composition of the present disclosure, the (B) polymer comprises a specific compound. In terms of easy synthesis of a polymer having a partial structure represented by the above formula (1) in a side chain, the specific compound as the polymer (B) is preferably a polymer having a constituent unit (a) (hereinafter, also referred to as "polymer (B1)"). The description of the colorant (A) can be applied to examples and preferred examples of the specific group-containing monomers used for the constituent unit (a).

In the polymer (B1), the content of the constituent unit (a) is preferably 2 mass% or more, more preferably 5 mass% or more, and still more preferably 10 mass% or more, relative to all constituent units of the polymer (B1), in terms of sufficiently improving the solvent resistance of the cured film. In order to maintain the storage stability of the coloring composition, the content of the constituent unit (a) is preferably 80 mass% or less, more preferably 70 mass% or less, and still more preferably 60 mass% or less, relative to all constituent units of the polymer (B1).

In the synthesis of the polymer (B1), a polymer having a partial structure represented by the above formula (1) and hydroxyl groups (hereinafter, also referred to as "polymer (B1-1)") can be obtained as the (B) polymer by using a hydroxyl group-containing monomer as the unsaturated monomer (B2). The colored composition containing the polymer (B1-1) is preferable in that a crosslinked structure is formed between the polymers (B1-1) to obtain a cured film having more excellent solvent resistance. Furthermore, the polymer (B1-1) is a specific compound or a hydroxyl group-containing compound. The description of the colorant (A) can be applied to examples and preferred examples of hydroxyl group-containing monomers used for the synthesis of the polymer (B1).

As a method for obtaining the polymer (B1-1), in addition to a method (method [ 1B ]) in which a hydroxyl group-containing monomer and a specific group-containing monomer are used in a raw material monomer and polymerized, the following methods [ 2B ] to [ 4B ] are exemplified.

Method [ 2b ]: and a method in which an epoxy group-containing monomer (or a carboxyl group-containing monomer) and a specific group-containing monomer are used in a raw material monomer and polymerized to obtain a polymer having an epoxy group in a side chain, and then the polymer is reacted with a carboxyl group-containing compound (or an epoxy group-containing compound) to introduce a hydroxyl group (more specifically, a secondary hydroxyl group) in the side chain.

Method [ 3b ]: a method of polymerizing a raw material monomer containing a specific group, using a polymerization initiator having a hydroxyl group (for example, 2' -azobis (2-methyl-N- (2-hydroxyethyl) propionamide) or the like).

Method [ 4b ]: a method of polymerizing a raw material monomer containing a monomer having a specific group, using a chain transfer agent having a hydroxyl group (for example, monoethanolamine thioglycolate, 2, 3-dihydroxy-1, 4-butanedithiol, etc.).

Furthermore, as specific examples of the epoxy group-containing monomer and the carboxyl group-containing compound used in the method [ 2b ], the description of the method [ 2a ] can be applied. In terms of easy adjustment of the amount of hydroxyl groups in the polymer and relatively easy obtainment of a hydroxyl group-containing polymer, the polymer (B1-1) is preferably a polymer having hydroxyl groups at least in side chains.

The unsaturated monomer (B2) used in synthesizing the polymer (B1) may be, for example, a monomer other than the monomer described above: n-substituted maleimides such as N-alkyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, and N-benzyl 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 (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclic (meth) acrylate [5.2.1.0 ^2,6 ](meth) acrylic esters such as decan-8-yl ester, dicyclopentenyl (meth) acrylate, glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3- [ (meth) acryloyloxymethyl ] oxetane, 3- [ (meth) acryloyloxymethyl ] -3-ethyloxetane;

cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ]Vinyl such as decan-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, and 3- (vinyloxymethyl) -3-ethyloxetaneAn ether;

and a macromer having a mono (meth) acryloyl group at a terminal of a polymer molecular chain, such as polystyrene, poly (meth) acrylic acid methyl ester, poly (meth) acrylic acid n-butyl ester, and polysiloxane. (B) The polymer may have only one constituent unit derived from the unsaturated monomer (b 2), or may have two or more kinds in combination.

(for hydroxyl group-containing Compound)

In one form of the coloring composition of the present disclosure, (B) the polymer comprises a hydroxyl-containing compound. When a polymer having a hydroxyl group is used as the polymer (B), examples of the polymer include a polymer having a hydroxyl group and not having a partial structure represented by the formula (1) (hereinafter, also referred to as "hydroxyl group-containing polymer (B2)") in addition to the polymer (B1-1). The hydroxyl group-containing polymer (B2) may have a hydroxyl group in a side chain, a hydroxyl group in a main chain terminal, or both of the side chain and the main chain terminal. Among these, the hydroxyl group-containing polymer (B2) is preferably a polymer having a hydroxyl group at least in a side chain, from the viewpoint of easy adjustment of the amount of the hydroxyl group and relatively easy obtainment of the hydroxyl group-containing polymer. As a method for obtaining the hydroxyl group-containing polymer (B2), there can be mentioned a method in which polymerization is carried out without using a monomer containing a specific group among the methods [ 1B ] to [ 4B ] described in the polymer (B1-1). The description of the colorant (A) can be applied to examples and preferred examples of hydroxyl group-containing monomers used for the synthesis of the polymer (B2). In the production of the hydroxyl group-containing polymer (B2), only one of the methods [ 1B ] to [ 4B ] may be used, or two or more of them may be used in combination.

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

(other polymers)

The coloring composition may contain only at least one of a specific compound and a hydroxyl group-containing compound as the polymer (B), or may use a polymer (hereinafter, also referred to as "other polymer") that does not have any of the partial structure and hydroxyl group represented by the above formula (1) as the polymer (B). In addition, in the case where a specific compound and a hydroxyl group-containing compound are contained as at least one selected from the group consisting of (a) a colorant and (C) a polymerizable compound, the coloring composition may contain only other polymer as the (B) polymer.

The other polymer is not particularly limited and may be appropriately selected according to the application. Specific examples of the other polymers include: copolymers disclosed in JP-A7-140654, JP-A8-259876, JP-A10-31308, JP-A10-300922, JP-A11-174224, JP-A11-258415, JP-A2000-56118, JP-A2004-101728, etc. Further, as the polymer (B), for example, a carboxyl group-containing polymer having a polymerizable unsaturated bond (for example, a carbon-carbon double bond in a (meth) acryloyl group) in a side chain may be used as disclosed in JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, JP-A-2008-181095, and the like.

(B) The polymer can be produced by a known method such as radical polymerization, anionic polymerization, cationic polymerization, living radical polymerization, living anionic polymerization, or living cationic polymerization. Further, for example, the structure, mw and Mw/Mn can be controlled by the methods disclosed in Japanese patent application laid-open No. 2003-222717, japanese patent application laid-open No. 2006-259680, international publication No. 07/029871, and the like. Further, as the polymer (B), one kind may be used alone or two or more kinds may be mixed and used.

For the polymer (B), the polystyrene-equivalent weight average molecular weight (Mw) measured by Gel Permeation Chromatography (GPC) using tetrahydrofuran as the eluting solvent is preferably 1,000 ～ 100,000.Mw is preferably 3,000 or more. Further, mw is preferably 50,000 or less. If Mw is 1,000 or more, the pattern shape is preferable in terms of ensuring the workability, and if Mw is 100,000 or less, the resolution time is not excessively long.

The ratio (Mw/Mn) of Mw to number average molecular weight (Mn) of the polymer (B) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. Mn is a polystyrene equivalent measured by GPC using tetrahydrofuran as the dissolution solvent.

In the coloring composition, the content of the (B) polymer is usually 10 parts by mass to 1,000 parts by mass relative to 100 parts by mass of the (a) colorant. When the content of the polymer (B) is within the above range, an appropriate alkali developability in terms of a coating film formation process, a sufficient storage stability as a product of the coloring composition, and a sufficient color density as a color filter for a desired film thickness can be ensured. (B) The content of the polymer is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, based on 100 parts by mass of the colorant (a). The content of the polymer (B) is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, based on 100 parts by mass of the colorant (a).

Polymerizable Compound (C)

(C) The polymerizable compound is a compound having preferably two or more polymerizable groups, and is a low-molecular compound functioning as a crosslinking agent. Further, (C) a polymerizable compound is different from (A) a colorant in that it does not have a pigment structure, and (B) a polymer in that it does not have a molecular weight distribution. That is, the compound having a polymerizable group and a pigment structure is classified as (a) a colorant. The polymer having a polymerizable group and having no pigment structure is classified as (B) polymer. (C) The molecular weight of the polymerizable compound is preferably 1,000 or less, more preferably 800 or less.

