KR20230125149A - Colored composition, colored cured film and manufacturing method thereof, color filter, display device, light receiving element, and curable composition - Google Patents

Abstract

(Problem) To provide a colored composition, a colored cured film, a method for producing the same, a color filter, a display element, a light receiving element, and a curable composition.
(Solution) (A) colorant, (B) polymer (except for (A) colorant), and (C) polymeric compound (except for (A) colorant and (B) polymer) In the coloring composition to contain, at least one selected from the group consisting of (A) a coloring agent, (B) a polymer, and (C) a polymerizable compound has a partial structure represented by formula (1), (A) a coloring agent, At least one selected from the group consisting of (B) polymers and (C) polymerizable compounds is used as a coloring composition having a hydroxyl group. In Formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, L ¹ is a divalent organic group, and X ¹ is a divalent linking group having an electron withdrawing property. n1 and n2 are each independently an integer of 0-2. "*" indicates that it is a bonding hand.

Description

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

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

As a method for producing a colored cured film such as a color filter, an inkjet method, an electrodeposition method, a printing method, a photolithography method, or the like are known. Among these, the photolithography method has become mainstream in recent years. In the case of manufacturing a color filter by photolithography, for example, after applying a colored curable composition on a substrate to form a coating film, exposing through a photomask having a predetermined opening pattern, and then developing, the unexposed portion A method of forming a pattern by dissolving and removing is employed (for example, refer to Patent Literature 1). After pattern formation, curing of the coating is accelerated by post-baking at a temperature of usually 200 to 250°C for about 30 to 60 minutes to improve the film hardness and solvent resistance of the film.

Japanese Unexamined Patent Publication No. Hei 2-144502

As a colorant contained in a colored cured film, a dye can increase the color and brightness of a displayed image when image is displayed due to the color purity of the dye itself and the vividness of its color, and also reduce coarse particles derived from the pigment. It is considered effective for improvement of contrast by this.

However, there is a problem that dyes are generally inferior in heat resistance. Therefore, it is difficult to heat a coating film formed using a coloring composition containing a dye at a postbaking temperature of 200 to 250°C. Moreover, with the expansion of uses, such as a display element, as a board|substrate, substitution from the conventional glass substrate to a flexible plastic substrate is examined. However, since plastic substrates generally have low heat resistance, when a coating film made of a coloring composition is formed on a plastic substrate and heated at a post-baking temperature of 200 to 250° C., there is a concern that elongation or shrinkage of the plastic substrate may occur. .

Regarding this problem, it is considered to perform post-baking at a temperature as low as possible. However, when post-baking is performed at a low temperature, the film is not sufficiently cured, and there is a risk that problems such as a decrease in solvent resistance may occur. In addition, a curable composition with high sensitivity at low temperature generally tends to be inferior in storage stability.

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

In order to solve the said subject, according to this invention, the manufacturing method of the following colored composition, colored cured film, color filter, display element, light receiving element, and colored cured film, and curable composition are provided.

[1] (A) colorant, (B) polymer (except for (A) colorant), and (C) polymerizable compound (except for (A) colorant and (B) polymer) ), wherein at least one selected from the group consisting of the (A) colorant, the (B) polymer, and the (C) polymerizable compound has a partial structure represented by the following formula (1), The coloring composition in which at least 1 sort(s) selected from the group which consists of the said (A) coloring agent, the said (B) polymer, and the said (C) polymeric compound has a hydroxyl group.

(In Formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms. L ¹ is a divalent organic group. 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] A colored cured film formed using the colored composition of [1] above.

[3] A color filter formed using the coloring composition of [1] above.

[4] A display element comprising the colored cured film of [2] above.

[5] A light-receiving element comprising the colored cured film of [2] above.

[6] A method for producing a colored cured film, comprising a step of applying the colored composition of [1] above to a substrate to form a coating film, and a step of removing a 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 the (B) polymer And at least one member selected from the group consisting of the polymerizable compound (C) has a partial structure represented by the following formula (1), and is selected from the group consisting of the polymer (B) and the polymerizable compound (C). A curable composition in which at least one type has a hydroxyl group.

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

Further, according to the curable composition of the present invention, at least one selected from the group consisting of (B) polymer and (C) polymerizable compound has a partial structure represented by the above formula (1), (B) polymer and (C) When at least 1 sort(s) selected from the group which consists of polymeric compounds has a hydroxyl group, even when post-baking is performed at low temperature, the cured film excellent in solvent resistance can be formed. 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.

(Mode for implementing the invention)

Hereinafter, matters related to embodiments will be described in detail. In addition, in this specification, the numerical range described using "-" is the meaning which includes the numerical value described before and after "-" as a lower limit and an upper limit. A "structural unit" is a unit mainly constituting the main chain structure, and refers to a unit contained at least two or more in the main chain structure.

[Coloring Composition]

The coloring composition is a composition used to form a colored layer such as each color pixel used in a color filter, a black matrix, a black spacer, and the like. The coloring composition of the present disclosure includes (A) a colorant, (B) a polymer (except for (A) the colorant. The same applies hereinafter), and (C) a polymeric compound (with the exception of (A) the colorant and (B) Excluding polymers, hereinafter the same). In particular, the coloring composition of the present disclosure is (A) a colorant, (B) a polymer, and (C) in at least one selected from the group consisting of a polymerizable compound in the same molecule or in different molecules, the following formula (1 ) and a hydroxyl group. 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), (A ) At least 1 sort(s) selected from the group which consists of a coloring agent, (B) polymer, and (C) polymeric compound has a hydroxyl group. In addition, the partial structure represented by the following formula (1) and the hydroxyl group may exist in the same molecule or may exist in different molecules.

(In Formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms. L ¹ is a divalent organic group. 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.)

Here, in the coloring composition of the present disclosure, "(A) colorant, (B) polymer, and (C) in the same molecule or in different molecules in at least one selected from the group consisting of polymeric compounds, formula The partial structure represented by (1) and a hydroxyl group" may mean that the partial structure represented by Formula (1) and the hydroxyl group exist in the same component, or the partial structure represented by Formula (1) It may be the sun in which a hydroxyl group exists in a heterogeneous component. For example, it is good also as a coloring composition containing the partial structure and hydroxyl group represented by Formula (1) by having (A) coloring agent having the partial structure and hydroxyl group represented by Formula (1). Or it is good also as a coloring composition containing the partial structure represented by Formula (1) and a hydroxyl group because (A) a coloring agent has a partial structure represented by Formula (1), and (B) a polymer has a hydroxyl group.

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

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

In addition, in this specification, "solid content" means components other than the (E) solvent contained in a coloring composition. Therefore, "total solid content" means (A) colorant, (B) polymer, and (C) polymerizable compound, (A) colorant, (B) polymer, (C) polymerizable compound, and (E) solvent. It means a combination of other ingredients. For example, even if it is a liquid photopolymerizable compound and an additive component (surfactant etc.), these shall be contained in solid content.

(Compound having a partial structure represented by the above formula (1))

In the above formula (1), the C1-C4 alkyl group of ^R1 and ^R2 may be linear or branched. From the viewpoint of allowing the reaction product of the partial structure represented by the formula (1) and the hydroxyl group to be discharged out of the membrane, R ¹ and R ² are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. .

n1 and n2 are preferably 0 or 1, more preferably 0, from the viewpoint of enabling higher reaction efficiency with hydroxyl groups.

X ¹ may be a divalent linking group having electron withdrawing property, and is not particularly limited. Here, "divalent linking group having electron withdrawing property" refers to a group obtained by removing a hydrogen atom 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 a new bond. The electron withdrawing group is a substituent having a Hammett substituent constant σp value of 0.15 or more, more preferably 0.2 or more. Regarding Hammett's substituent constants, it follows Journal of Medicinal Chemistry, 1973, Vol.16, No.11, 1207-1216.

X ¹ is a carbonyl group (-CO-), an amide group (-CONR ⁴ -* ¹ ), an imide group (-CONR ⁴ CO-), an ester group (from the viewpoint of efficiently advancing the reaction with a hydroxyl group at a low temperature) -CO-O-* ¹ ), a sulfonyl group (-SO ₂ -), a sulfinyl group (-SO-), a thiocarbonyl group (-CS-), and a carbonimide group (-C(=NH)-) At least one member selected from the group consisting of (provided that R ⁴ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and “* ¹ ” represents a bond bonded to L ¹ in the above formula (1) ) is preferred. Among these, X ¹ is more preferably an amide group, a carbonyl group or an ester group, and still more preferably an amide group or a carbonyl group.

As the divalent organic group of L ¹ , -O-, -CO-, -COO-, -NH-, -between the carbon-carbon bonds of the alkanediyl group of 1 to 20 carbon atoms and the alkanediyl group of 1 to 20 carbon atoms groups having CONH- and the like; and the like.

The compound having a partial structure represented by the above formula (1) (hereinafter also referred to as "specific compound") may be a low molecular compound having no repeating unit (hereinafter also referred to simply as "low molecular compound") or may be a polymer. In addition, in this specification, a "low molecular weight compound" is a compound that does not have a molecular weight distribution and preferably has a molecular weight of 1,000 or less. It is preferable that a specific compound is a polymer at the point from which the colored film excellent in solvent resistance can be obtained, and, specifically, it is preferable that it is a polymer containing the structural unit (a) which has a partial structure represented by said formula (1). When the specific compound is a polymer, the specific compound may be (A) a colorant or (B) a polymer. Moreover, as a specific compound, (A) coloring agent and (B) polymer may be contained in a coloring composition.

The structural unit (a) should just have a partial structure represented by said formula (1), and other partial structures are not specifically limited. Since the partial structure represented by the above formula (1) is easily introduced into the side chain of the polymer, the structural unit (a) is a structural unit derived from a monomer having an ethylenically unsaturated group (hereinafter also referred to as "ethylenically unsaturated monomer") It is preferable, and it is more preferable that it is a structural unit derived from at least 1 sort(s) selected from the group which consists of a (meth)acrylic monomer, a styrenic monomer, and a maleimide type monomer. Among these, it is preferable that structural unit (a) is a structural unit derived from a (meth)acrylic-type monomer, and it is especially preferable that it is a structural unit represented by following formula (1-2). In addition, in this specification, "(meth)acryl" is a concept containing an acryl and methacryl.

(In formula (1-2), R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹ , R ² , L ¹ , X ¹ , n1 and n2 have the same meaning as in the formula (1) above, respectively. am.)

In the above formula (1-2), the description of the above formula (1) applies to the specific examples and preferred examples of R ¹ , R ² , L ¹ , X ¹ , n1 and n2.

R ³ is preferably a hydrogen atom or a methyl group. L ¹ is preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, from the viewpoint of obtaining a colored film having excellent solvent resistance.

(hydroxyl group-containing compound)

The compound having a hydroxyl group (hereinafter also referred to as a "hydroxyl group-containing compound") may be a compound having at least one hydroxyl group in one molecule. This hydroxyl group-containing compound may be a low molecular compound or a polymer. In addition, the compound containing a hydroxyl group may be a compound identical to or different from a specific compound. When a hydroxyl-containing compound and a specific compound are the same compound, the said compound has the partial structure represented by said formula (1) and a hydroxyl group in 1 molecule. In this case, the partial structure represented by the above formula (1) may contain a hydroxyl group, but the partial structure represented by the above formula (1) and the hydroxyl group preferably exist at different sites (ie, in different structural units).

Here, in the composition of the present disclosure containing the partial structure represented by the formula (1) and a hydroxyl group, at least one of the groups “OR ¹ ” and the group “OR ² ” in the formula (1) is transesterified with the hydroxyl group It is considered that a reaction takes place and, as a result, a cross-linked structure is formed in the molecule or between molecules to cure it. This transesterification reaction is a reversible reaction, and progress of the transesterification reaction is suppressed in a state where equilibrium is maintained. Accordingly, it is considered that the coloring composition is not cured in a state where the equilibrium is maintained before heating, and the mixed state of (A) colorant, (B) polymer and (C) polymerizable compound is stably maintained.

On the other hand, when the composition is applied and heated to shift the equilibrium, a transesterification reaction between at least one of the groups “OR ¹ ” and “OR ² ” in the above formula (1) and a hydroxyl group occurs. It is thought that the transesterified “HO-R ¹ ” or “H-OR ² ” is discharged out of the system to cause an equilibrium shift, thereby forming a cross-linked structure between the specific compound and the hydroxyl group-containing compound and curing the composition. In addition, this transesterification reaction can proceed at a low temperature of, for example, 180° C. or less to cause film curing. According to the coloring composition of this indication, by using such a transesterification reaction, it is estimated that storage stability and low-temperature hardenability are compatible.

(Formulation of coloring composition)

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

As a specific aspect of the composition of the coloring composition, the following [1] to [8] blending aspects are exemplified.

[1] (A) contains a polymer having a partial structure represented by the above formula (1) and a hydroxyl group as a colorant, (B) contains a polymer having a hydroxyl group and not having a partial structure represented by the above formula (1) as a polymer, , (C) The aspect containing the compound which has a hydroxyl group as a polymeric compound and does not have the partial structure represented by said formula (1).

[2] (B) containing a polymer having a partial structure represented by the formula (1) and a hydroxyl group as a polymer, (C) a compound having a hydroxyl group as a polymerizable compound and not having a partial structure represented by the formula (1) containing sun. However, (A) the coloring agent does not have the partial structure represented by said formula (1) and a hydroxyl group.

[3] (A) containing a compound having a hydroxyl group as a colorant and not having a partial structure represented by the above formula (1), and (B) a polymer having a partial structure represented by the above formula (1) and having no hydroxyl group as a polymer (C) The aspect which contains the compound which has a hydroxyl group as a polymeric compound and does not have the partial structure represented by said formula (1).

[4] (B) contains a polymer having a partial structure represented by the above formula (1) and not having a hydroxyl group as the polymer, (C) having a hydroxyl group as a polymerizable compound and not having a partial structure represented by the above formula (1) Sun containing compounds. However, (A) the coloring agent does not have the partial structure represented by said formula (1) and a hydroxyl group.

[5] (A) contains a polymer having a partial structure represented by the above formula (1) and a hydroxyl group as a colorant, (B) contains a polymer having a partial structure represented by the above formula (1) and a hydroxyl group as a polymer, ( C) The aspect containing the compound which has a hydroxyl group as a polymeric compound and does not have the partial structure represented by said formula (1).

[6] (A) contains a polymer having a partial structure represented by the formula (1) and a hydroxyl group as a colorant, and (B) contains a polymer having a hydroxyl group and not having a partial structure represented by the formula (1) as a polymer sun. However, (C) a polymeric compound does not have the partial structure represented by said formula (1) and a hydroxyl group.

[7] (A) contains a polymer having a hydroxyl group as a colorant and not having a partial structure represented by the above formula (1), and (B) a polymer having a partial structure represented by the above formula (1) and having no hydroxyl group as the polymer (C) The aspect which contains the compound which has a hydroxyl group as a polymeric compound and does not have the partial structure represented by said formula (1).

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

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

<(A) Colorant>

(A) As for the colorant, the color and type are appropriately selected depending on the use. (A) As the coloring agent, any of pigments, dyes, quantum dots, and natural pigments can be used. From the viewpoint of obtaining a pixel having high luminance and color purity, (A) the coloring agent is preferably at least any of a pigment and a dye, and particularly preferably contains a dye. Pigments and dyes to be blended in the coloring composition are preferably organic. (A) As a coloring agent, a specific compound, a hydroxyl-containing compound, and the other coloring agent which does not have the partial structure represented by said formula (1) and a hydroxyl group are mentioned.

(for specific compounds)

In one aspect of the coloring composition of the present disclosure, (A) the coloring agent contains a specific compound. (A) The specific compound as a coloring agent should just have a partial structure represented by said formula (1), and is not specifically limited. When the specific compound is a polymer, the polymer having the partial structure represented by the above formula (1) can be obtained relatively easily using a conventional polymerization method, so the specific compound as a colorant (A) is a structural unit (a) ) and a polymer (hereinafter, also referred to as "polymer (A1)") containing a structural unit (b) having a dye structure is preferable.

Here, in this specification, "dye structure" is a partial structure derived from a dye, and is a chromophore. The dye structure may have an electric charge. When the dye structure has an electric charge, the dye structure may be in either form of an intramolecular salt or an intermolecular salt. The dye structure can adopt a structure derived from a known dye and is not particularly limited. Specifically, for example, dipyrromethene pigment, diarylmethane pigment, triarylmethane pigment, xanthene pigment, acridine pigment, anthraquinone pigment, azo pigment, quinoneimine pigment, polymethine pigment (oxonol pigment, Melocyanine pigment, arylidene pigment, styryl pigment, cyanine pigment, squarylium pigment, croconium pigment, etc.), phthalocyanine pigment, subphthalocyanine pigment, and a structure derived from a pigment selected from metal complex pigments thereof can be heard Among them, from the viewpoint of color characteristics, a structure derived from a pigment selected from the group consisting of triarylmethane pigments, xanthene pigments, anthraquinone pigments, azo pigments, quinoneimine pigments, polymethine pigments, subphthalocyanine pigments, and phthalocyanine pigments. Preferably, a structure derived from a pigment selected from the group consisting of triarylmethane pigments, xanthene pigments, quinoneimine pigments, and polymethine pigments is more preferable, and consists of triarylmethane pigments, xanthene pigments, quinoneimine pigments, and cyanine pigments. A structure derived from a dye selected from the group is more preferred. In addition, for specific dyes capable of forming a dye structure, "New Edition Dye Handbook" (edited by the Society of Organic Synthetic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), "Color Handbook" ( Compiled by Ogawara et al; Kodansha, 1986).

The dye structure may be composed of a cationic moiety or an anionic moiety, and examples thereof include a salt of a cationic chromophore and a counter anion, and a salt of an anionic chromophore and a counter cation. The counter ion may be an organic ion or an inorganic ion. Here, in this specification, "cationic chromophore" refers to an atomic group having an electrostatic charge. In addition, when an atomic group has a functional group having a positive charge and a functional group having a negative charge, and these charges are added together to have a positive charge as a whole, it is considered to be included in the cationic chromophore. "Anionic chromophore" refers to an atomic group having a negative charge. In addition, when an atomic group has a functional group having a positive charge and a functional group having a negative charge, and the total of these charges becomes a negative charge, it is considered to be included in the anionic chromophore. Further, the dye structure may be an electrically neutral chromophore. An "electrically neutral chromophore" is an atomic group that does not correspond to either a cationic or anionic chromophore, and does not have a functional group having a positive charge or a functional group having a negative charge, or a functional group having a positive charge and a negative charge. Even if it has a functional group, the total number of positive charges and the total number of negative charges are the same, and it refers to an atomic group that is electrically neutral as a whole.

The structural unit (a) is preferably a structural unit derived from a compound represented by the following formula (a1), since a polymer having a partial structure represented by the formula (1) can be obtained relatively easily. Specific examples of the compound represented by the following formula (a1) include compounds represented by each of the following formulas (a1-1) to (a1-9).

(In formula (a1), R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹ , R ² , L ¹ , X ¹ , n1 and n2 each have the same meaning as in formula (1) above. )

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

In the polymer (A1), the content ratio of the structural unit (a) is preferably 5% by mass or more with respect to all the structural units of the polymer (A1) from the viewpoint of sufficiently increasing the solvent resistance of the cured film, It is more preferable that it is 10 mass % or more, and it is still more preferable that it is 15 mass % or more. The content of the structural unit (a) is preferably 50% by mass or less with respect to all the structural units of the polymer (A1) from the viewpoint of maintaining workability and good colorability when preparing a coloring composition, It is more preferably 45% by mass or less, and even more preferably 40% by mass or less.

It is preferable that structural unit (b) is a structural unit derived from the ethylenically unsaturated monomer which has a dye structure. The dye structure of the constituent unit (b) is preferably a structure derived from a dye selected from the group consisting of ionic dyes and nonionic dyes from the viewpoint of obtaining pixels with high luminance and color purity. Here, in this specification, an ionic dye in which a chromophore has an acidic group is referred to as an "anionic dye". Anionic dyes are meant to include ionic dyes that form salts with acidic groups. Similarly, ionic dyes in which a chromophore has a basic group are referred to as "cationic dyes". A cationic dye is the meaning containing the ionic dye which forms the salt with a basic group. "Nonionic dyes" are dyes other than cationic dyes and anionic dyes.

The constituent unit (b) is at least one member selected from the group consisting of (meth)acrylic monomers, styrenic monomers, and maleimide monomers among ethylenically unsaturated monomers in view of the ease of introducing a dye structure into the side chain of the polymer. It is preferable that it is a structural unit derived from . Among these, a structural unit derived from a (meth)acrylic monomer is preferable, and a structural unit represented by the following formula (b1) is particularly preferable.

(In formula (b1), 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, and Y ¹ is a structure derived from an ionic dye or a nonionic dye It is a monovalent group having

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

Examples of structures derived from nonionic dyes in Y ¹ include triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, coumarin dyes, and pyrazolone. and structures derived from known dyes such as dyes, quinoline dyes, nitro dyes, quinoneimine dyes, phthalocyanine dyes, and squarylium dyes. Among these, from the viewpoint of heat resistance, the structure derived from a nonionic dye is a structure derived from a triarylmethane dye, cyanine dye, xanthene dye, anthraquinone dye, dipyrromethene dye, squarylium dye or phthalocyanine dye desirable.

In Y ¹ , specific examples of the structure derived from an ionic dye include a structure composed of a cationic chromophore and a counter anion, and a structure composed of an anionic chromophore and a counter cation. In the formula (b1), when the dye structure of Y ¹ is bonded to L ² , when the dye structure of Y ¹ is composed of a cationic chromophore and a counter anion, either of the cationic chromophore and the counter anion directly Or it is formed by bonding to L ² through a divalent linking group. Further, when the dye structure of Y ¹ is composed of an anionic chromophore and a counter cation, the bond between the dye structure ^of Y 1 and L ² is either directly or through a divalent linking group. It is formed by bonding to L ² .

As the cationic chromophore, for example, triarylmethane chromophore, cyanine chromophore, xanthene chromophore, polymethine chromophore, azo chromophore, diarylmethane chromophore, quinoneimine chromophore, anthraquinone chromophore, phthalocyanine chromophore, squarylium chromophore, quinop A talon chromophore etc. are mentioned. Among these, the cationic chromophore is preferably a triarylmethane chromophore, a cyanine chromophore, a xanthene chromophore, a polymethine chromophore, or an azo chromophore, and a triarylmethane chromophore or a cyanine chromophore is more preferable. As the cationic chromophore, the cationic portion of a dye classified as C.I. basic in the color index (C.I.; published by The Society of Dyers and Colourists) can also be used.

In the structure composed of a cationic chromophore and a counter anion, the counter anion is not particularly limited, and examples thereof include an anion described in paragraph 0034 of Japanese Unexamined Patent Publication 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 sulfonylimide anion is still more preferable.

Examples of the anionic chromophore include triarylmethane chromophore, polymethine chromophore, azo chromophore, diarylmethane chromophore, quinoneimine chromophore, anthraquinone chromophore, phthalocyanine chromophore, xanthene chromophore, squarylium chromophore, quinophthalone chromophore, etc. can be heard Among these, the anionic chromophore is preferably a triarylmethane chromophore, an azo chromophore, a phthalocyanine chromophore, or a xanthene chromophore, and has a substituent of at least one of -SO ₃ - and -CO ₂ -, a triarylmethane chromophore, an azo chromophore, A phthalocyanine chromophore or a xanthene chromophore is more preferred. As the anionic chromophore, an anionic portion of a dye classified as a CI acid in the above color index may be used.

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

In the polymer (A1), the content ratio of the structural unit (b) is preferably 30% by mass or more, and 40% by mass with respect to all the structural units of the polymer (A1) from the viewpoint of obtaining a coloring agent exhibiting good colorability. It is more preferable that it is more than that, and it is still more preferable that it is 50% by mass or more. The content of the structural unit (b) is preferably 99% by mass or less, and preferably 98% by mass or less, with respect to all the structural units of the polymer (A1) from the viewpoint of ensuring the solubility of the polymer (A1) in a developing solution. It is more preferable, and it is still more preferable that it is 95 mass % or less.

The polymer (A1) may have only the structural unit (a) and the structural unit (b), but any of the partial structure and dye structure represented by the above formula (1) from the viewpoint of improving solvent resistance, heat resistance, and dispersibility. It is preferable to further have a structural unit (c) having neither. The structural unit (c) is preferably a structural unit derived from an ethylenically unsaturated monomer, and is a structural unit derived from at least one selected from the group consisting of (meth)acrylic monomers, styrenic monomers, and maleimide monomers. is more preferable.