Examples of the polymerizable group include an ethylenically unsaturated group, an oxetanyl group, and an N-alkoxymethylamino group. Among these, (C) polymerizable compounds are preferably compounds having two or more (meth) acryloyl groups or compounds having two or more N-alkoxymethylamino groups, and particularly preferably compounds having two or more (meth) acryloyl groups. (C) The number of polymerizable groups in one molecule of the coincidence compound is preferably 2 to 10, more preferably 2 to 8.

(for hydroxyl group-containing Compound)

In one form of the coloring composition of the present disclosure, the (C) polymerizable compound includes a hydroxyl group-containing compound (hereinafter, also referred to as "hydroxyl group-containing crosslinking agent (C1)"). By using the hydroxyl group-containing crosslinking agent (C1), the group "-OR" in the formula (1) can be introduced relatively easily ¹ "and base" -OR ² "and the content of hydroxyl groups in the coloring composition are easily adjusted.

The number of hydroxyl groups in one molecule of the hydroxyl group-containing crosslinking agent (C1) is preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4, from the viewpoint of both solvent resistance and storage stability. In addition, the hydroxyl group-containing crosslinking agent (C1) is particularly preferably a compound having two or more (meth) acryloyl groups in terms of high reactivity to heat and light.

In the case where the coloring composition of the present disclosure contains only the hydroxyl group-containing crosslinking agent (C1) as the hydroxyl group-containing compound, the hydroxyl group value of the hydroxyl group-containing crosslinking agent (C1) is preferably 10mgKOH/g to 500mgKOH/g. When the hydroxyl value of the hydroxyl group-containing crosslinking agent (C1) is set to a value within the above range, the effect of improving the solvent resistance of the colored cured film obtained by using the coloring composition of the present disclosure and the effect of improving the storage stability of the coloring composition can be balanced and well-balanced, and this is preferable. The hydroxyl value of the hydroxyl group-containing crosslinking agent (C1) is more preferably 25mgKOH/g or more, and still more preferably 50mgKOH/g or more, from the viewpoint of solvent resistance. In addition, from the viewpoint of storage stability, the hydroxyl value of the hydroxyl group-containing crosslinking agent (C1) is more preferably 400mgKOH/g or less, and still more preferably 300mgKOH/g or less. In the present specification, the term "hydroxyl value" means the mg number of potassium hydroxide (potassium hydroxide, KOH) required to neutralize 1g of the solid content of the hydroxyl group-containing crosslinking agent (C1).

The hydroxyl group-containing crosslinking 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. Among these, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol polyacrylate are particularly preferable in terms of increasing the intermolecular or intramolecular crosslinking density and further improving the hardenability of the film even by low-temperature calcination. Further, as the hydroxyl group-containing crosslinking agent (C1), one kind may be used alone, or two or more kinds may be used in combination.

(other polymerizable Compound)

The coloring composition may contain only a hydroxyl group-containing compound as the (C) polymerizable compound, or may use a polymerizable compound (hereinafter, also referred to as "other polymerizable compound") that does not have any of the partial structure represented by the above formula (1) and the hydroxyl group as the (C) polymerizable compound. In addition, in the case where 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) a colorant and (B) a polymer, the coloring composition may contain only other polymerizable compounds as (C) polymerizable compounds.

Specific examples of the other polymerizable compound include a compound having two or more (meth) acryloyl groups: a multifunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, a caprolactone-modified multifunctional (meth) acrylate, an alkylene oxide-modified multifunctional (meth) acrylate, a multifunctional urethane (meth) acrylate obtained by reacting a hydroxyl-containing (meth) acrylate with a multifunctional isocyanate, a carboxyl-containing multifunctional (meth) acrylate obtained by reacting a hydroxyl-containing (meth) acrylate with an acid anhydride, and the like.

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

Among them, preferable examples of the other polymerizable compound include a multifunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, a caprolactone-modified multifunctional (meth) acrylate, a multifunctional urethane (meth) acrylate, a carboxyl group-containing multifunctional (meth) acrylate, N, N, N ', N', N ", N" -hexa (alkoxymethyl) melamine, N, N, N ', N' -tetra (alkoxymethyl) benzoguanamine, more preferably a multifunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound having trivalent or more atoms with (meth) acrylic acid, a multifunctional urethane (meth) acrylate, or a multifunctional (meth) acrylate having a carboxyl group. As the other polymerizable compound, one kind may be used alone or two or more kinds may be mixed and used.

The content of the polymerizable compound (C) in the coloring composition is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, based on 100 parts by mass of the colorant (a). The content of the polymerizable compound (C) is preferably 1,000 parts by mass or less, more preferably 500 parts by mass or less, per 100 parts by mass of the colorant (a). When the content ratio of the polymerizable compound (C) is within the above range, it is preferable in terms of ensuring sufficient hardenability and sufficient alkali developability as a colored hardened film and sufficiently suppressing the occurrence of stains, film residues, and the like on the substrate of the unexposed portion or on the light shielding layer.

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

(D) photopolymerization initiator

(D) The photopolymerization initiator is a compound that generates an active species capable of initiating polymerization of the polymerizable compound (C) by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like. Examples of such photopolymerization initiators include: thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime initiators, onium salt compounds, benzoin compounds, benzophenone compounds, alpha-diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, and the like. Among these, the photopolymerization initiator (D) preferably contains an oxime initiator in terms of sufficiently generating radicals and sufficiently curing the film. As the oxime-based initiator, an O-acyl oxime-based initiator can be preferably used.

Specific examples of the O-acyloxime initiator include: 1, 2-octanedione, 1- [ 4- (phenylsulfanyl) phenyl ] -2- (O-benzoyl oxime), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyl oxime), ethanone, 1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyl oxime), ethanone, 1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxacyclopentyl) methoxybenzoyl } -9H-carbazol-3-yl ] -1- (O-acetyl oxime), 1, 2-propanedione, 3-cyclohexyl-1- [ 4- (phenylsulfanyl) phenyl ] -1- (O-acetyl oxime) (a compound represented by the following formula (D-1)), a compound represented by the following formula (D-2), and the like.

[ chemical 8]

As the O-acyl oxime initiator, commercially available products such as NCI-831, NCI-930 (above, manufactured by Ai Dike (ADEKA) Co., ltd.), PBG-3057 (above, manufactured by Hezhou powerful electronic New material Co., ltd.), and Brilliant good (Irgacure) OXE03 (above, manufactured by BASF Japan Co., ltd.) can also be used.

As the O-acyl oxime initiator, a compound represented by the following formula (d-10), formula (d-11) and formula (d-12) may be preferably used.

[ chemical 9]

(in the formula (d-10), X ¹ X is X ² Each independently is a single bond or-CO-; wherein X is ¹ X is X ² At least one of them is-CO-; r is R ¹ Is alkyl with 2-6 carbon atoms, R ² Is alkyl with 4-10 carbon atoms; r is R ⁴ Is a monovalent organic group having a hydrocarbon ring or a heterocyclic ring; r is R ³ R is R ⁵ Independently of each other, an alkyl group having 1 to 6 carbon atoms or a phenyl group

[ chemical 10]

(in the formula (d-11) and the formula (d-12), X ³ Is a single bond or an alkanediyl group having 1 to 5 carbon atoms, X ⁴ is-O-, -S-or-NR ¹⁰ - (wherein R ¹⁰ A monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which is a hydrogen atom); x is X ⁵ X is X ⁶ Each independently is a single bond or-CO-, R ⁶ R is R ⁷ Each independently is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ⁸ R is R ⁹ Each independently is a substituted or unsubstituted C1-20 Monovalent hydrocarbon groups, or substituted or unsubstituted heterocyclic groups having 3 to 20 carbon atoms; r is R ¹¹ R is R ¹² Each independently a hydrogen atom or a monovalent substituent)

In the formula (d-10), R ¹ Preferably ethyl or propyl. R is R ² The compound may be linear or branched, and is preferably linear. R is R ⁴ Preferably, the hydrocarbon ring or the heterocyclic ring is bonded to the carbon atom of the oxime ester group via a divalent linking group. The divalent linking group is preferably at least one selected from the group consisting of alkanediyl groups having 1 to 4 carbon atoms, -S-, -O-and-CO-, and more preferably methylene, ethylene, -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 formula (d-11) and the formula (d-12), R ⁶ 、R ⁷ 、R ⁸ Or R is ⁹ In the case of having a substituent, examples of the substituent include: halogen atom, nitro group, hydroxyl group, carboxyl group, sulfonic group, amino group, cyano group, etc. As R ¹¹ R is R ¹² The substituents of (2) may be as follows: halogen atom, nitro group, hydroxyl group, carboxyl group, sulfonic group, amino group and cyano group, and a group in which at least one hydrogen atom of alkyl group, cycloalkyl group, cycloalkylalkyl group or alkylcycloalkyl group is substituted with halogen atom, nitro group, hydroxyl group, carboxyl group, sulfonic group, amino group or cyano group, and the like.

As the O-acyl oxime initiator, at least one selected from the group consisting of an acyl oxime compound having a diphenyl sulfide skeleton, an acyl oxime compound having a carbazole skeleton, and an acyl oxime compound having a fluorene skeleton is preferably used in order to make the contrast ratio of the cured film better. The O-acyloxime initiator is more preferably at least one selected from the group consisting of an acyloxime compound having a diphenyl sulfide skeleton and an acyloxime compound having a fluorene skeleton.

(D) The content ratio of the photopolymerization initiator is preferably 0.01 parts by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the polymerizable compound (C). The content of the photopolymerization initiator (D) is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, based on 100 parts by mass of the polymerizable compound (C). When the content of the photopolymerization initiator (D) is within the above range, the occurrence of stains and film residues on the substrate or the light-shielding layer in the unexposed portion can be sufficiently suppressed while ensuring sufficient hardening of the coating film by an appropriate exposure amount and sufficient alkali developability as a coloring composition. In addition, the decrease in the brightness of the coating film due to yellowing of the polymerization initiator at the time of post baking can be sufficiently suppressed. (D) The photopolymerization initiator may be used singly or in combination of two or more.

Solvent < (E)

The coloring composition of the present disclosure is prepared in the form of a liquid composition by formulating the solvent (E). As the solvent (E), a solvent which disperses or dissolves the respective components (a), component (B), component (C) or other components constituting the coloring composition, does not react with these components, and has a moderate volatility 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, 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, and the like (poly) alkylene glycol monoalkyl ethers;

alkyl lactate esters such as methyl lactate and ethyl lactate; alkyl alcohols which may have a linear, branched or cyclic structure such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol and the like; ketone alcohols such as diacetone alcohol;

(poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

diacetates such as propylene glycol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanediol diacetate;

alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate;

other esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene;

Amides such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, lactams, and the like.

Among these, the solvent (E) is preferably at least one selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1, 3-butanediol diacetate, 1, 6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, and ethyl pyruvate from the viewpoints of solubility, pigment dispersibility, coatability, and the like. Further, the solvent (E) may be used singly or in combination of two or more.

The coloring composition of the present disclosure preferably contains at least one solvent selected from the group consisting of primary alcohols and secondary alcohols (hereinafter, also referred to as "specific alcohols") in a range of a predetermined amount or less, so that the coloring composition can have good storage stability. In order to achieve low-temperature calcination, the specific alcohol is preferably a solvent having a boiling point of 150 ℃ or less. As preferable examples of the specific alcohols, methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol; examples of the secondary alcohol include propane-2-ol, butane-2-ol, pentane-2-ol and hexane-2-ol. Among these, the primary alcohol is preferable in terms of obtaining a coloring composition excellent in storage stability.

In the coloring composition of the present disclosure, the formation of the cross-links at the time of film formation is performed by transesterification, and since the transesterification is a reversible reaction, the equilibrium is maintained by allowing a specific alcohol to exist in the coloring composition, and the progress of the transesterification is suppressed, whereby it is considered that the storage stability of the coloring composition can be improved.

In the coloring composition of the present disclosure, the content ratio of the specific alcohol is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 7% by mass or less, relative to the total amount of the (E) solvent contained in the coloring composition, from the viewpoint of maintaining the dispersibility of the (a) colorant. In order to obtain the effect of improving the storage stability, the content of the specific alcohol is preferably more than 0 mass%, more preferably 0.01 mass% or more, still more preferably 0.5 mass% or more, and still more preferably 1 mass% or more. As the specific alcohol, one kind may be used alone or two or more kinds may be used in combination.

Additive (F)

The coloring composition may contain various additives other than those described above, if necessary. Examples of the additive include: fillers such as glass and alumina; high molecular compounds such as polyvinyl alcohol and poly (fluoroalkylacrylate); a surfactant such as a fluorine-based surfactant and a silicon-based surfactant; a sealing accelerator; an antioxidant; an ultraviolet absorber; polyfunctional thiols; zirconium compounds, titanium compounds, aluminum compounds, and other metal chelating compounds. The blending ratio of these may be appropriately set according to the kind of each additive within a range that does not impair the effects of the present disclosure.

In the coloring composition of the present disclosure, the content ratio of the specific compound and the hydroxyl group-containing compound may be appropriately set so that the content of the partial structure represented by the above formula (1) and the content of the hydroxyl group are in the appropriate ranges, respectively, depending on the formulation form of the specific compound and the hydroxyl group-containing compound.

< preparation of coloring composition >

The coloring compositions of the present disclosure may be prepared using suitable methods. Examples of the production method include those disclosed in japanese patent application laid-open publication No. 2008-58442 and japanese patent application laid-open publication No. 2010-132874. In the case of using both a dye and a pigment as the (a) colorant, the following method can be adopted: as disclosed in japanese patent application laid-open No. 2010-132874, a dye solution is passed through a first filter, the dye solution passed through the first filter is mixed with a pigment dispersion liquid or the like prepared separately, and the obtained coloring composition is passed through a second filter, whereby the coloring composition is prepared. In addition, the following method may be adopted: the dye, the polymer (B) and the polymerizable compound (C) and other components if necessary are dissolved in a solvent, the obtained solution is passed through a first filter, the solution passed through the first filter is mixed with a pigment dispersion prepared separately, and the obtained colored composition is passed through a second filter. In addition, the following method may be adopted: after passing the dye solution through the first filter, the dye solution having passed through the first filter, the (B) polymer, the (C) polymerizable compound, and other components if necessary, are mixed and dissolved, the obtained solution is passed through the second filter, the solution having passed through the second filter is further mixed with a pigment dispersion liquid prepared separately, and the obtained colored composition is passed through the third filter, whereby the dye composition is prepared.

[ color Filter and method for producing the same ]

The color filter of the present disclosure includes a colored layer formed using the colored composition.

As a method of manufacturing a color filter, first, a light shielding layer (black matrix) is formed on the surface of a substrate in such a manner as to divide portions where pixels are formed as needed. Then, after the green colored composition (liquid composition) is applied to the substrate, the solvent is evaporated by drying under reduced pressure or prebaking, and a coating film is formed (film forming step). Then, the coating film is exposed to light through 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. Thereafter, a post baking (heating step) is performed to form a pixel array in which green pixel patterns are arranged in a predetermined arrangement.

Then, each coloring composition of red or blue is used, and the application, drying, exposure, development, and post baking of each coloring composition are performed in the same manner as described above, so that a red pixel array and a blue pixel array are sequentially formed on the same substrate. Thus, a color filter having a pixel array of three primary colors, green, red, and blue, disposed on a substrate is obtained. The order in which the pixels of the respective colors are formed is not limited to the order. The black matrix can be formed by forming a metal thin film of chromium or the like formed by sputtering or vapor deposition into a desired pattern by photolithography. In addition, a coloring composition in which a black coloring agent is dispersed may be used and formed in the same manner as in the case of forming the pixel.

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

When the coloring composition is applied to the substrate, a suitable coating method such as a spray method, a roll coating method, a spin coating method (spin coat method), a slit die coating method (slit coating method), or a bar coating method can be used. Among these, spin coating and slot die coating are preferable in particular in terms of obtaining a coating film having a uniform film thickness. After the coating, drying under reduced pressure is performed, whereby a coating film is formed on the substrate. The drying under reduced pressure is usually carried out at room temperature for 1 to 15 minutes, preferably 1 to 10 minutes, and usually at a pressure of 50 to 200 Pa. The formation of the coating film can be performed by a heat treatment (pre-baking) at a temperature lower than the post-baking temperature. The thickness of the coating is usually 0.6 μm to 8 μm, preferably 1.2 μm to 5 μm, in terms of the film thickness after drying.

Examples of the light source of the radiation used for exposure include: a light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, or a low-pressure mercury lamp, or a laser light source such as an argon ion laser, a Yttrium-Aluminum-Garnet (YAG) laser, a XeCl excimer laser, or a nitrogen laser. An ultraviolet Light Emitting Diode (LED) may also be used as the exposure Light source. The radiation having a wavelength in the range of 190nm to 450nm is preferable, and the radiation having a wavelength in the range of 300nm to 450nm is more preferable. The exposure to radiation is generally preferably 10J/m ² ～10,000J/m ² . The exposure to radiation is more preferably 100J/m ² The above is more preferably 200J/m ² The above. In addition, the exposure to radiation is more preferably 5,000J/m ² Hereinafter, 2,000J/m is more preferable ² The following is given.