Specific examples of the monomers forming the structural unit (c) (hereinafter also referred to as “other monomers”) include, for example, alkyl (meth)acrylates, alkenyl (meth)acrylates, aryl (meth)acrylates, Hydroxyalkyl (meth)acrylate, primary amino group-containing alkyl (meth)acrylate, secondary amino group-containing alkyl (meth)acrylate, tertiary amino group-containing alkyl (meth)acrylate, alicyclic hydrocarbon group-containing (meth) Acrylic acid esters, aromatic vinyl compounds, (meth)acrylic acid esters of polyhydric alcohols, N-substituted maleimides, vinyl ethers, ethylenically unsaturated monomers having oxygen-containing saturated heterocycles, mono(meta) at the ends of polymer molecular chains and macromonomers having an acryloyl group. The polymer (A1) may have only one type of structural unit (c), or may have two or more types.

As the other monomer, by using a monomer having a hydroxyl group (hereinafter also referred to as "hydroxyl group-containing monomer"), (A) as a coloring agent, 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. By using such a polymer (A1-1) as the (A) colorant, a crosslinked structure is formed between the molecules of the polymer (A1-1) and the elution of the colorant from the cured film can be sufficiently suppressed, which is preferable. In addition, the polymer (A1-1) is also a specific compound and is also a hydroxyl group-containing compound. The hydroxyl group-containing monomer is preferably an ethylenically unsaturated monomer, and more preferably at least one selected from the group consisting of (meth)acrylic monomers, styrene-based monomers, and maleimide-based monomers, and (meth)acrylic monomers and styrene It is more preferable that it is at least 1 type selected from the group which consists of type monomers, and it is especially preferable that it is a (meth)acrylic type monomer.

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

Side chain glycols such as 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, and glycidyl (meth)acrylate A monomer obtained by adding an acid monomer such as (meth)acrylic acid to a cydyl group, 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, 3,4 -A monomer obtained by adding an acid monomer such as (meth)acrylic acid to an alicyclic epoxy group of a side chain such as epoxycyclohexylmethyl (meth)acrylate, or 3,4-epoxycyclohexylmethyl to an acid monomer such as (meth)acrylic acid (meth)acrylic acid, etc. 2, such as a monomer to which an acid monomer is added and a monomer to which a side chain oxetanyl group such as (3-ethyl-3-oxetanyl)methoxymethyl (meth)acrylate is added to an acid monomer such as (meth)acrylic acid a monomer containing a quaternary hydroxyl group;

and tertiary hydroxyl group-containing monomers such as 2,2-dimethyl-2-hydroxyethyl (meth)acrylate. As a hydroxyl-containing monomer, you may use individually by 1 type, and may use 2 or more types together.

The hydroxyl group-containing monomer used in the synthesis of the polymer (A1-1) is excellent in reactivity with the groups "OR ¹ " and "OR ² " of the partial structure represented by the above formula (1), so that the polymer side chain has a first class and/or a monomer having a secondary alcoholic hydroxyl group is preferred. Among them, the hydroxyl group-containing monomer is preferably at least one selected from the group consisting of a primary hydroxyl group-containing monomer, a primary hydroxyl group- and secondary hydroxyl group-containing monomer, and a secondary hydroxyl group-containing monomer. Examples of the primary hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. , (meth)acrylic acid hydroxyalkyl esters such as 8-hydroxyoctyl (meth)acrylate are particularly preferred. As a monomer containing a primary hydroxyl group and a secondary hydroxyl group, glycerol mono(meth)acrylate is particularly preferred. As the secondary hydroxyl group-containing monomer, a monomer obtained by adding an acid monomer such as (meth)acrylic acid to a glycidyl group of a side chain such as glycidyl (meth)acrylate, and glycidyl to an acid monomer such as (meth)acrylic acid Monomers to which a side chain glycidyl group is added such as (meth)acrylate, and acid monomers such as (meth)acrylic acid are added to a side chain alicyclic epoxy groups such as 3,4-epoxycyclohexylmethyl (meth)acrylate. monomers, monomers in which an alicyclic epoxy group of a side chain such as 3,4-epoxycyclohexylmethyl (meth)acrylate is added to an acid monomer such as (meth)acrylic acid, (3-ethyl-3-oxetanyl)methoxy (3-ethyl-3-oxetanyl) methyl (3-ethyl-3-oxetanyl) monomers to which acid monomers such as (meth)acrylic acid are added to side chain oxetanyl groups such as methyl (meth)acrylate, and acid monomers such as (meth)acrylic acid Monomers to which a side chain oxetanyl group is added, such as oxymethyl (meth)acrylate, are particularly preferred.

As a method for obtaining the polymer (A1-1), in addition to the method of polymerizing the above-described hydroxyl group-containing monomer, the specific group-containing monomer, and the monomer having a dye structure as raw material monomers (method [1a]), the following method [2a] - [4a] are mentioned.

Method [2a]: A polymer having an epoxy group in a side chain is obtained by polymerization using an epoxy group-containing monomer (or a carboxyl group-containing monomer), a specific group-containing monomer, and a monomer having a dye structure as raw material monomers, and then the polymer and the carboxyl group A method of introducing a hydroxyl group (more specifically, a secondary hydroxyl group) into a side chain by reacting a group-containing compound (or an epoxy group-containing compound).

Method [3a]: Using a polymerization initiator having a hydroxyl group (for example, 2,2'-azobis(2-methyl-N-(2-hydroxyethyl)propionamide), etc.), A method of polymerizing a raw material monomer containing a monomer having a dye structure.

Method [4a]: Using a chain transfer agent containing a hydroxyl group (for example, thioglycolic acid monoethanolamine, 2,3-dihydroxy-1,4-butanedithiol, etc.), a specific group-containing monomer and a dye A method of polymerizing a raw material monomer including a monomer having a structure.

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

In method [2a], the epoxy group-containing monomer is preferably a (meth)acrylic monomer, and examples thereof include oxiranyl group-containing (meth)acrylic monomers 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, etc. are mentioned. As the carboxy group-containing compound, a compound having a carboxy group and an ethylenically unsaturated bond is preferable, a (meth)acrylic compound is more preferable, and (meth)acrylic acid is particularly preferable. The polymer (A1-1) is preferably a polymer having a hydroxyl group at least in the side chain from the viewpoint of being easy to adjust the amount of hydroxyl groups the polymer has and from the viewpoint of being able to obtain a hydroxyl group-containing polymer relatively easily.

In the polymer (A1-1), the content ratio of the structural unit having a hydroxyl group is preferably 0.5% by mass or more with respect to all the structural units of the polymer (A1-1) from the viewpoint of obtaining a colored cured film with high solvent resistance. And, it is more preferably 1% by mass or more, and more preferably 5% by mass or more. From the viewpoint of improving the storage stability, the content of the structural unit having a hydroxyl group is preferably 50% by mass or less, and more preferably 45% by mass or less, with respect to all the structural units of the polymer (A1-1). and more preferably 40% by mass or less.

In addition, the method for obtaining the polymer (A1) is not particularly limited. The polymer (A1) can be produced using the above monomers 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 method [2a], the reaction between the epoxy group-containing monomer and the carboxy group-containing compound can be carried out in a solution, for example, according to a known method.

(About hydroxyl group-containing compounds)

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

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 achieving both solvent resistance and storage stability.

As a hydroxyl group-containing dye (A2-1), the hydroxyl group-containing dye of Unexamined-Japanese-Patent No. 2013-173850, international publication 2014/192973 pamphlet etc. is mentioned, for example. Moreover, it can manufacture by a well-known method using the well-known dye illustrated above as a raw material. As for the hydroxyl group-containing dye (A2-1), one type may be used alone, or two or more types may be used.

(A) In the case of using a polymer having a hydroxyl group as the coloring agent, as the polymer, in addition to the polymer (A1-1), a polymer having a hydroxyl group and a pigment structure and not having a partial structure represented by the above formula (1) (hereinafter , also referred to as “hydroxyl group-containing polymer (A2-2)”). The hydroxyl group-containing polymer (A2-2) should just have a hydroxyl group and a dye structure, and the position of a hydroxyl group is not specifically limited. That is, the hydroxyl group-containing polymer (A2-2) may have a hydroxyl group in a side chain, may have a hydroxyl group in a main chain terminal, or may have 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), in the methods [1a] to [4a] described for the polymer (A1-1), a method of polymerizing without using a specific group-containing monomer is exemplified. In addition, when manufacturing a hydroxyl-containing polymer (A2-2), only 1 type of these methods may be used, or 2 or more types may be combined. The polymer (A2-2) is preferably a polymer having a hydroxyl group in at least a side chain from the viewpoint of being easy to adjust the amount of hydroxyl groups and being able to obtain a hydroxyl-containing polymer relatively easily.

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

(A) When the colorant is a polymer, the weight average molecular weight (Mw) of the polymer measured by gel permeation chromatography (GPC) is preferably 1,000 to 100,000. Mw is preferably 3,000 or more. Also, Mw is preferably 50,000 or less. When Mw is 1,000 or more, it is preferable in that the pattern shape becomes good, and when it is 100,000 or less, the resolution time does not become too long, and it is preferable from the viewpoint of ensuring fairness. Moreover, (A) When a coloring agent is a polymer, ratio (Mw/Mn) of Mw of the polymer and number average molecular weight (Mn) 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 (A) a coloring agent, but a coloring agent having neither a partial structure represented by the above formula (1) nor a hydroxyl group (hereinafter also referred to as "other coloring agents"). ) may be used in combination. Further, in the case where the partial structure represented by the formula (1) and a hydroxyl group are included in at least one component selected from the group consisting of (B) polymer and (C) polymerizable compound, the coloring composition is (A) the colorant As such, it may contain only other colorants.

Other colorants are not particularly limited, and colors and types can be appropriately selected according to the intended use. As other colorants, any of pigments, dyes, quantum dots, and natural pigments can be used. When the coloring composition of the present disclosure is used to form pixels of each color constituting a color filter, pixels having high luminance and color purity can be obtained, and other colorants include at least one selected from the group consisting of pigments and dyes Species are preferred, and at least one selected from the group consisting of organic pigments and organic dyes is more preferred.

Examples of organic pigments include compounds classified as pigments in the color index (C.I.; published by The Society of Dyers and Colourists), that is, those with the following color index (C.I.) names, and the following organic pigments can be preferably used.

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. red pigments such as Pigment Red 279;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. green pigments such as Pigment Green 59;

C.I. Pigment Blue 15:6, C.I. Pigment Blue 16, C.I. Pigment Blue 79, C.I. Pigment Blue 80, C.I. blue pigments such as Pigment Blue 60;

C.I. 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, C.I. yellow pigments such as Pigment Yellow 231;

C.I. orange pigments such as Pigment Orange 38; C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. purple pigments such as Pigment Violet 29; Black pigments such as lactam-based black pigments and perylene-based black pigments.

Moreover, as an organic pigment, a brominated diketopyrrolopyrrole pigment represented by Formula (Ic) of Unexamined-Japanese-Patent No. 2011-523433 can also be used besides the above.

Carbon black, titanium black, etc. are mentioned as an inorganic pigment. As an inorganic pigment, in addition, Japanese Unexamined Patent Publication No. 2001-081348, Japanese Unexamined Patent Publication No. 2010-026334, Japanese Unexamined Patent Publication No. 2010-237384, Japanese Unexamined Patent Publication No. 2010-237569, Japanese Unexamined Patent Publication 2011-006602 No., the lake pigment of Unexamined-Japanese-Patent No. 2011-145346 etc. is mentioned.

In the case of using a pigment, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof before use. Further, if desired, the surface of the pigment particle may be modified with a resin and used. In addition, when using an organic pigment, you may refine|miniaturize a primary particle by what is called salt milling, and you may use it. As a method of salt milling, the method described in Unexamined-Japanese-Patent No. 08-179111 is employable, for example.

The dye is not particularly limited, and known dyes other than compounds classified as dyes in the color index can be used, for example. As such a dye, the well-known dye illustrated above is mentioned. Among the above, from the viewpoint of heat resistance, triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, and phthalocyanine dyes are preferable.