As the alkali developer, for example, aqueous solutions of sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline (choline), 1, 8-diazabicyclo- [5.4.0] -7-undecene, 1, 5-diazabicyclo- [4.3.0] -5-nonene, and the like are preferable. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline developer. Further, after alkali development, water washing is usually performed. As the development treatment method, there can be applied: spray development, dip (dip) development, liquid coating (pump) development, and the like. The development conditions are preferably carried out at normal temperature for 5 seconds to 300 seconds.

Post baking is performed by heating the patterned coating film at 70-230 ℃. The post baking temperature may be set at, for example, 70 to 120 ℃, or 120 to 180 ℃, 180 to 240 ℃ or the like, depending on the application, in view of the hardening property, solvent resistance, improvement of adhesion to a substrate, suppression of color shift, substrate protection, and the like. At this time, in order to make the group "OR" of a specific compound ¹ "and base" OR ² The transesterification reaction between at least one of the "and the OH group of the hydroxyl group-containing compound proceeds sufficiently, and the temperature higher than the boiling point of the alcohol contained in the coloring composition may be set as the heating temperature at the time of post baking. The heating time in post baking can be set appropriately according to the heating temperature, and is usually 5 minutes to 120 minutes, preferably 30 minutes to 100 minutes, for example, at a low temperature of 70 to 120 ℃. The thickness of the colored cured film (i.e., pixel) formed on the substrate is usually 0.5 μm to 5. Mu.m, preferably 1.0 μm to 3. Mu.m.

After a protective film is formed as needed on the pixel pattern thus obtained, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to manufacture a color filter. In general, a transparent photosensitive resin composition is used to form the spacer, but a spacer having light shielding properties (black spacer) may be produced. In this case, a photosensitive coloring composition in which a black colorant is dispersed is used. The coloring composition of the present disclosure may also be suitably used to form the black spacer.

The coloring composition of the present disclosure can also be suitably used for forming any of colored cured films of pixels of respective colors, black matrices, black spacers, and the like used in color filters. The color filter thus formed has high brightness and color purity, and is particularly useful for color liquid crystal display elements, solid-state imaging elements, color sensors, organic Electroluminescence (EL) display elements, electronic papers, and the like.

[ display element ]

The display element of the present disclosure includes the color filter of the present disclosure. As the display element, there can be mentioned: color liquid crystal display elements, organic EL display elements, electronic paper, and the like.

A color liquid crystal display element including the color filter of the present disclosure may include a backlight unit using a white LED as a light source, in addition to a cold cathode fluorescent tube (CCFL: cold Cathode Fluorescent Lamp). Examples of the white LED include: a white LED that combines a red LED, a green LED, and a blue LED and obtains white light by color mixing; a white LED in which a blue LED, a red LED, and a green phosphor are combined and mixed to obtain white light; a white LED in which a blue LED, a red light-emitting phosphor, and a green light-emitting phosphor are combined and mixed to obtain white light; a white LED that obtains white light by mixing a blue LED with a YAG-based phosphor; a white LED in which a blue LED, an orange light-emitting phosphor, and a green light-emitting phosphor are combined and mixed to obtain white light; a white LED in which ultraviolet LEDs, red light-emitting phosphors, green light-emitting phosphors, and blue light-emitting phosphors are combined and mixed to obtain white light, and the like.

The organic EL display element including the color filter of the present disclosure may be of a suitable structure, and for example, a structure disclosed in japanese patent laid-open No. 11-307242 is exemplified. Further, an electronic paper including the color filter of the present disclosure may be a structure disclosed in japanese patent laid-open No. 2007-4169, for example.

[ light-receiving element ]

The light receiving element of the present disclosure includes a colored hardened film formed using the coloring composition. The light receiving element of the present disclosure may be configured as appropriate, for example, by using the colored cured film as a color filter constituting a solid-state imaging element and combining the colored cured film with a photodiode, whereby an imaging element such as a solid-state imaging element can be constituted. In addition, the cured film of the present disclosure may be used as an infrared light transmitting filter and combined with a photodiode, thereby constituting an infrared light detecting pixel.

[ curable composition ]

The curable composition of the present disclosure contains the (B) polymer and (C) polymerizable compound. In particular, in the curable composition of the present disclosure, at least one selected from the group consisting of (B) a polymer and (C) a polymerizable compound has a partial structure represented by the formula (1), and at least one selected from the group consisting of (B) a polymer and (C) a polymerizable compound has a hydroxyl group. The partial structure represented by the 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 for forming a cured film. Examples of the cured film include: each color pixel, an interlayer insulating film, a planarizing film, a bank (partition wall) defining a region where a light-emitting layer is formed, a black matrix, a spacer, a protective film, and the like used in a display element or a light-receiving element. Examples of the display element include a color liquid crystal display element, an organic EL element, and an electronic paper, and examples of the light receiving element include a charge coupled device (Charge Coupled Device, CCD) image sensor, and a complementary metal oxide semiconductor (Complementary Metal Oxide Semiconductor, CMOS) image sensor.

Examples (example)

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The "parts" and "%" in examples and comparative examples are mass-based 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)

[ chemical 11]

(other monomers)

[ chemical 12]

(dye monomer)

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

[ chemical 13]

(dye)

[ chemical 14]

[ 15]

[ 16]

[ chemical 17]

[ chemical 18]

[ chemical 19]

(hydroxyl group-containing dye)

[ chemical 20]

[ chemical 21]

(photopolymerization initiator)

[ chemical 22]

(polymerizable Compound)

[ chemical 23]

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

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

1. Synthesis of dye resins

Synthesis examples 1 to 1

Into a reaction vessel equipped with a cooling tube, 8.70g of a dye monomer I, 1.41g of Methacrylic Acid (MA), 0.42g of malonic acid-2- [ [ [ [ [ 2-methyl-1-oxo-2-propenyl ] oxy ] ethyl ] amino ] carbonyl ] -1, 3-diethyl ester (manufactured by Showa electric company under the trade name "Karenz" MOI-DEM ", hereinafter referred to as" Compound (M-1) ") 2.25g, 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate, HEMA) 1.97g, 2-ethylhexyl-3-mercaptopropionate (2-ethylhexyl-3-mercapto propionate, EHMP) 0.42g were added so as to be dissolved in propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate, PGMEA) 25.4g and n-butanol 59.2 g. The solution was heated to 75 ℃ under nitrogen flow while stirring. 0.42g of 2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile) (trade name "V-70", hereinafter also simply referred to as "V-70" manufactured by Wako pure chemical industries, ltd.) was added while stirring at the same temperature, and stirring was continued for 3 hours. Thereafter, 0.42g of V-70 was further added thereto, and stirring was continued for 3 hours. Then, after the reaction solution was cooled to room temperature, 60g of PGMEA was added to prepare a uniform solution, which was added dropwise to 1.1L of hexane. The precipitate formed was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50℃to obtain 15.30g of a polymer (which was designated as "polymer (A-1)"). Regarding the obtained polymer (A-1), mw was found to be 19,000 and Mn was found to be 9,800 by GPC.

Synthesis examples 1-2 to 1-10, synthesis examples 1-12 to 1-22 and comparative Synthesis examples 1-1 to 1-4

The same operations as in Synthesis example 1-1 were carried out, except that the types and the amounts of the monomers used were changed as shown in Table 1 below, to synthesize polymers (A-2) to (A-10), polymers (A-12) to (A-22) and polymers (AR-1) to (AR-4), respectively. In table 1, "-" indicates a component which is not blended (the same applies to the following table).

Synthesis examples 1 to 11

Into a reaction vessel equipped with a cooling tube, 8.70g of a dye monomer I, 1.41g of MA, 2.25g of a compound (M-1), 1.97g of glycerol monomethacrylate (glycerol monomethacrylate, GLM), and 0.42g of thioglycollic acid monoethanolamine (thioglycolic acid-monoethanolamine, TG-MEA) were added and dissolved in 25.4g of PGMEA and 59.2g of n-butanol. The solution was heated to 75 ℃ under nitrogen flow while stirring. 0.42g of 2,2' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ] (a water-soluble radical initiator, trade name "VA-086", hereinafter also referred to simply as "VA-086", manufactured by Wako pure chemical industries, ltd.) was added while stirring at the same temperature, and stirring was continued for 3 hours. Thereafter, 0.42g of VA-086 was further added thereto, and stirring was continued for 3 hours. Then, after the reaction solution was cooled to room temperature, 60g of PGMEA was added to prepare a uniform solution, which was added dropwise to 1.1L of hexane. The precipitate formed was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50℃to obtain 15.30g of a polymer (which was designated as "polymer (A-11)"). Regarding the obtained polymer (A-11), mw was found to be 19,300 and Mn was found to be 10,000 by GPC.