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

In the coloring composition of the present disclosure, if desired, a dispersant may be blended together with the coloring agent (A). Moreover, you may contain a dispersing aid together with a dispersing agent in a coloring composition. A well-known thing can be used as a dispersing agent and a dispersing aid. Specifically, as a dispersing agent, for example, a urethane-based dispersing agent, a polyethyleneimine-based dispersing agent, a polyoxyethylene alkyl ether-based dispersing agent, a polyoxyethylene alkylphenyl ether-based dispersing agent, a polyethylene glycol diester-based dispersing agent, a sorbitan fatty acid ester-based dispersing agent, poly ester-based dispersants, acrylic-based dispersants, and the like; As a dispersing aid, a pigment derivative etc. are mentioned, respectively, for example.

Specific examples of the dispersant are basic dispersants such as Solspers 11200, Solspers 13240, Solspers 13650, Solspers 13940, Solspers 16000, Solspers 17000, Solspers 18000, Solspers 20000, Solspers 24000SG, Solspers 24000GR, Solspurs 28000, Solspurs 31845, Solspurs 32000, Solspurs 32500, Solspurs 32550, Solspurs 32600, Solspurs 33000, Solspurs 34750, Solspurs 35100, Solspurs 35200, Solspurs 37500, Solspurs 38500; Solspers 39000, Solspers 56000, Solspers 71000, Solspers 76400, Solspers 76500, Solspers X300, Solsperse 9000, Solspers J200 (manufactured by Lubrizol), DISPERBYK-108, DISPERBYK-109, DISPERBYK- 112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-182, DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBYK-2000, DISPERBYK-2008, DISPERBYK-2009, DISPERBYK-2022, DISPERBYK-2050, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164, BYK-9077 (above, manufactured by Big Chemie) , Ajisper PB821, PB822, PB823, PB824, PB827 (above, manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like.

As the acidic dispersant, Solspers 3000, Solspers 21000, Solspers 26000, Solspers 36600, Solspers 41000, Solspers 41090, Solspers 43000, Solspers 44000, Solspers 46000, Solspers 47000, Solspers 55000 (above, manufactured by Lubrizol), DISPERBYK-102, DISPERBYK-111, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-2096, BYK-P104, BYK-P104S, BYK-P105, BYK-220S (above, Big Chemistry) production), etc. A dispersing agent may be used individually by 1 type, or may be used in combination of 2 or more types.

(A) The content ratio of the coloring agent can be appropriately selected depending on the application or the like. From the viewpoint of forming a pixel having high luminance and excellent color purity, or forming a black matrix having excellent light-shielding properties, the content ratio of the coloring agent (A) is preferably 5 to 5 to the total solid content of the coloring composition. It is 70 mass %. (A) The content ratio of the coloring agent is more preferably 8% by mass or more, still more preferably 10% by mass or more, and particularly preferably 12% by mass or more with respect to the total amount of the total solid content of the coloring composition. Further, the content ratio of the coloring agent (A) is more preferably 60% by mass or less, still more preferably 55% by mass or less, and particularly preferably 45% by mass or less with respect to the total amount of the total solid content of the coloring composition. .

(A) It is preferable that the content rate of dye in a coloring agent shall be 5 mass % or more with respect to the total amount of the coloring agent (A). In general, since dyes are inferior in heat resistance, when forming a cured film using a coloring composition containing a dye, it is difficult to heat the coated film at a postbaking temperature of 200°C 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°C, preferably 180°C or less. Therefore, the coloring composition of this indication can increase the content rate of a dye, and can be used suitably for preparation of various color filters. From the viewpoint of obtaining a colored cured film having high luminance and color purity, the content ratio of the dye is more preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 30% by mass or more with respect to the total amount of the coloring agent (A). This is particularly preferred.

<(B) polymer>

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

When the polymer (B) is an alkali-soluble polymer, the polymer (B) is not particularly limited as long as it is soluble in an alkali solution, but is preferably a polymer having an acidic functional group such as a carboxy group or a phenolic hydroxyl group. (B) The polymer is preferably a polymer having a carboxyl group (hereinafter, also referred to as a "carboxyl group-containing polymer") among these. As the carboxyl group-containing polymer, for example, an ethylenically unsaturated monomer having at least one carboxy group (hereinafter also referred to as "unsaturated monomer (b1)") and an ethylenically unsaturated monomer copolymerizable with the unsaturated monomer (b1) (hereinafter, and copolymers with "unsaturated monomer (b2)").

Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, monosuccinic acid [2-(meth)acryloyloxyethyl], ω-carboxypolycaprolactone mono(meth)acrylate, p - Vinyl benzoic acid, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalic acid, etc. are mentioned. The carboxy group-containing polymer may have only one type of structural unit derived from the unsaturated monomer (b1), or may have a combination of two or more types.

In the above copolymer, the content ratio of the structural units derived from the unsaturated monomer (b1) is 5% by mass relative to all the structural units of the polymer (B) from the viewpoint of obtaining a colored cured film having excellent alkali developability. It is preferable that it is above, and it is more preferable that it is 8 mass % or more. In addition, the content ratio of the structural unit derived from the unsaturated monomer (b1) is preferably 30% by mass or less, and 20% by mass, based on all the structural units of the copolymer, from the viewpoint of improving the solubility in the solvent. It is more preferable that it is below.

The unsaturated monomer (b2) can be appropriately selected depending on the application and the like, and is not particularly limited. (B) In synthesizing the polymer, by using an ethylenically unsaturated monomer having a partial structure represented by the formula (1) as the unsaturated monomer (b2) (hereinafter also referred to as "specific group-containing monomer"), (B) Certain compounds can be obtained as polymers. Moreover, by using an ethylenically unsaturated monomer having a hydroxyl group as the unsaturated monomer (b2), a hydroxyl group-containing compound can be obtained as the (B) polymer.

(for specific compounds)

In one aspect of the coloring composition of the present disclosure, the polymer (B) contains a specific compound. (B) Since the specific compound as a polymer is easy to synthesize a polymer having a partial structure represented by the above formula (1) in a side chain, a polymer having a structural unit (a) (hereinafter also referred to as "polymer (B1)") It is desirable to be For examples and preferable examples of the specific group-containing monomer used to have the constituent unit (a), the description of the colorant (A) applies.

In the polymer (B1), the content ratio of the structural unit (a) is preferably 2% by mass or more with respect to all the structural units of the polymer (B1) from the viewpoint of sufficiently increasing the solvent resistance of the cured film, It is more preferable that it is 5 mass % or more, and it is still more preferable that it is 10 mass % or more. In addition, the content ratio of the structural unit (a) is preferably 80% by mass or less, and preferably 70% by mass or less with respect to all the structural units of the polymer (B1) from the viewpoint of being able to maintain the storage stability of the coloring composition. It is more preferable, and it is still more preferable that it is 60 mass % or less.

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

As a method for obtaining the polymer (B1-1), the following methods [2b] to [4b] can be cited in addition to the method of polymerizing a hydroxyl group-containing monomer and a specific group-containing monomer as raw material monomers (method [1b]). can

Method [2b]: A polymer having an epoxy group in a side chain is obtained by polymerization using an epoxy group-containing monomer (or a carboxy group-containing monomer) and a specific group-containing monomer as raw material monomers, and then the polymer and a carboxy group-containing compound (or an epoxy group-containing compound) compound) to introduce a hydroxyl group (more specifically, a secondary hydroxyl group) into the side chain.

Method [3b]: Using a polymerization initiator having a hydroxyl group (for example, 2,2'-azobis(2-methyl-N-(2-hydroxyethyl)propionamide), etc.), a specific group-containing monomer is A method of polymerizing raw material monomers comprising

Method [4b]: containing a specific group-containing monomer using a chain transfer agent containing a hydroxyl group (eg, thioglycolic acid monoethanolamine, 2,3-dihydroxy-1,4-butanedithiol, etc.) A method for polymerizing a raw material monomer that

In addition, the description of the said method [2a] applies to the specific example of the epoxy-group-containing monomer and carboxy-group-containing compound used in method [2b]. The polymer (B1-1) is preferably a polymer having a hydroxyl group at least in the side chain from the viewpoints of being easy to adjust the amount of hydroxyl groups the polymer has and from the viewpoint of being able to obtain a hydroxyl group-containing polymer relatively easily.

Examples of the unsaturated monomer (b2) used in the synthesis of the polymer (B1) include N-alkylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide in addition to the above. N-substituted maleimides such as; Aromatic vinyl compounds, such as styrene, (alpha)-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-methoxy Ethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane- 8-yl(meth)acrylate, dicyclopentenyl(meth)acrylate, glycidyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, 3-[(meth)acrylo (meth)acrylic acid esters such as yloxymethyl]oxetane and 3-[(meth)acryloyloxymethyl]-3-ethyloxetane;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane vinyl ethers such as;

and macromonomers having mono(meth)acryloyl groups at the ends of polymer molecular chains such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane. (B) The polymer may have only 1 type of structural unit derived from an unsaturated monomer (b2), and may have it in combination of 2 or more types.

(About hydroxyl group-containing compounds)

In one aspect of the coloring composition of the present disclosure, the polymer (B) contains a hydroxyl group-containing compound. (B) When a polymer having a hydroxyl group is used as the polymer, the polymer, other than the polymer (B1-1), has a hydroxyl group and does not have a partial structure represented by the above formula (1) (hereinafter referred to as "hydroxyl group"). Also referred to as "containing polymer (B2)"). The hydroxyl group-containing polymer (B2) may have a hydroxyl group in a side chain, may have a hydroxyl group in a main chain terminal, or may have a hydroxyl group in both a side chain and a main chain terminal. Among these, it is preferable that the hydroxyl group-containing polymer (B2) is a polymer having a hydroxyl group at least in the side chain from the viewpoint of easy adjustment of the amount of hydroxyl group and the ability to obtain the hydroxyl group-containing polymer relatively easily. As a method of obtaining the hydroxyl group-containing polymer (B2), a method of polymerization without using a specific group-containing monomer in the methods [1b] to [4b] described in the polymer (B1-1) can be mentioned. For examples and preferred examples of the hydroxyl group-containing monomer used in the synthesis of polymer (B2), the description of the colorant (A) applies. In addition, when manufacturing a hydroxyl-containing polymer (B2), only 1 type of method [1b] - [4b] may be used, or you may combine 2 or more types.

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

(other polymers)

The coloring composition may contain only at least one of a specific compound and a hydroxyl group-containing compound as the (B) polymer, but a polymer having neither the partial structure represented by the above formula (1) nor a hydroxyl group (hereinafter also referred to as "other polymers"). ) may be used in combination. In addition, when a specific compound and a hydroxyl group-containing compound are included 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 polymers as the (B) polymer. good night.

Other polymers are not particularly limited and can be appropriately selected according to the intended use. Specific examples of other polymers include, for example, Japanese Unexamined Patent Publication No. 7-140654, Japanese Unexamined Patent Publication No. 8-259876, Japanese Unexamined Patent Publication No. Hei 10-31308, Japanese Unexamined Patent Publication No. Hei 10-300922, Copolymers disclosed in Japanese Unexamined Patent Publication No. 11-174224, Japanese Unexamined Patent Publication No. Hei 11-258415, Japanese Unexamined Patent Publication No. 2000-56118, Japanese Unexamined Patent Publication No. 2004-101728 and the like are exemplified. Moreover, as (B) polymer, for example, Japanese Unexamined Patent Publication No. 5-19467, Japanese Unexamined Patent Publication No. 6-230212, Japanese Unexamined Patent Publication No. 7-207211, Japanese Unexamined Patent Publication No. 9-325494 , As disclosed in Japanese Unexamined Patent Publication No. 11-140144, Japanese Unexamined Patent Publication No. 2008-181095, etc., a polymerizable unsaturated bond (for example, a carbon-carbon double bond in a (meth)acryloyl group) is attached to a side chain. It is also possible to use a carboxy group-containing polymer having

(B) The polymer can be produced by known methods such as radical polymerization, anionic polymerization, cationic polymerization, living radical polymerization, living anionic polymerization, and living cationic polymerization, for example. Further, the structure, Mw, and Mw/Mn thereof can also be controlled by methods disclosed in, for example, Japanese Laid-Open Patent Publication No. 2003-222717, Japanese Laid-Open Patent Publication No. 2006-259680, International Publication No. 07/029871, etc. . Moreover, as a (B) polymer, it can use individually by 1 type or in mixture of 2 or more types.

(B) It is preferable that the polystyrene equivalent weight average molecular weight (Mw) of the polymer measured by gel permeation chromatography (GPC) using tetrahydrofuran as the elution solvent is 1,000 to 100,000. Mw is preferably 3,000 or more. Also, Mw is preferably 50,000 or less. When Mw is 1,000 or more, it is preferable in terms of making the pattern shape good, and when it is 100,000 or less, the resolution time does not become too long, and it is preferable from the viewpoint of ensuring fairness.

Further, the ratio (Mw/Mn) of the Mw of the polymer (B) to the number average molecular weight (Mn) is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, Mn is a polystyrene conversion value measured by GPC using tetrahydrofuran as an elution solvent.

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

<(C) polymerizable compound>

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

As a polymeric group, an ethylenically unsaturated group, oxiranyl group, oxetanyl group, N-alkoxymethylamino group etc. are mentioned, for example. Among these, (C) the polymerizable compound is preferably a compound having two or more (meth)acryloyl groups or a compound having two or more N-alkoxymethylamino groups, and two or more (meth)acryloyl groups. It is particularly preferred that it is a compound having (C) The number of polymerizable groups in one molecule of the polymerizable compound is preferably 2 to 10, more preferably 2 to 8.

(About hydroxyl group-containing compounds)

In one aspect of the coloring composition of the present disclosure, (C) the polymerizable compound contains 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 reaction point with the group "-OR ¹ " and the group "-OR ² " in the formula (1) can be relatively easily introduced, and the content of the hydroxyl group in the coloring composition can be adjusted. Preferable in terms of ease.

From the viewpoint of achieving both solvent resistance and storage stability, the hydroxyl group-containing crosslinking agent (C1) preferably has 1 to 8 hydroxyl groups per molecule, more preferably 1 to 6, and even more preferably 1 to 4 hydroxyl groups. do. Moreover, it is especially preferable that the hydroxyl group-containing crosslinking agent (C1) is a compound having two or more (meth)acryloyl groups in view of its high reactivity to heat and light.

When the coloring composition of this indication contains only the hydroxyl-containing crosslinking agent (C1) as a hydroxyl-containing compound, the hydroxyl-containing crosslinking agent (C1) preferably has a hydroxyl value of 10 to 500 mgKOH/g. By setting the hydroxyl value of the hydroxyl group-containing crosslinking agent (C1) to a value within the above range, the effect of increasing the solvent resistance of the colored cured film obtained using the colored composition of the present disclosure and the effect of storage stability of the colored composition can be well-balanced. It is desirable in that it can be From the viewpoint of solvent resistance, the hydroxyl value of the hydroxyl group-containing crosslinking agent (C1) is more preferably 25 mgKOH/g or more, still more preferably 50 mgKOH/g or more. From the viewpoint of storage stability, the hydroxyl value of the hydroxyl group-containing crosslinking agent (C1) is more preferably 400 mgKOH/g or less, and still more preferably 300 mgKOH/g or less. In addition, in this specification, "hydroxyl value" shows the number of mg of KOH required to neutralize 1g of solid content of a hydroxyl-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, for example, pentaerythritol tri(meth)acrylic acid. )Acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, trimethylol Propane di(meth)acrylate, dipentaerythritol polyacrylate, etc. are mentioned. Among these, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol poly are considered to increase the cross-linking density between molecules or within molecules and improve film curability even by low-temperature baking. Acrylates are particularly preferred. Moreover, as a hydroxyl-containing crosslinking agent (C1), you may use individually by 1 type, and may use it in combination of 2 or more types.

(other polymerizable compounds)

The coloring composition may contain only a hydroxyl group-containing compound as (C) a polymerizable compound, but a polymerizable compound having neither a partial structure represented by the above formula (1) nor a hydroxyl group (hereinafter also referred to as “other polymerizable compounds”). ) may be used in combination. 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 coloring agent and (B) a polymer, the coloring composition is (C) a polymerizable compound. It may contain only other polymeric compounds.

Specific examples of other polymerizable compounds include compounds having two or more (meth)acryloyl groups, polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, and modified caprolactone. polyfunctional (meth)acrylate, alkylene oxide-modified polyfunctional (meth)acrylate, polyfunctional urethane (meth)acrylate obtained by reacting (meth)acrylate having a hydroxyl group and polyfunctional isocyanate, having a hydroxyl group The polyfunctional (meth)acrylate etc. which have a carboxyl group obtained by making (meth)acrylate and an acid anhydride react are mentioned.

Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, a melamine structure and a benzoguanamine structure mean the chemical structure which has at least one triazine ring or phenyl substituted triazine ring as a basic frame|skeleton, and is a concept also containing melamine, benzoguanamine, or those condensates. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, N,N,N',N'- Tetra(alkoxymethyl)benzoguanamine, N,N,N',N'-tetra(alkoxymethyl)glycoluril, etc. are mentioned.

As other polymerizable compounds, among others, polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylate, and polyfunctional urethane ( meth)acrylate, multifunctional (meth)acrylate having a carboxyl group, N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, N,N,N',N' -Tetra(alkoxymethyl)benzoguanamine is preferred, polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, polyfunctional urethane (meth)acrylate, having a carboxyl group Polyfunctional (meth)acrylates are more preferred. As another polymeric compound, it can use individually by 1 type or in mixture of 2 or more types.

It is preferable that it is 10 mass parts or more with respect to 100 mass parts of (A) coloring agents, and, as for content of the (C) polymeric compound in a coloring composition, it is more preferable that it is 20 mass parts or more. Moreover, it is preferable that it is 1,000 mass parts or less, and, as for content of (C) polymeric compound, it is more preferable that it is 500 mass parts or less with respect to 100 mass parts of (A) colorants. (C) When the content ratio of the polymerizable compound is within the above range, sufficient curability and sufficient alkali developability can be secured as a colored cured film, and scumming on the substrate or light-shielding layer in the unexposed area, film It is preferable from the viewpoint that the generation of residues and the like can be sufficiently suppressed.

The coloring composition of this indication may contain various components as needed other than the (A) coloring agent, (B) polymer, and (C) polymeric compound. The other component which may be contained in the coloring composition of this indication is demonstrated below.

<(D) Photopolymerization Initiator>

(D) Photopolymerization initiator is a compound that generates an active species capable of initiating polymerization of the (C) polymerizable compound by exposure to radiation such as visible rays, ultraviolet rays, deep ultraviolet rays, electron beams, and X-rays. Examples of such photopolymerization initiators include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acyloxime-based initiators, onium salt-based compounds, benzoin-based compounds, benzophenone-based compounds, and α-diketone-based compounds. compounds, polynuclear quinone-based compounds, diazo-based compounds, imide sulfonate-based compounds, and the like. Among these, it is preferable that the photoinitiator (D) contains an oxime-based initiator from the viewpoint of sufficiently generating radicals and sufficiently advancing film curing. As the oxime-based initiator, an O-acyloxime-based initiator can be preferably used.

Specific examples of O-acyloxime initiators include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6 -(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofura Nylmethoxybenzoyl) -9H-carbazol-3-yl] -,1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl -1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-,1-(O-acetyloxime), 1,2-propanedione,3-cyclohexyl-1-[4 -(phenylthio)phenyl]-,1-(O-acetyloxime) (a compound represented by the following formula (D-1)), a compound represented by the following formula (D-2)

etc. can be mentioned. As the O-acyloxime-based initiator, NCI-831, NCI-930 (above, manufactured by ADEKA Co., Ltd.), PBG-3057 (above, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Irgacure OXE03 (above, BASF You may use commercial items, such as Japan Co., Ltd. product).

As an O-acyloxime system initiator, it can use suitably also about the compound represented by each of the following formula (d-10), a formula (d-11), and a formula (d-12).

(In formula (d-10), X ¹ and X ² are each independently a single bond or -CO-. However, at least one of X ¹ and X ² is -CO-. R ¹ has 2 to 6 carbon atoms. is an alkyl group, R ² is an alkyl group having 4 to 10 carbon atoms, R ⁴ is a monovalent organic group having a hydrocarbon ring or a heterocyclic ring, and R ³ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms; It is a phenyl group.)

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

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

In the formulas (d-11) and (d-12), when R ⁶ , R ⁷ , R ⁸ or R ⁹ has a substituent, the substituent is a halogen atom, a nitro group, a hydroxyl group, a carboxy group, or a sulfonic acid. group, amino group, cyano group, etc. are mentioned. As the substituent for R ¹¹ and R ¹² , a halogen atom, a nitro group, a hydroxyl group, a carboxy group, a sulfonic acid group, an amino group and a cyano group, and at least one hydrogen atom selected from an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, or an alkylcycloalkyl group is selected from halogen and groups substituted with atoms, nitro groups, hydroxyl groups, carboxy groups, sulfonic acid groups, amino groups, or cyano groups.

As an O-acyloxime system initiator, since the contrast ratio of a cured film can be made more favorable, the acyl oxime compound which has a diphenyl sulfide skeleton, the acyl oxime compound which has a carbazole skeleton, and the acyl oxime which has a fluorene skeleton At least one selected from the group consisting of compounds can be preferably used. The O-acyloxime-based initiator is more preferably at least one selected from the group consisting of an acyloxime compound having a diphenylsulfide skeleton and an acyloxime compound having a fluorene skeleton.

(D) As for the content rate of a photoinitiator, 0.01 mass part or more is preferable with respect to 100 mass parts of (C) polymerizable compounds, and 1 mass part or more is more preferable. Moreover, 120 mass parts or less are preferable with respect to 100 mass parts of (C) polymeric compounds, and, as for the content rate of the photoinitiator (D), 100 mass parts or less are more preferable. (D) When the content of the photopolymerization initiator is in the above range, sufficient curing of the coating film by an appropriate amount of exposure and sufficient alkali developability as a coloring composition can be ensured, scumming on the substrate or light-shielding layer of the unexposed area, Generation of film residue can be sufficiently suppressed. Moreover, the decrease in luminance of the coating film due to yellowing of the polymerization initiator at the time of post-baking can be sufficiently suppressed. (D) A photoinitiator can be used individually by 1 type or in mixture of 2 or more types.

<(E) Solvent>

The colored composition of the present disclosure is prepared as a liquid composition by blending (E) a solvent. (E) As the solvent, those that disperse or dissolve the components (A), (B), and (C) and other components constituting the coloring composition, do not react with these components, and have appropriate volatility can be preferably used. there is.

(E) As specific examples of the solvent, 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, (poly)alkylene glycol monoalkyl ethers such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether;

lactate alkyl esters such as methyl lactate and ethyl lactate; Alkyl alcohols which may have straight-chain, branched or cyclic structures such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol and cyclohexanol; keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether (poly)alkylene glycol monoalkyl ether acetates such as 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-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxycarboxylic acids such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate esters;

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene;

amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and the like.

Among these, (E) solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol from the viewpoints of solubility, pigment dispersibility, coating properties, etc. Monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1 ,6-Hexanedioldiacetate, ethyl lactate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, At least one selected from the group consisting of i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate and ethyl pyruvate is preferred. In addition, (E) solvent can be used individually by 1 type or in mixture of 2 or more types.

The coloring composition of the present disclosure 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, It is preferable at the point which can improve the storage stability of. For specific alcohols, a solvent having a boiling point of 150°C or less is preferable in order to realize low-temperature baking. Preferred examples of specific alcohols include methanol, ethanol, propan-1-ol, butan-1-ol, and pentan-1-ol as primary alcohols; Examples of the secondary alcohol include propan-2-ol, butan-2-ol, pentan-2-ol, and hexan-2-ol. Among these, primary alcohols are preferred from the viewpoint of being able to obtain a colored composition having excellent storage stability.

In addition, in the coloring composition of the present disclosure, crosslinking at the time of film formation is due to a transesterification reaction, and since the transesterification reaction is a reversible reaction, the equilibrium is maintained by the presence of specific alcohols in the coloring composition, and the transesterification reaction It is thought that the storage stability of the coloring composition was able to be quantified by suppressing the progress of.

In the coloring composition of the present disclosure, the content ratio of the specific alcohol is 10% by mass or less with respect to the total amount of the solvent (E) contained in the coloring composition from the viewpoint of maintaining the dispersibility of the (A) coloring agent. It is preferable, 8 mass % or less is more preferable, and 7 mass % or less is still more preferable. The content of specific alcohols is preferably more than 0% by mass, more preferably 0.01% by mass or more, more preferably 0.5% by mass or more, and more preferably 1% by mass or more in order to obtain the effect of improving storage stability. more desirable than this. Moreover, as specific alcohol, it can use individually by 1 type or in combination of 2 or more types.