TABLE 1

Synthesis examples 1 to 23

To a reaction vessel equipped with a cooling tube, 8.45g of p- (vinylphenyl) trifluoromethanesulfonyl imide triethylamine salt (referred to as "acid monomer I"), 1.41g of MA, 2.25g of Compound (M-1), 1.97g of HEMA, 0.42g of pentaerythritol tetrakis (3-mercaptopropionate) (pentaerythritol tetrakis (3-mercapto propionate), PEMP) was added and dissolved in 25.40g of Cyclohexanone (CHN) and 59.20g of n-butanol. The solution was heated to 75 ℃ under nitrogen flow while stirring. V-70.84 g was added while stirring at the same temperature, and stirring was continued for 4 hours. Then, after the reaction solution was cooled to room temperature, 60g of acetone was added to prepare a uniform solution, which was added dropwise to 1.1L of hexane. The precipitate formed was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50℃to obtain 15.01g of an anionic group-containing polymer represented by the following structural formula (which was designated as "polymer (A-23-1)"). Regarding the obtained polymer (A-23-1), mw was found to be 11,100 and Mn was found to be 6,900 by GPC.

[ chemical 24]

2.0g of the synthesized polymer (A-23-1) was dissolved in 40mL of acetone. Next, as shown in the following scheme, a molar amount of C.I. Basic Red 12 (Basic Red I) was added to the number of moles of the constituent units derived from the triethylammonium p- (vinylphenyl) triflate calculated from the copolymerization ratio of the polymer (A-23-1), and stirred at room temperature for 1 hour. Thereafter, the reaction solution was concentrated under reduced pressure to obtain a residue, 200mL of ion-exchanged water was added to the obtained residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50℃to obtain 2.61g of a polymer represented by the following structural formula (which was designated as "polymer (A-23)").

[ chemical 25]

Synthesis examples 1 to 24 and Synthesis examples 1 to 25

The same operations as in Synthesis examples 1 to 23 were carried out, except that the types of basic dyes used were changed as shown in Table 2 below, to synthesize the polymer (A-24) and the polymer (A-25), respectively.

Synthesis examples 1 to 26

In a reaction vessel equipped with a cooling tube, 8.45g of methacryloyl propyl trimethyl ammonium chloride (basic monomer I), 1.41g of MA, 2.25g of Compound (M-1), 1.97g of HEMA, and 0.42g of PEMP were dissolved in 25.0g of CHN and 60.0g of n-butanol. The solution was heated to 75 ℃ under nitrogen flow while stirring. V-70.80 g was added while stirring at the same temperature, and stirring was continued for 4 hours. Then, after the reaction solution was cooled to room temperature, 60.0g of acetone was added to prepare a uniform solution, which was added dropwise to 1.10L of hexane. The precipitate formed was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50℃to obtain 15.11g of a cationic group-containing polymer represented by the following structural formula (which was designated as "polymer (A-26-1)"). Regarding the obtained polymer (A-26-1), mw was found to be 10,500 and Mn was found to be 7,000 by GPC.

[ chemical 26]

2.00g of the synthesized polymer (A-26-1) was dissolved in 40.0mL of acetone. Next, as shown in the following scheme, c.i. Acid Blue 93 (Acid dye I) was added in the same molar amount to the number of moles of the constituent units derived from the ammonium salt calculated from the copolymerization ratio of the polymer (a-26-1), and stirred at room temperature for 1 hour. Thereafter, the reaction solution was concentrated under reduced pressure to obtain a residue, 200mL of ion-exchanged water was added to the obtained residue, and the resulting precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure at 50℃to obtain 2.62g of a pigment polymer represented by the following structural formula (which was referred to as "polymer (A-26)"). Regarding the obtained polymer (A-26), mw was 12,600 and Mn was 7,500 as confirmed by GPC.

[ chemical 27]

Synthesis examples 1 to 27

The same operations as in Synthesis examples 1 to 26 were conducted except that the cationic monomer was changed to dimethylaminoethyl methacrylate (the basic monomer II) to obtain 15.02g of a cationic group-containing polymer represented by the following structural formula (the polymer was referred to as "polymer (A-27-1)"). Regarding the obtained polymer (A-27-1), mw was found to be 11,400 and Mn was found to be 6,800 by GPC. Then, the same operation as in the above-described synthesis examples 1 to 26 was performed using the polymer (A-27-1), whereby a pigment polymer of the polymer (A-27-1) and the C.I. Acid Blue (Acid Blue) 93 (Acid dye I) (this polymer was referred to as "polymer (A-27)") was obtained.

[ chemical 28]

Synthesis examples 1 to 28

The same operations as in Synthesis examples 1 to 26 were conducted except that the cationic monomer was changed to N, N-dimethylaminomethyl styrene (which was referred to as "basic monomer III"), whereby 15.07g of a cationic group-containing polymer represented by the following structural formula (which was referred to as "polymer (A-28-1)") was obtained. Regarding the obtained polymer (A-28-1), mw was found to be 11,300 and Mn was found to be 7,100 by GPC. Then, the same operation as in the above-described synthesis examples 1-26 was performed using the polymer (A-28-1), whereby a pigment polymer of the polymer (A-28-1) and the C.I. Acid Blue (Acid Blue) 93 (Acid dye I) (this was referred to as "polymer (A-28)") was obtained.

[ chemical 29]

Synthesis examples 1 to 29

The same operations as in Synthesis examples 1 to 26 were conducted except that the cationic monomer was changed to N-vinylpyrrolidone (which was referred to as "basic monomer IV"), whereby 15.03g of a cationic group-containing polymer represented by the following structural formula (which was referred to as "polymer (A-29-1)") was obtained. Regarding the obtained polymer (A-29-1), mw was 12,100 and Mn was 7,400 as confirmed by GPC. Then, the same operation as in the above-described synthesis examples 1-26 was performed using the polymer (A-29-1), whereby a pigment polymer of the polymer (A-29-1) and the C.I. Acid Blue (Acid Blue) 93 (Acid dye I) (this was referred to as "polymer (A-29)") was obtained.

[ chemical 30]

Synthesis examples 1 to 30

The same operation as in Synthesis examples 1-26 was conducted except that C.I. Acid Red 289 (Acid Red II) was used as an Acid dye, whereby a pigment polymer of polymer (A-26-1) and C.I. Acid Red 289 (Acid dye II) (which was designated as "polymer (A-30)") was obtained.

TABLE 2

In table 2, the abbreviations of the compounds are as follows.

Acidic monomer I: triethylamine salt of p- (vinylphenyl) trifluoro methanesulfonyl imide acid

Basic monomer I: methacryloylpropyl trimethyl ammonium chloride

Basic monomer II: dimethylaminoethyl methacrylate

Basic monomer III: n, N-dimethylaminomethyl styrene

Basic monomer IV: n-vinylpyrrolidone

2. Synthesis of binder resin

Synthesis examples 2 to 1

In a reaction vessel, 28.0g of compound (M-1), 24.5g of 2-hydroxyethyl methacrylate (HEMA), 7.0g of N-cyclohexylmaleimide (N-cyclohexyl maleimide, CHMI), 3.5g of styrene (styrene, ST), 7.0g of Methacrylic Acid (MA), 4.92g of 2,2' -azobis (2, 4-dimethylvaleronitrile) were weighed and dissolved in 40g of propylene glycol monomethyl ether acetate and 90g of N-butanol. The temperature of the reaction solution was raised to 75℃under nitrogen flow while stirring, and stirring was continued for 5 hours. After cooling the reaction solution to room temperature, 200g of a polymer solution having a solid content concentration of 35% by mass was recovered. Regarding the obtained polymer (referred to as "polymer (B-1)"), mw of 16,000 and Mn of 7,000 were confirmed by GPC measurement.

Synthesis examples 2-2 to 2-7, synthesis examples 2-9 to 2-17 and comparative Synthesis examples 2-1 to 2-5

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

Synthesis examples 2 to 8

In a reaction vessel, 28.0g of compound (M-1), 24.5g of glycerol monomethacrylate (glycerin monomethacrylate, GLM), 7.0g of N-Cyclohexylmaleimide (CHMI), 3.5g of Styrene (ST), 7.0g of Methacrylic Acid (MA), 4.60g of 2,2' -azobis [ 2-methyl-N- (2-hydroxyethyl) propanamide ] (manufactured by Wako pure chemical industries, ltd., trade name: VA-086 "), and 40g of propylene glycol monomethylether acetate and 90g of N-butanol were weighed and dissolved. The temperature of the reaction solution was raised to 75℃under nitrogen flow while stirring, and stirring was continued for 5 hours. After cooling the reaction solution to room temperature, 200g of a polymer solution having a solid content concentration of 35% by mass was recovered. Regarding the obtained polymer (referred to as "polymer (B-8)"), mw of 15,200 and Mn of 6,800 were confirmed by GPC measurement.