<(F) Additives>

The coloring composition may contain various additives other than the above as needed. Examples of additives include fillers such as glass and alumina; high molecular compounds such as polyvinyl alcohol and poly(fluoroalkylacrylates); surfactants such as fluorine-based surfactants and silicone-based surfactants; adhesion promoter; antioxidants; UV absorbers; polyfunctional thiols; Metal chelate compounds, such as a zirconium compound, a titanium compound, and an aluminum compound, etc. are mentioned. These blending ratios can be appropriately set according to the type 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 is within a suitable range for the content of the partial structure represented by the formula (1) and the content of the hydroxyl group, depending on the blending form of the specific compound and the hydroxyl group-containing compound. can be set appropriately so that

<Preparation of coloring composition>

The coloring composition of this indication can be prepared by an appropriate method. As its preparation method, the method disclosed in Unexamined-Japanese-Patent No. 2008-58642, Unexamined-Japanese-Patent No. 2010-132874 etc. is mentioned, for example. (A) When using both a dye and a pigment as a colorant, as disclosed in Japanese Laid-Open Patent Publication No. 2010-132874, after passing the dye solution through the first filter, the dye solution passed through the first filter, A method of preparing by mixing with a separately prepared pigment dispersion or the like and passing the obtained colored composition through a second filter can be adopted. In addition, after dissolving the dye, the above (B) polymer and (C) polymerizable compound, and other components used as necessary in a solvent, passing the obtained solution through a first filter, the solution passed through the first filter You may employ|adopt the method of preparing by mixing with the pigment dispersion liquid prepared separately, and passing the obtained coloring composition through a 2nd filter. Further, after passing the dye solution through the first filter, mixing and dissolving the dye solution that has passed through the first filter, the above (B) polymer and (C) polymerizable compound, and other components used as necessary, You may adopt the method prepared by passing the obtained solution through a 2nd filter, mixing the solution which passed through the 2nd filter with the pigment dispersion liquid prepared separately, and passing the obtained coloring composition through a 3rd filter.

[Color filter and manufacturing method thereof]

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

As a method of manufacturing a color filter, first, a light-shielding layer (black matrix) is formed on the surface of a substrate so as to partition a portion where pixels are formed, as needed. Next, after applying, for example, a green coloring composition (liquid composition) on this substrate, drying under reduced pressure or prebaking is performed to evaporate the solvent to form a coating film (film formation step). Next, after exposing this coating film through a photomask (exposure process), it develops using an alkaline developing solution (development process). 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, by post-baking (heating step), a pixel array in which green pixel patterns are arranged in a predetermined arrangement is formed.

Next, using each red or blue coloring composition, applying, drying, exposure, developing and post-baking each coloring composition in the same manner as above, and sequentially forming a red pixel array and a blue pixel array on the same substrate. form Thus, a color filter in which pixel arrays of three primary colors of green, red, and blue are disposed on the substrate is obtained. However, the order of forming pixels of each color is not limited to the above. The black matrix can be formed by using a photolithography method to form a metal thin film such as chromium formed into a film by sputtering or vapor deposition into a desired pattern. Moreover, it can also form by carrying out similarly to the case of formation of the said pixel using the coloring composition in which the black colorant was disperse|distributed.

As a board|substrate used when forming a color filter, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide etc. are mentioned, for example. These substrates may be subjected to appropriate pretreatment such as chemical treatment using a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction method, or vacuum deposition, as desired.

When applying the coloring composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), or a bar coating method can be employed. Among these, it is preferable to employ a spin coating method or a slit die coating method from the viewpoint of being able to obtain a coating film having a uniform film thickness. After coating, by drying under reduced pressure, a coating film is formed on the substrate. Reduced pressure drying is usually carried out at room temperature for 1 to 15 minutes, preferably 1 to 10 minutes, and is usually performed at a pressure reaching 50 to 200 Pa. Formation of the coating film may be performed by heat treatment (pre-baking) at a lower temperature than the post-baking temperature. The coating thickness, as the film thickness after drying, is usually 0.6 to 8 μm, preferably 1.2 to 5 μm.

As the light source of the radiation used during exposure, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a lamp 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, a low-pressure mercury lamp, an argon ion laser, a YAG laser, and XeCl Laser light sources, such as an excimer laser and a nitrogen laser, etc. are mentioned. As an exposure light source, an ultraviolet LED can also be used. The wavelength is preferably radiation in the range of 190 to 450 nm, more preferably radiation in the range of 300 to 450 nm. As for the exposure amount of radiation, 10-10,000 J/m<2> is generally preferable. The exposure amount of radiation is more preferably 100 J/m 2 or more, and still more preferably 200 J/m 2 or more. Further, the exposure dose of radiation is more preferably 5,000 J/m 2 or less, and still more preferably 2,000 J/m 2 or less.

Examples of the alkaline developer include sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1, An aqueous solution such as 5-diazabicyclo-[4.3.0]-5-nonene is preferred. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can also be added to the alkaline developer, for example. In addition, after alkali development, it is usually washed with water. As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (drilling) developing method, or the like can be applied. As for image development conditions, 5 to 300 second is preferable at normal temperature.

Post-baking is performed by heating the patterned coating film at 70 to 230°C. The post-baking temperature is, for example, 70 to 120 ° C., 120 ° C. to 180 ° C., 180 ° C. to 240 ° C., etc., taking into account the improvement of curing properties, solvent resistance, adhesion to the substrate, suppression of color transfer, and substrate protection. The heating temperature can be set accordingly. At that time, in order to sufficiently advance the transesterification reaction between at least one of the groups “OR ¹ ” and “OR ² ” of the specific compound and the OH group of the hydroxyl group-containing compound, alcohols contained in the coloring composition What is necessary is just to set a temperature higher than the boiling point of as the heating temperature at the time of post-baking. Although the heating time at the time of post-baking can be suitably set according to the heating temperature, in the low temperature of 70-120 degreeC, for example, it is 5-120 minutes normally, Preferably it is 30-100 minutes. The film thickness of the colored cured film (ie, pixel) formed on the substrate is usually 0.5 to 5 µm, preferably 1.0 to 3 µm.

On the pixel pattern obtained in this way, after forming a protective film as needed, a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to obtain a color filter. The spacer is usually formed using a transparent photosensitive resin composition, but it can also be used as a spacer (black spacer) having light-shielding properties. In this case, a photosensitive coloring composition in which a black colorant is dispersed is used. The coloring composition of this indication can be used suitably also for formation of such a black spacer.

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

[Display element]

The display element of the present disclosure includes the color filter of the present disclosure. As a display element, a color liquid crystal display element, an organic EL display element, electronic paper, etc. are mentioned.

The 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 Lamp (CCFL). As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixture by combining a blue LED, a red LED, and a green phosphor, and a blue LED. A white LED obtained by mixing a red light emitting phosphor and a green light emitting phosphor to obtain white light by color mixing, a white LED obtained by mixing a blue LED and a YAG phosphor to obtain white light, and a color mixture by combining a blue LED, an orange light emitting phosphor, and a green light emitting phosphor. A white LED that obtains white light by color mixing, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor.

The organic EL display element provided with the color filter of this indication can take an appropriate structure, and the structure currently disclosed in Unexamined-Japanese-Patent No. 11-307242 is mentioned, for example. In addition, the structure disclosed in Unexamined-Japanese-Patent No. 2007-41169 is mentioned for the electronic paper provided with the color filter of this indication, for example.

[Light Receiving Element]

The light-receiving element of the present disclosure includes a colored cured film formed using the coloring composition described above. The light-receiving element of the present disclosure can have an appropriate structure. For example, by using the above colored cured film as a color filter constituting a solid-state imaging element and combining it with a photodiode, an imaging element such as a solid-state imaging element can be constituted. can In addition, by using the cured film of the present disclosure as an infrared light transmission filter and combining it with a photodiode, an infrared light detecting pixel can be configured.

[Curable composition]

The curable composition of the present disclosure contains the polymer (B) and the polymerizable compound (C). In particular, the curable composition of the present disclosure has a partial structure in which at least one selected from the group consisting of (B) polymer and (C) polymerizable compound is represented by the above formula (1), (B) polymer and (C) polymerization At least one selected from the group consisting of sex compounds has a hydroxyl group. In addition, the partial structure represented by the above formula (1) and the hydroxyl group may exist in the same molecule or may exist in different molecules.

The curable composition of the present disclosure is a composition used to form a cured film. Examples of the cured film include color pixels used in display elements and light receiving elements, interlayer insulating films, planarization films, banks (partition walls) defining regions in which light emitting layers are formed, black matrices, spacers, protective films, and the like. As a display element, a color liquid crystal display element, an organic EL element, electronic paper, etc. are mentioned, for example, and as a light-receiving element, a CCD image sensor, a CMOS image sensor, etc. are mentioned, for example.

[Example]

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

(Crosslinkable Monomer)

(other monomers)

(dye monomer)

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

(dyes)

(hydroxyl group-containing dye)

(Photopolymerization Initiator)

(polymerizable compound)

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

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

1. Synthesis of dye resin

[Synthesis Example 1-1]

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

[Synthesis Examples 1-2 to 1-10, 1-12 to 1-22 and Comparative Synthesis Examples 1-1 to 1-4]

Polymers (A-2) to (A-10) and (A-12) to polymers (A-2) to (A-10), (A-12) to (A-22) and polymers (AR-1) to (AR-4) were synthesized, respectively. In Table 1, "-" indicates that the corresponding component was not blended (the same applies to the tables below).

[Synthesis Example 1-11]

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

[Synthesis Example 1-23]

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

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

[Synthesis Example 1-24, 1-25]

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

[Synthesis Example 1-26]

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

2.00 g of the polymer (A-26-1) synthesized above was dissolved in 40.0 mL of acetone. Next, as shown in the following reaction formula, an equivalent molar amount of C.I.Acid Blue 93 (acid dye I) was added to the number of moles of structural units derived from ammonium salt, calculated from the copolymerization ratio of polymer (A-26-1), and was stirred for 1 hour. Thereafter, 200 mL of ion-exchanged water was added to the residue obtained by concentrating the reaction solution under reduced pressure, and the resulting precipitate was filtered off and washed with water. The obtained solid was dried under reduced pressure at 50°C to obtain 2.62 g of a dye multimer (this is referred to as "polymer (A-26)") represented by the following structural formula. The obtained polymer (A-26) confirmed by GPC that Mw was 12,600 and Mn was 7,500.

[Synthesis Example 1-27]

Except for changing the cationic monomer to dimethylaminoethyl methacrylate (this is referred to as "basic monomer II"), by performing the same operation as in Synthesis Example 1-26, a cationic group-containing polymer represented by the following structural formula ( 15.02 g of this was referred to as "Polymer (A-27-1)". The obtained polymer (A-27-1) confirmed by GPC that Mw was 11,400 and Mn was 6,800. Subsequently, the dye of the polymer (A-27-1) and C.I.Acid Blue 93 (Acid Dye I) was obtained by performing the same operation as in Synthesis Example 1-26 using the polymer (A-27-1). A multimer (which is referred to as "polymer (A-27)") was obtained.

[Synthesis Example 1-28]

Except for changing the cationic monomer to N,N-dimethylaminomethylstyrene (this is referred to as “basic monomer III”), the cationic group represented by the following structural formula was carried out by carrying out the same operation as in Synthesis Example 1-26 above. 15.07 g of polymer (this is called "polymer (A-28-1)") was obtained. The obtained polymer (A-28-1) confirmed by GPC that Mw was 11,300 and Mn was 7,100. Subsequently, the dye of the polymer (A-28-1) and C.I.Acid Blue 93 (Acid Dye I) was obtained by performing the same operation as in Synthesis Example 1-26 using the polymer (A-28-1). A multimer (which is referred to as "polymer (A-28)") was obtained.

[Synthesis Example 1-29]

Except for changing the cationic monomer to N-vinylpyrrolidone (this is referred to as "basic monomer IV"), the cationic group-containing polymer represented by the following structural formula by performing the same operation as in Synthesis Example 1-26 above ( 15.03 g of this was referred to as "Polymer (A-29-1)"). The obtained polymer (A-29-1) confirmed by GPC that Mw was 12,100 and Mn was 7,400. Subsequently, the dye of the polymer (A-29-1) and C.I.Acid Blue 93 (Acid Dye I) was obtained by performing the same operation as in Synthesis Example 1-26 using the polymer (A-29-1). A multimer (referred to as "polymer (A-29)") was obtained.

[Synthesis Example 1-30]

Polymer (A-26-1) and C.I. Acid Red 289 (Acid Dye II) were prepared by performing the same operation as in Synthesis Example 1-26 except for using C.I. Acid Red 289 (Acid Dye II) as the acid dye. A dye multimer (this is referred to as "polymer (A-30)") was obtained.

In Table 2, the abbreviated names of the compounds are as follows.

Acidic monomer I: p-(vinylphenyl)trifluoromethanesulfonylimide acid triethylamine salt

Basic monomer I: methacryloylpropyltrimethylammonium chloride

Basic monomer II: dimethylaminoethyl methacrylate

Basic monomer III: N,N-dimethylaminomethylstyrene

Basic monomer IV: N-vinylpyrrolidone

2. Synthesis of Binder Resin

[Synthesis Example 2-1]

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

[Synthesis Examples 2-2 to 2-7, 2-9 to 2-17 and Comparative Synthesis Examples 2-1 to 2-5]

Polymers (B-2) to (B-7) and (B-9) to polymers (B-2) to (B-7), (B-9) to (B-17) and polymers (BR-1) to (BR-5) were synthesized, respectively.

[Synthesis Example 2-8]

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

[Synthesis Example 2-18]

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

[Synthesis Example 2-19]

In a reaction vessel, 19.4 g of compound (M-1), 26.4 g of methacrylic acid (MA), 24.2 g of butyl methacrylate (BMA), and 2,2'-azobis (2,4-dimethylvaleronitrile) were added. 7.0 g was weighed and dissolved in 100 g of propylene glycol monomethyl ether acetate and 30 g of n-butanol. The temperature of the reaction solution was raised to 75°C while stirring under a nitrogen stream, stirring was continued for 3 hours, then the temperature of the reaction solution was raised to 90°C, and 200 g of polymer solution was obtained by further polymerization for 1 hour. After cooling to room temperature, it was switched under an air flow, 27.0 g of methacrylic acid [(3,4-epoxycyclohexane)-1-yl]methyl and 1.9 g of tetrabutylammonium bromide (TBAB) were added thereto, and the temperature was 105°C. The heating reaction was performed for 10 hours. After cooling the reaction solution to room temperature, 240 g of a polymer solution having a solid content concentration of 40% by mass was recovered. The obtained polymer (this is called "polymer (B-19)") had Mw of 11,900 and Mn of 6,600.

[Synthesis Example 2-20]

3 parts by mass of 2,2'-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer. To this flask, 12 parts by mass of N-cyclohexylmaleimide (CHMI), 10 parts by mass of styrene, 20 parts by mass of methacrylic acid (MA), 15 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 2-ethyl 29 parts by mass of hexyl methacrylate (EHMA), 14 parts by mass of benzyl methacrylate (BzMA), and 5 parts by mass of pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd.) and nitrogen substitution. Thereafter, by stirring slowly, the temperature of the reaction solution was raised to 80°C, and the temperature was maintained at this temperature for 3 hours to perform polymerization. Thereafter, the temperature of the reaction solution was raised to 100°C and further polymerized for 1 hour to obtain a binder resin solution containing 33.3% by mass of a binder resin (this is referred to as "Polymer (BA-1)"). Polymer (BA-1) had Mw of 9,700 and Mn of 5,700.

[Synthesis Example 2-21]

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

3. Synthesis of hydroxyl-containing dyes

[Synthesis Example 3-1]

Using dye A1, 1 equivalent of succinic anhydride was stirred at room temperature in a pyridine solvent in the presence of a catalytic amount of dimethylaminopyridine, followed by solvent distillation, water washing, and dehydration followed by solvent distillation to obtain a terminal carbonic acid. Subsequently, 1 equivalent of tris(hydroxymethyl)aminomethane was stirred at room temperature using 1.2 equivalent of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride in a dichloromethane solvent, followed by washing with water. , After dehydration, solvent distillation was performed to obtain dye A3.

[Synthesis Example 3-2]

The target dye A4 was obtained in the same manner as in Synthesis Example 3-1 except that a dye in which the anion of the dye A2 was changed to an iodine anion was used instead of the dye A1.

[Synthesis Example 3-3]

Instead of dye A1, dye C as a target object was obtained in the same manner as in Synthesis Example 3-1 except for using the dye described in paragraph 0003 of Japanese Laid-open Patent Publication No. 2004-506775.

[Synthesis Example 3-4]

A target dye E was obtained in the same manner as in Synthesis Example 3-1 except for using the compound [2] described in Chinese Patent CN102786459 instead of dye A1.

In addition, dye A1 was synthesized by a known method, and dye D was synthesized by a known method with reference to Japanese Patent No. 2812624.

4. Preparation of colorant dispersion

[Preparation Example 4-1]

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

[Preparation Example 4-2]

The type of colorant is C.I. Except for changing to Pigment Green 59, preparation was performed in the same manner as in Preparation Example 4-1 above to obtain a colorant dispersion (MB-G-2).

[Preparation Example 4-3]

The type of colorant is C.I. Except for changing to Pigment Green 7, preparation was performed in the same manner as in Preparation Example 4-1 above to obtain a colorant dispersion (MB-G-3).

[Preparation Example 4-4]

The type of colorant is C.I. Except for changing to Pigment Yellow 138, preparation was performed in the same manner as in Preparation Example 4-1 above to obtain a colorant dispersion (MB-Y-1).

[Preparation Example 4-5]

The type of colorant is C.I. Except for changing to Pigment Yellow 139, preparation was performed in the same manner as in Preparation Example 4-1 above to obtain a colorant dispersion (MB-Y-2).

[Preparation Example 4-6]

The type of colorant is C.I. Except for changing to Pigment Yellow 185, preparation was performed in the same manner as in Preparation Example 4-1 above to obtain a colorant dispersion (MB-Y-3).

[Preparation Example 4-7]

The type of colorant is C.I. Except having changed to Pigment Red 177, it prepared similarly to the said Preparation Example 4-1, and obtained the coloring agent dispersion liquid (MB-R-1).

[Preparation Example 4-8]

The type of colorant is C.I. Except having changed to Pigment Blue 15:6, it prepared similarly to the said Preparation Example 4-1, and obtained the coloring agent dispersion liquid (MB-B-1).

[Preparation Example 4-9]

As a colorant, C.I. Pigment Blue 60 7 parts by mass, C.I. A colorant dispersion (MB-Bk-1) was prepared in the same manner as in Preparation Example 4-1 above, except that 6 parts by mass of Pigment Violet 29 was used.

[Preparation Example 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 colorant was changed to a lactam pigment (Irgaphor Black S0100 CF manufactured by BASF).

[Preparation Example 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 colorant was changed to a perylene pigment (Lumogen Black FK4280 manufactured by BASF).

[Preparation Example 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 colorant was changed to carbon black (TPX1227R manufactured by Cabot).

5. Preparation and evaluation of coloring composition [1]

[Example 1-1]

(1) Preparation of coloring composition

5.7 parts by mass of the polymer (A-1) obtained in the above Synthesis Example 1-1, 0.7 parts by mass of Valifast Orange32 (manufactured by Orient Chemical Industry Co., Ltd.), 11.7 parts by mass of a colorant dispersion (MB-Y-2), and a polymer (BA as binder resin) -1) as a polymer solution (solid content concentration: 33.3% by mass), 3.2 parts by mass of dipentaerythritol penta/hexaacrylate as 5.6 parts by mass, (C) a polymerizable compound, and (D) an oxime-based initiator as a photopolymerization initiator ( D-1) 1.0 parts by mass and 0.03 parts by mass of Megapack F-554 (manufactured by DIC Co., Ltd.) as a fluorine-based surfactant were mixed to 10% by mass of the total amount of solvents so that the solid content concentration of the final composition was 15.0% by mass. A corresponding amount of methoxybutyl acetate is added, an amount of n-butanol corresponding to 5% by mass of the total amount of solvents is added, diacetone alcohol in an amount corresponding to 20% by mass of the total amount of solvents is added, and the remainder is further added. A colored composition (G1-1) was prepared by adding propylene glycol monomethyl ether acetate in an amount corresponding to the amount of the solvent.

(2) Evaluation

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

(i) Evaluation of solvent resistance

The coloring composition (G1-1) was applied onto a soda glass substrate having a SiO ₂ film for preventing sodium ion elution formed on the surface using a spin coater, and then dried under reduced pressure at room temperature to form a coating film having a thickness of 2.5 μm. did.

Subsequently, radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to the coating film at an exposure amount of 600 J/m 2 using a high-pressure mercury lamp through a photomask. Thereafter, shower development was performed for 60 seconds by discharging a developing solution composed of a 0.04% by mass aqueous solution of potassium hydroxide at 23° C. to the substrate at a developing pressure of 1 kgf/cm 2 (nozzle diameter 1 mm). Thereafter, this substrate was washed with ultrapure water and air-dried, and then post-baked in a clean oven at 150°C for 30 minutes to form a rectangular pattern on the substrate. For this rectangular pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), chromaticity coordinate values (x, y) and stimulus values (Y) in the CIE color system in a C light source and a 2-degree field of view was measured.

Next, a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used for the rectangular pattern after being immersed in a mixed solvent of diethylene glycol methyl ethyl ether/ethylene glycol monobutyl ether = 50/50 (mass ratio) for 5 minutes. Chromaticity coordinate values (x, y) and stimulus values (Y) in the CIE color system were measured under a C light source and a 2-degree field of view. The color change before and after immersion, i.e., ΔE*ab, was calculated. The evaluation criteria are as follows.

(Evaluation standard)

◎: The value of ΔE*ab is 3.0 or less

○: The value of ΔE*ab is greater than 3.0 and less than or equal to 7.0

△: The value of ΔE*ab is greater than 7.0 and less than or equal to 15.0

×: the value of ΔE*ab is greater than 15.0

As a result of the evaluation, in Example 1-1, the solvent resistance was "◎".

(ii) Evaluation of storage stability

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

(Evaluation standard)

○: increase rate ΔV is less than 5%

△: The increase rate ΔV is 5% or more and less than 10%

×: increase rate ΔV is 10% or more

As a result of the evaluation, in Example 1-1, the storage stability was "○".

[Examples 1-2 to 1-30 and Comparative Examples 1-1 to 1-4]

In Example 1-1, except that the type of colorant and other components was changed as shown in Table 4 below, the chromaticity coordinate values (x, y) in the CIE color system in the C light source were changed. Example 1 In the same manner as in -1, coloring compositions (G1-2) to (G1-30) and (G1-1R) to (G1-4R) were prepared, respectively. About the obtained coloring composition (G1-2) - (G1-30) and (G1-1R) - (G1-4R), it carried out similarly to Example 1-1, and evaluated solvent resistance and storage stability. Their results are shown in Table 4 below.

In Table 4, the abbreviated names of the compounds are as follows (the same applies to Tables 5 to 9 below).

Q-1: Validast Orange3209

C-1: dipentaerythritol penta/hexaacrylate (manufactured by Toagose Co., Ltd., trade name Aronix M-402)

D-1: oxime-based initiator (compound represented by the above formula (D-1))

E1: methoxybutyl acetate

E2: propylene glycol monomethyl ether acetate

E3: n-butanol

E4: diacetone alcohol

E5: cyclohexanone

F-1: Mega Pack F-554 (manufactured by DIC Co., Ltd.)

6. Preparation and evaluation of coloring composition [2]

[Example 2-1]

(1) Preparation of coloring composition

28.5 parts by mass of colorant dispersion (MB-G-1), 29.1 parts by mass of colorant dispersion (MB-Y-1), 2.7 parts by mass of polymer (B-3) as a binder resin in a polymer solution (solid content concentration: 35% by mass), (C) 4.2 parts by mass of dipentaerythritol penta/hexaacrylate as a polymerizable compound, (D) 0.5 parts by mass of an oxime-based initiator (D-1) as a photopolymerization initiator, and Megapack F-554 as a fluorine-based surfactant ( 0.03 parts by mass of DIC Co., Ltd.) was mixed, and methoxybutyl acetate in an amount corresponding to 10% by mass of the total amount of solvents was added so that the solid content concentration of the final composition was 15.0% by mass, and 5% by mass of the total amount of solvents was added. A colored composition (G2-1) was prepared by adding an amount of n-butanol corresponding to , and further adding an amount of propylene glycol monomethyl ether acetate corresponding to the amount of the remaining solvent.