TABLE 3

Synthesis examples 2 to 18

In a reaction vessel, 32.0g of glycidyl methacrylate (glycidyl methacrylate, GMA), 10.9g of Styrene (ST), 27.1g of butyl methacrylate (butyl methacrylate, BMA) and 7.0g of 2,2' -azobis (2, 4-dimethylvaleronitrile) were weighed and dissolved in 130g of propylene glycol monomethyl ether acetate. The reaction solution was heated to 75℃under stirring under a nitrogen gas stream, and stirring was continued for 3 hours, after which the temperature of the reaction solution was heated to 100℃and polymerization was further carried out for 1 hour, whereby 200g of a polymer solution was obtained. After cooling the polymer solution to room temperature, the flow was changed to an air flow, 16.5g of Acrylic Acid (AA) and 2.2g of tetrabutylammonium bromide (tetrabutylammonium bromide, TBAB) were added thereto, and the reaction was heated at 105℃for 10 hours. Subsequently, 22.6g of tetrahydrophthalic anhydride and 33g of propylene glycol monomethyl ether acetate were added and reacted at 105℃for 3 hours. After cooling the reaction solution to room temperature, 270g of a polymer solution having a solid content concentration of 40 mass% was recovered. Regarding the obtained polymer (which was designated as "polymer (B-18)"), mw was 11,700 and Mn was 6,700.

Synthesis examples 2 to 19

In a reaction vessel, 19.4g of compound (M-1), 26.4g of Methacrylic Acid (MA), 24.2g of Butyl Methacrylate (BMA) and 7.0g of 2,2' -azobis (2, 4-dimethylvaleronitrile) were weighed and dissolved in 100g of propylene glycol monomethyl ether acetate and 30g of n-butanol. The reaction solution was heated to 75℃under stirring under a nitrogen gas stream, stirring was continued for 3 hours, and thereafter, the temperature of the reaction solution was heated to 90℃and polymerization was carried out for 1 hour, whereby 200g of a polymer solution was obtained. After cooling to room temperature, the reaction mixture was switched to an air flow, 27.0g of [ (3, 4-epoxycyclohexane) -1-yl ] methyl methacrylate and 1.9g of tetrabutylammonium bromide (TBAB) were added thereto, and the reaction mixture was heated at 105℃for 10 hours. After cooling the reaction solution to room temperature, 240g of a polymer solution having a solid content concentration of 40 mass% was recovered. Regarding the obtained polymer (which was designated as "polymer (B-19)"), mw was 11,900 and Mn was 6,600.

Synthesis examples 2 to 20

Into a flask including a cooling tube and a stirrer, 3 parts by mass of 2,2' -azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate were charged. The flask was charged with 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), 29 parts by mass of 2-ethylhexyl methacrylate (2-ethylhexyl methacrylate, EHMA), 14 parts by mass of benzyl methacrylate (benzyl methacrylate, bzMA), and 5 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakuh chemical industry (Co.)) and nitrogen gas was replaced. Thereafter, the reaction solution was slowly stirred to raise the temperature to 80℃and the temperature was maintained for 3 hours to carry out polymerization. Thereafter, the temperature of the reaction solution was raised to 100℃and polymerization was further carried out for 1 hour, whereby a binder resin solution containing 33.3 mass% of a binder resin (referred to as "polymer (BA-1)") was obtained. The Mw of the polymer (BA-1) was 9,700 and the Mn was 5,700.

Synthesis examples 2 to 21

A polymer (B-20) having Mw of 16,000 and Mn of 7,000 was synthesized in the same manner as in Synthesis example 2-1, except that ethanol was used instead of n-butanol.

3. Synthesis of hydroxy-containing dyes

Synthesis example 3-1

Using the dye A1, 1 equivalent of succinic anhydride was stirred at room temperature in a pyridine solvent in the presence of a catalyst amount of dimethylaminopyridine, and then solvent was distilled off, washed with water, and dehydrated, followed by solvent distillation to obtain a terminal carboxylic acid. Then, 1.2 equivalents of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was used to stir 1 equivalent of tris (hydroxymethyl) aminomethane at room temperature in a dichloromethane solvent, followed by washing with water, dehydration, and solvent distillation to obtain dye A3.

Synthesis example 3-2

Dye A4 as a target was obtained in the same manner as in synthesis example 3-1, except that a dye in which the anion of dye A2 was changed to an iodide anion was used instead of dye A1.

Synthesis examples 3 to 3

Dye C as a target was obtained in the same manner as in Synthesis example 3-1 except that the dye described in paragraph 0003 of Japanese patent application laid-open No. 2004-506775 was used in place of dye A1.

Synthesis examples 3 to 4

Dye E was obtained as a target substance in the same manner as in Synthesis example 3-1 except that the compound [2] described in Chinese patent CN102786459 was used instead of the dye A1.

The dye A1 may be synthesized by a known method, and the dye D may be synthesized by a known method with reference to japanese patent No. 2812624.

4. Preparation of colorant dispersions

[ preparation example 4-1]

A colorant dispersion (MB-G-1) was prepared by mixing 58 parts by mass of c.i. pigment green 58 as a colorant, 11.8 parts by mass of Bek (BYK) -LPN21116 (manufactured by BYK Chemie) as a dispersant in terms of a solution, a solid content concentration of 40.0% by mass), 13.0 parts by mass of a polymer (BA-1) as a binder resin in terms of a polymer solution (solid content concentration of 33.3% by mass), and a mixed solution containing 55.0 parts by mass of propylene glycol methyl ether acetate and 8 parts by mass of propylene glycol methyl ether as a solvent with a bead mill, and dispersing for 12 hours.

[ preparation example 4-2]

A colorant dispersion (MB-G-2) was obtained in the same manner as in preparation example 4-1, except that the kind of the colorant was changed to C.I. pigment green 59.

[ preparation examples 4-3]

A colorant dispersion (MB-G-3) was obtained in the same manner as in preparation example 4-1, except that the kind of the colorant was changed to C.I. pigment green 7.

[ preparation examples 4-4]

A colorant dispersion (MB-Y-1) was obtained in the same manner as in preparation example 4-1, except that the type of the colorant was changed to C.I. pigment yellow 138.

[ preparation examples 4-5]

A colorant dispersion (MB-Y-2) was obtained in the same manner as in preparation example 4-1, except that the type of the colorant was changed to C.I. pigment yellow 139.

[ preparation examples 4-6]

A colorant dispersion (MB-Y-3) was obtained in the same manner as in preparation example 4-1, except that the type of the colorant was changed to C.I. pigment yellow 185.

[ preparation examples 4-7]

A colorant dispersion (MB-R-1) was obtained in the same manner as in preparation example 4-1, except that the kind of the colorant was changed to C.I. pigment Red 177.

[ preparation examples 4-8]

Except that the kind of colorant was changed to c.i. pigment blue 15:6, a colorant dispersion (MB-B-1) was obtained in the same manner as in preparation example 4-1.

[ preparation examples 4-9]

A colorant dispersion (MB-Bk-1) was prepared in the same manner as in preparation example 4-1, except that 60 parts by mass of C.I. pigment blue and 29 parts by mass of C.I. pigment violet were used as colorants.

[ preparation examples 4-10]

A colorant dispersion (MB-Bk-2) was obtained in the same manner as in preparation example 4-1, except that the type of the colorant was changed to a lactam-based pigment (Irgaphor Black) S0100 CF manufactured by Basf Co., ltd.).

[ preparation examples 4-11]

A colorant dispersion (MB-Bk-3) was obtained in the same manner as in preparation example 4-1 except that the type of the colorant was changed to perylene pigment (Lumogen Black) FK4280 manufactured by Basf Co.

[ preparation examples 4-12]

A colorant dispersion (MB-Bk-4) was obtained in the same manner as in preparation example 4-1, except that the type of the colorant was changed to carbon black (TPX 1227R manufactured by Cabot (Cabot)) and the like.

5. Preparation and evaluation of coloring composition [ 1]

Examples 1 to 1

(1) Preparation of coloring composition

5.7 parts by mass of the polymer (A-1) obtained in Synthesis example 1-1, 0.7 part by mass of Wallion Orange (Valifast Orange) 32 (manufactured by Orient chemical industry Co., ltd.), 11.7 parts by mass of a colorant dispersion (MB-Y-2), 5.6 parts by mass of the polymer (BA-1) as a binder resin based on a polymer solution (solid content: 33.3% by mass), 3.2 parts by mass of dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate as a polymerizable compound (C), 1.0 part by mass of an oxime initiator (D-1) as a photopolymerization initiator (D), 0.03 part by mass of a Megafac F-554 (Di. Izosin (DIC) Co., ltd.) as a fluorine-based surfactant, and further, 10% by mass of methoxybutyl acetate as a solvent amount equivalent to 15.0% by mass of the solid content of the final composition, and 20% by mass of the remainder of methyl ether as a solvent equivalent to 20% by mass of the total amount of the total of the composition were mixed.