(2) Evaluation

About the coloring composition (G2-1), it carried out similarly to Example 1-1, and evaluated solvent resistance and storage stability. Their results are shown in Table 5 below.

[Examples 2-2 to 2-27 and Comparative Examples 2-1 to 2-5]

In Example 2-1, except that the type of colorant and other components was changed as shown in Table 5 below, the chromaticity coordinate values (x, y) in the CIE color system in the C light source were changed. Example 2 In the same manner as in -1, coloring compositions (G2-2) to (G2-27) and (G2-1R) to (G2-5R) were prepared, respectively. About the obtained coloring composition, it carried out similarly to Example 1-1, and evaluated solvent resistance and storage stability. Their results are shown in Table 5 below.

[Examples 2-28 to 2-31 and Comparative Examples 2-6 to 2-9]

Regarding the coloring composition (G2-4) and the coloring composition (G2-3R), the contents were the same as in Example 1-1 except that the temperature in the clean oven during post-baking was changed as shown in Table 6 below. The quality was evaluated. Their results are listed in Table 6 below.

[Example 2-32]

In Example 2-1, except that the type of colorant and other components was changed as shown in Table 6 below, the chromaticity coordinate values (x, y) in the CIE color system in the C light source were changed as in Example 2 It carried out similarly to -1, and prepared the coloring composition (G2-4A). About the obtained coloring composition (G2-4A), solvent resistance was evaluated like Example 1-1 except having changed the temperature in the clean oven at the time of post-baking to 85 degreeC. The results are listed in Table 6 below.

7. Preparation and evaluation of coloring composition [3]

[Example 3-1]

(1) Preparation of coloring composition

3.4 parts by mass of dye A1, 0.7 parts by mass of Valifast Orange3209 (manufactured by Orient Chemical Industry Co., Ltd.), 11.7 parts by mass of colorant dispersion (MB-Y-2), and polymer (B-13) as a binder resin in a polymer solution (solid content concentration) 35% by mass), 7.9 parts by mass, (C) 3.2 parts by mass of dipentaerythritol penta/hexaacrylate as a polymerizable compound, (D) 1.0 parts by mass of an oxime-based initiator (D-1) as a photopolymerization initiator, As a fluorine-based surfactant, 0.03 parts by mass of Megapack F-554 (manufactured by DIC Co., Ltd.) was mixed, and methoxybutyl acetate in an amount equivalent to 10% by mass of the total solvent amount so that the solid content concentration of the final composition was 15.0% by mass is added, an amount of n-butanol corresponding to 5% by mass of the total amount of solvents is added, diacetone alcohol in an amount corresponding to 20% by mass of the total amount of solvents is added, and an amount corresponding to the amount of the remaining solvents is added. A colored composition (G3-1) was prepared by adding propylene glycol monomethyl ether acetate.

(2) Evaluation

About the coloring composition (G3-1), it carried out similarly to Example 1-1, and evaluated solvent resistance and storage stability. Their 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, except that the type of colorant and other components was changed as shown in Table 7 below, the chromaticity coordinate values (x, y) in the CIE color system in the C light source were changed. In the same manner as, coloring compositions (G3-2) to (G3-13) and (G3-1R) to (G3-5R) were prepared, respectively. The obtained coloring compositions (G3-2) to (G3-13) and (G3-1R) to (G3-5R) were evaluated for solvent resistance and storage stability in the same manner as in Example 1-1. Their results are shown in Table 7 below.

8. Preparation and evaluation of coloring composition [4]

[Example 4-1]

(1) Preparation of coloring composition

30.9 parts by mass of dye IX, 24.2 parts by mass of colorant dispersion (MB-Y-1), 6.5 parts by mass of polymer (B-12) as a binder resin (solid content concentration: 35% by mass), (C) polymerizable compound As, 3.9 parts by mass of dipentaerythritol penta/hexaacrylate having a hydroxyl value of 100 to 140 mgKOH/g, (D) 0.8 parts by mass of an oxime-based initiator (D-1) as a photopolymerization initiator, mega as a fluorine-based surfactant Mix 0.03 parts by mass of Pack F-554 (manufactured by DIC Corporation), add methoxybutyl acetate in an amount equivalent to 10% by mass of the total amount of solvents so that the solid content concentration of the final composition is 15.0% by mass, and Add n-butanol in an amount corresponding to 5% by mass of the amount, add cyclohexanone in an amount corresponding to 40% by mass of the total solvent amount, and further propylene glycol monomethyl ether in an amount corresponding to the remaining solvent amount Acetate was added to prepare a coloring composition (G4-1).

(2) Evaluation

About the coloring composition (G4-1), it carried out similarly to Example 1-1, and evaluated solvent resistance and storage stability. Their results are shown in Table 8 below.

[Examples 4-2 to 4-11]

In Example 4-1, except that the type of colorant and other components was changed as shown in Table 8 below, the chromaticity coordinate values (x, y) in the CIE color system in the C light source were changed. In the same manner as, coloring compositions (G4-2) to (G4-11) were prepared respectively. About the obtained coloring compositions (G4-2) - (G4-11), it carried out similarly to Example 1-1, and evaluated solvent resistance and storage stability. Their results are shown in Table 8 below.

In Table 8, the abbreviated names of the compounds are as follows.

C-2A: dipentaerythritol penta/hexaacrylate (hydroxyl value: 60 to 100 mgKOH/g)

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

9. Preparation and evaluation of coloring composition [5]

[Example 5-1]

(1) Preparation of coloring composition

16 parts by mass of colorant dispersion (MB-Bk-1), 1.4 parts by mass of colorant dispersion (MB-Bk-4), 25.2 parts by mass of polymer (B-1) as a polymer solution (solid content concentration: 35% by mass) as a binder resin, (C) 3.9 parts by mass of dipentaerythritol penta/hexaacrylate as a polymerizable compound, (D) 1.9 parts by mass of an oxime-based initiator (D-1) as a photopolymerization initiator, Megapack RS-72- as a fluorine-based surfactant 0.2 parts by mass of K (manufactured by DIC Corporation) was mixed, and methoxybutyl acetate in an amount corresponding to 10% by mass of the total amount of solvents was added so that the solid content concentration of the final composition was 30.0% by mass, and 5 parts by mass of the total amount of solvents were added. A coloring composition (Bk5-1) was prepared by adding n-butanol in an amount corresponding to the mass% and further adding an amount of propylene glycol monomethyl ether acetate corresponding to the remaining solvent amount.

(2) Evaluation

About the coloring composition (Bk5-1), solvent resistance was evaluated according to following (i). Further, storage stability was evaluated in the same manner as in Example 1-1. Their results are shown in Table 9 below.

(i) Evaluation of solvent resistance

The coloring composition (Bk5-1) was applied onto a soda glass substrate having a SiO ₂ film for preventing sodium ion elution formed on the surface using a spin coater, and then dried under reduced pressure at room temperature to form a coating film having a thickness of 10 μm. did.

Subsequently, radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to the coating film at an exposure amount of 600 J/m 2 using a high-pressure mercury lamp through a photomask. Thereafter, shower development was performed for 60 seconds by discharging a developing solution composed of a 0.04% by mass aqueous solution of potassium hydroxide at 23° C. to the substrate at a developing pressure of 1 kgf/cm 2 (nozzle diameter 1 mm). Thereafter, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 85° C. for 60 minutes to form a substrate having a width of 3 to 50 μm (every 1 μm) and a length of 1 mm. Formed a line pattern.

Next, the formed line pattern was immersed in a mixed solvent of propylene glycol monomethyl ether/propylene glycol monomethyl ether acetate = 50/50 (mass ratio) for 5 minutes, and the line pattern after immersion was observed under an optical microscope. . Solvent resistance was evaluated by the minimum line width among the remaining patterns after immersion.

(Evaluation standard)

◎: The minimum line width is 5 μm or less

○: The minimum line width is 6 μm or more and 10 μm or less

△: The minimum line width is 11 μm or more and 30 μm or less

×: Minimum line width is 31 μm or more

As a result of the evaluation, in Example 5-1, the solvent resistance was "○".

[Examples 5-2 to 5-6 and Comparative Examples 5-1 to 5-6]

In Example 5-1, the coloring composition (Bk5- 2) to (Bk5-6) and (Bk5-1R) to (Bk5-6R) were prepared respectively. For the obtained coloring compositions (Bk5-2) to (Bk5-4), (Bk5-6), (Bk5-2R) to (Bk5-4R) and (Bk5-6R), the film of the coating film in the solvent resistance evaluation Solvent resistance and storage stability were evaluated in the same manner as in Example 5-1 except that the thickness was changed to 1 μm. Their results are shown in Table 9 below.

In Table 9, the abbreviated names of the compounds are as follows.

E6: Ethanol

F-2: Megapack RS-72-K (manufactured by DIC Corporation)

From the above results, in the (A) colorant, (B) polymer, and (C) polymerizable compound, the curable composition containing the partial structure represented by the formula (1) and a hydroxyl group in the same molecule or in different molecules has a viscosity It became clear that a cured film excellent in solvent resistance could be produced even when the change with time was small and the storage stability was excellent, and the post-baking temperature was set to a low temperature.

Claims (17)

(A) colorant, (B) polymer (except for (A) colorant) and (C) polymeric compound (excluding (A) colorant and (B) polymer) As a coloring composition to be said, the said (B) polymer has a partial structure represented by following formula (1), The said (B) polymer has a hydroxyl group, The coloring composition.

(In Formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms; L ¹ is a divalent organic group; X ¹ is a divalent linking group having an electron withdrawing property; n1 and n2 are each independently an integer of 0 to 2; "*" indicates a bond) According to claim 1,
The coloring composition in which the said (B) polymer contains the polymer containing the structural unit (a) which has a partial structure represented by said formula (1). According to claim 2,
The coloring composition in which the said structural unit (a) is a structural unit derived from at least 1 sort(s) selected from the group which consists of a (meth)acrylic monomer, a styrene-type monomer, and a maleimide-type monomer. According to claim 2,
The said structural unit (a) is a coloring composition which is a structural unit represented by following formula (1-2).

(In formula (1-2), R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ¹ , R ² , L ¹ , X ¹ , n1 and n2 have the same meaning as in formula (1) above, respectively. lim) According to claim 2,
The coloring composition containing the alkali-soluble polymer which has the said structural unit (a) as said (B) polymer. According to claim 5,
The coloring composition in which the said alkali-soluble polymer further has a structural unit which has a hydroxyl group. According to claim 6,
The coloring composition in which the structural unit which has the said hydroxyl group is a structural unit derived from the monomer which has an ethylenically unsaturated group. According to claim 1,
The coloring composition containing the polymer containing the structural unit which has a hydroxyl group as said (B) polymer. According to claim 8,
The coloring composition in which the structural unit which has the said hydroxyl group is a structural unit derived from the monomer which has an ethylenically unsaturated group. According to claim 1,
Said X ¹ is a group having at least one electron withdrawing group selected from the group consisting of a carbonyl group, an amide group, an imide group, an ester group, a sulfonyl group, a sulfinyl group, a thiocarbonyl group, and a carbonimideyl group, colored composition. A colored cured film formed using the coloring composition according to any one of claims 1 to 10. A color filter formed using the coloring composition according to any one of claims 1 to 10. A display element comprising the colored cured film according to claim 11. A light-receiving element comprising the colored cured film according to claim 11. A step of applying the coloring composition according to any one of claims 1 to 10 on a substrate to form a coating film;
Step of removing the solvent contained in the coating film
Including, a method for producing a colored cured film. According to claim 15,
A step of exposing the coating film;
Process of developing the exposed coating film
Further comprising, a method for producing a colored cured film. A curable composition containing (B) a polymer (but excluding the colorant) and (C) a polymerizable compound (but excluding the colorant and the (B) polymer),
The (B) polymer has a partial structure represented by the following formula (1),
The said (B) polymer has a hydroxyl group, The curable composition.

(In Formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms; L ¹ is a divalent organic group; X ¹ is a divalent linking group having an electron withdrawing property; n1 and n2 are each independently an integer of 0 to 2; "*" indicates a bond)