(2) Evaluation

The coloring composition (G1-1) was evaluated according to the following (i) and (ii).

(i) Evaluation of solvent resistance

The colored composition (G1-1) was applied to SiO having a sodium ion elution preventing function formed on the surface thereof by using a spin coater ₂ After drying under reduced pressure at room temperature, a coating film having a film thickness of 2.5 μm was formed on the sodium glass substrate of the film.

Then, a high-pressure mercury lamp was used at 600J/m via a photomask ² The exposure of the coating film contains radiation of each wavelength of 365nm, 405nm and 436 nm. Thereafter, the substrate was subjected to a development pressure of 1kgf/cm ² (nozzle diameter 1 mm) a developing solution containing 0.04 mass% aqueous potassium hydroxide solution at 23℃was discharged, whereby 60 seconds of spray development was performed. Thereafter, the substrate was rinsed with ultrapure water and air-dried, and then further baked in a clean oven at 150 ℃ for 30 minutes, thereby forming a long pattern on the substrate. For the long-shaped pattern, chromaticity coordinate values (x, Y) and stimulus values (Y) in the international commission on illumination (International Commission on Illumination, CIE) color system were measured with a C light source, a 2-degree field of view using a color analyzer (MCPD 2000 manufactured by kouka electronics (thigh)).

Next, the long pattern was immersed in a mixed solvent of diethylene glycol methyl ethyl ether/ethylene glycol monobutyl ether=50/50 (mass ratio) for 5 minutes, and then the chromaticity coordinate values (x, Y) and the stimulus value (Y) in the CIE color system were measured with a C light source and a 2-degree field of view using a color analyzer (MCPD 2000 manufactured by tsuka electronics (strand)). The color change before and after dipping, i.e., Δe×ab, was calculated. The evaluation criteria are as follows.

(evaluation criterion)

And (3) the following materials: the value of ΔE×ab is 3.0 or less

O: the value of ΔE ab is greater than 3.0 and 7.0 or less

Delta: the value of ΔE×ab is greater than 7.0 and 15.0 or less

X: a value of ΔE.times.ab greater than 15.0

Regarding the evaluation result, in example 1-1, the solvent resistance was "good".

(ii) Evaluation of storage stability

The viscosity Vo immediately after the preparation of the coloring composition (G1-1) was measured using an E-type viscometer (manufactured by Tokyo counter). Next, the coloring composition (G1-1) was filled in a light-shielding glass container, allowed to stand in a sealed state at 25 ℃ for 14 days, and then the viscosity was measured again by using an E-type viscometer (manufactured by tokyo counter). The rate of increase Δv [% ] (= ((Va-Vo)/Vo) ×100) of the viscosity Va after 14 days of storage relative to the viscosity Vo immediately after preparation was calculated, and the storage stability was evaluated based on the rate of increase Δv. The evaluation criteria are as follows.

(evaluation criterion)

O: the increase rate DeltaV is less than 5%

Delta: the increase rate DeltaV is more than 5% and less than 10%

X: the increase rate DeltaV is more than 10 percent

As to the evaluation result, in example 1-1, the storage stability was "O".

Examples 1-2 to 1-30 and comparative examples 1-1 to 1-4

In example 1-1, coloring compositions (G1-2) to (G1-30) and coloring compositions (G1-1R) to (G1-4R) were prepared in the same manner as in example 1-1, except that the types of the coloring agents and other components were changed so that chromaticity coordinate values (x, y) in the CIE color system under the C light source showed values of Table 4 below. The solvent resistance and storage stability of the obtained colored compositions (G1-2) to (G1-30) and colored compositions (G1-1R) to (G1-4R) were evaluated in the same manner as in example 1-1. 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: walifast Orange (Valifast Orange) 3209

C-1: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate (manufactured by east Asia Synthesis Co., ltd., trade name: luo Nisi (Aronix) M-402)

D-1: oxime initiator (Compound represented by the formula (D-1))

E1: methoxybutyl acetate

E2: propylene glycol monomethyl ether acetate

E3: n-butanol

E4: diacetone alcohol

E5: cyclohexanone

F-1: megafac (Megafac) F-554 (manufactured by Dielsen (DIC) Co., ltd.)

6. Preparation and evaluation of coloring composition [ 2 ]

Examples 2 to 1

(1) Preparation of coloring composition

28.5 parts by mass of a colorant dispersion (MB-G-1), 29.1 parts by mass of a colorant dispersion (MB-Y-1), 2.7 parts by mass of a polymer (B-3) as a binder resin in terms of a polymer solution (solid content concentration: 35% by mass), 4.2 parts by mass of dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate as a polymerizable compound (C), 0.5 parts by mass of an oxime initiator (D-1) as a photopolymerization initiator (D), and 0.03 parts by mass of a Megafac F-554 (Di) manufactured by Di-Ala Co., ltd.) as a fluorine-based surfactant were mixed, and methoxybutyl acetate in an amount of 10% by mass corresponding to the total solvent amount, n-butanol in an amount of 5% by mass corresponding to the total solvent amount, and propylene glycol monomethyl ether acetate in an amount corresponding to the remaining solvent amount were added to prepare a colorant composition (G2-1).

(2) Evaluation

The solvent resistance and storage stability of the coloring composition (G2-1) were evaluated 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, coloring compositions (G2-2) to (G2-27) and coloring compositions (G2-1R) to (G2-5R) were prepared in the same manner as in example 2-1, except that the types of the coloring agents and other components were changed so that chromaticity coordinate values (x, y) in the CIE color system under the C light source showed values of Table 5 below. The solvent resistance and storage stability of the obtained coloring composition were evaluated in the same manner as in example 1-1. The results are shown in table 5 below.

Examples 2 to 28 to 2 to 31 and comparative examples 2 to 6 to 2 to 9

The solvent resistance of the colored compositions (G2-4) and the colored compositions (G2-3R) 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 as shown in Table 6 below. The results are shown in Table 6 below.

Examples 2 to 32

A coloring composition (G2-4A) was prepared in the same manner as in example 2-1 except that the types of the coloring agent and other components were changed so that the chromaticity coordinate values (x, y) in the CIE color system under the C light source showed the values of Table 6 below in example 2-1. The solvent resistance of the obtained colored 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 ℃. The results are set forth in Table 6 below.

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7. Preparation and evaluation of coloring composition [ 3 ]

Examples 3 to 1

(1) Preparation of coloring composition

Dye A1.4 parts by mass, walliant Orange (Valifast Orange) 3209 (Orient chemical industry Co., ltd.) 0.7 parts by mass, colorant dispersion (MB-Y-2) 11.7 parts by mass, polymer (B-13) as a binder resin in an amount of 7.9 parts by mass based on a polymer solution (solid content concentration: 35 mass%), dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate as a polymerizable compound (C) 3.2 parts by mass, oxime initiator (D-1) 1.0 parts by mass as a photopolymerization initiator (D), megafac F-554 (Di loving) Co., ltd.) 0.03 parts by mass as a fluorine surfactant, and further, diacetone acetate in an amount of 10 mass% corresponding to the total amount of the solvent, n-butanol in an amount of 5 mass% corresponding to the total amount of the solvent, and diacetone acetate in an amount of 20% corresponding to the total amount of the solvent were added so as to make the solid content of the final composition 15.0 mass%, and further, 3 parts by mass of propylene glycol acetate in an amount corresponding to the total amount of the remaining amount of the remainder was prepared.

(2) Evaluation

The solvent resistance and storage stability of the coloring composition (G3-1) were evaluated in the same manner as in example 1-1. The results are shown in table 7 below.

Examples 3-2 to 3-13 and comparative examples 3-1 to 3-5

In example 3-1, coloring compositions (G3-2) to (G3-13) and coloring compositions (G3-1R) to (G3-5R) were prepared in the same manner as in example 3-1, except that the types of colorants and other components were changed in the chromaticity coordinate values (x, y) in the CIE color system under the C light source as shown in Table 7 below. The solvent resistance and storage stability of the obtained colored compositions (G3-2) to (G3-13) and colored compositions (G3-1R) to (G3-5R) were evaluated in the same manner as in example 1-1. The results are shown in table 7 below.

8. Preparation and evaluation of coloring composition [ 4 ]

Examples 4 to 1

(1) Preparation of coloring composition

A colorant composition (1) was prepared by mixing 30.9 parts by mass of dye IX, 24.2 parts by mass of colorant dispersion (MB-Y-1), 6.5 parts by mass of polymer (B-12) as a binder resin in terms of a polymer solution (solid content: 35% by mass), 3.9 parts by mass of dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate having a hydroxyl value of 100mgKOH/G to 140mgKOH/G as (C) polymerizable compound, 0.8 part by mass of oxime initiator (D-1) as (D) photopolymerization initiator, and 0.03 part by mass of Megafac F-554 (manufactured by Di-Alternatives, inc.) as a fluorine surfactant, and adding methoxybutyl acetate in an amount of 10% by mass corresponding to the total amount of solvent, adding n-butanol in an amount of 5% by mass corresponding to the total amount of solvent, adding cyclohexanone in an amount of 40% by mass corresponding to the total amount of solvent, and further adding propylene glycol monoacetate in an amount of 40% by mass corresponding to the amount of solvent, G, thereby obtaining a colorant composition (1-4).

(2) Evaluation

The solvent resistance and storage stability of the coloring composition (G4-1) were evaluated 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, coloring compositions (G4-2) to (G4-11) were prepared in the same manner as in example 4-1 except that the types of the coloring agent and other components were changed as shown in table 8 below in the chromaticity coordinate values (x, y) in the CIE color system under the C light source. The solvent resistance and storage stability of the obtained colored compositions (G4-2) to (G4-11) were evaluated 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 pentaacrylate/dipentaerythritol hexaacrylate (hydroxyl value: 60 mgKOH/g-100 mgKOH/g)

C-2B: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate (hydroxyl value: 100 mgKOH/g-140 mgKOH/g)

9. Preparation and evaluation of coloring composition [ 5 ]

Examples 5 to 1

(1) Preparation of coloring composition

16.0 parts by mass of a colorant dispersion (MB-Bk-1), 1.4 parts by mass of a colorant dispersion (MB-Bk-4), 25.2 parts by mass of a polymer (B-1) as a binder resin in terms of a polymer solution (solid content concentration: 35% by mass), 3.9 parts by mass of dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate as a polymerizable compound (C), 1.9 parts by mass of an oxime initiator (D-1) as a photopolymerization initiator (D), and 0.2 parts by mass of a Megafac RS-72-K (Di Depending (DIC) Co., ltd.) as a fluorine-based surfactant were mixed, and methoxybutyl acetate in an amount of 10% by mass in terms of the total amount of the solvent was added so that the solid content concentration of the final composition became 30.0% by mass, n-butanol in an amount of 5% by mass in terms of the total amount of the solvent, and propylene glycol monomethyl ether in an amount of the remaining amount of the solvent was added, to prepare a colorant composition (Bk 5-1).

(2) Evaluation

The solvent resistance of the coloring composition (Bk 5-1) was evaluated in accordance with the following (i). Further, 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 colored composition (Bk 5-1) was applied to SiO having a sodium ion elution prevention function formed on the surface thereof by using a spin coater ₂ After drying under reduced pressure at room temperature, a coating film having a thickness of 10 μm was formed on the sodium glass substrate.

Then, a high-pressure mercury lamp is usedLight-isolating mask of 600J/m ² The exposure of the coating film contains radiation of each wavelength of 365nm, 405nm and 436 nm. Thereafter, the substrate was subjected to a development pressure of 1kgf/cm ² (nozzle diameter 1 mm) a developing solution containing 0.04 mass% aqueous potassium hydroxide solution at 23℃was discharged, whereby 60 seconds of spray development was performed. Thereafter, the substrate was rinsed with ultrapure water and air-dried, and then, further, post-baking was performed in a clean oven at 85 ℃ for 60 minutes, whereby a line pattern having a width of 3 μm to 50 μm (1 μm unit) and a length of 1mm was formed on the substrate.

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, and the line pattern after immersion was observed. The solvent resistance was evaluated based on the minimum line width in the residual pattern after dipping.

(evaluation criterion)

And (3) the following materials: a minimum line width of 5 μm or less

O: a minimum line width of 6 μm or more and 10 μm or less

Delta: a minimum line width of 11 μm or more and 30 μm or less

X: a minimum line width of 31 μm or more

As to the evaluation results, in example 5-1, the solvent resistance was "O".

[ examples 5-2 to 5-6 and comparative examples 5-1 to 5-6]

In example 5-1, coloring compositions (Bk 5-2) to (Bk 5-6) and coloring compositions (Bk 5-1R) to (Bk 5-6R) were prepared in the same manner as in example 5-1, except that the types, parts by mass, and concentrations of the solvent and solid components of the coloring agents and other components were changed as shown in Table 9 below. Solvent resistance and storage stability were evaluated in the same manner as in example 5-1, except that the film thickness of the coating film in the solvent resistance evaluation was changed to 1. Mu.m, with respect to the obtained colored compositions (Bk 5-2) to (Bk 5-4), colored composition (Bk 5-6), colored composition (Bk 5-2R) to (Bk 5-4R) and colored composition (Bk 5-6R). The results are shown in table 9 below.

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In table 9, the abbreviations of the compounds are as follows.

E6: ethanol

F-2: megafac (Megafac) RS-72-K (manufactured by Dielsen (DIC) Co., ltd.)

From the above results, it is clear that: the curable composition containing the partial structure represented by the above formula (1) and hydroxyl groups in the same molecule or in different molecules among the colorant (a), the polymer (B) and the polymerizable compound (C) has little change with time in viscosity and excellent storage stability, and can produce a cured film having excellent solvent resistance even when the post-baking temperature is low.

Claims

1. A coloring composition comprising: a colorant (A), a polymer (B), and a polymerizable compound (C), wherein the polymer (B) excludes the colorant (A), the polymerizable compound (C) excludes the colorant (A) and the polymer (B), and the coloring composition,

the polymer (B) has a partial structure represented by the following formula (1),

the polymer (B) has hydroxyl groups,

in the formula (1), R ¹ R is R ² Each independently represents an alkyl group having 1 to 4 carbon atoms; l (L) ¹ Is a divalent organic radical; x is X ¹ Is a divalent linking group having electron withdrawing property; n1 and n2 are each independently an integer of 0 to 2; "×" indicates a bond.

2. The coloring composition according to claim 1, wherein the (B) polymer contains a polymer containing a constituent unit (a) having a partial structure represented by the formula (1).

3. The coloring composition according to claim 2, wherein the constituent unit (a) is a constituent unit derived from at least one selected from the group consisting of a (meth) acrylic monomer, a styrene monomer, and a maleimide monomer.

4. The coloring composition according to claim 2 or 3, wherein the constituent unit (a) is a constituent 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 is R ¹ 、R ² 、L ¹ 、X ¹ N1 and n2 are each as defined in the above formula (1).

5. A coloring composition according to claim 2 or 3, containing an alkali-soluble polymer having the constituent unit (a) as the (B) polymer.

6. The coloring composition according to claim 5, wherein the alkali-soluble polymer further contains a constituent unit having a hydroxyl group.

7. The coloring composition according to claim 6, wherein the constituent unit having a hydroxyl group is a constituent unit derived from a monomer having an ethylenically unsaturated group.

8. The coloring composition according to any one of claims 1 to 3, comprising a polymer containing a constituent unit having a hydroxyl group as the (B) polymer.

9. The coloring composition according to claim 8, wherein the constituent unit having a hydroxyl group is a constituent unit derived from a monomer having an ethylenically unsaturated group.

10. The coloring composition according to any one of claims 1 to 3, wherein the X ¹ Is a group having at least one electron-withdrawing group selected from the group consisting of carbonyl, amido, imido, ester, sulfonyl, sulfinyl, thiocarbonyl, and carbodiimide groups.

11. A colored hardened film formed using the colored composition according to any one of claims 1 to 10.

12. A color filter formed using the coloring composition according to any one of claims 1 to 10.

13. A display element comprising the colored cured film according to claim 11.

14. A light-receiving element comprising the colored hardened film according to claim 11.

15. A method for producing a colored cured film, comprising:

a step of forming a coating film by applying the coloring composition according to any one of claims 1 to 10 on a substrate; and

and removing the solvent contained in the coating film.

16. The method for producing a colored cured film according to claim 15, further comprising:

exposing the coating film; and

and developing the exposed coating film.

17. A curable composition comprising: (B) A polymer, and (C) a polymerizable compound, wherein the (B) polymer excludes a colorant, the (C) polymerizable compound excludes the colorant and the (B) polymer, and the curable composition,

the polymer (B) has hydroxyl groups,