Coloring composition, film, color filter, solid-state imaging element and image display device

Abstract

A coloring composition comprising a coloring agent A containing a dye, a polymerization initiator B, a polymerizable compound C, a compound d1 having an acidic group and a cationic group, and a salt of a relative anion d2 having a molecular weight of 50 or more, wherein the compound D has a weight average molecular weight of 2000 or more and a specific absorbance of 5 or less as represented by the formula (Aλ). A membrane, a color filter, a solid-state imaging element, and an image display device using the coloring composition described above.

Description

Technology Field

[0001] The present invention relates to a coloring composition comprising a dye. In addition, the present invention relates to a film, a color filter, a solid-state imaging element, and an image display device using the coloring composition. Background Technology

[0002] Recently, due to the widespread adoption of digital cameras and smartphones, the demand for solid-state imaging devices, such as complementary metal-oxide-semiconductor (CMOS) image sensors, has increased significantly. Color filters are used as key devices for displays and optical devices. Color filters typically have pixels of the three primary colors—red, green, and blue—and play the role of decomposing transmitted light into the three primary colors.

[0003] Each color pixel of a color filter is manufactured by forming a pattern using a photolithography method, for example, using a coloring composition containing a coloring agent. For example, Patent Document 1 describes forming a pixel of a color filter by forming a pattern using a photolithography method using a coloring composition containing an acid dye, a binder resin, a predetermined ionic compound having a maximum molar extinction coefficient ε in the visible light region of 0 or more and 3000 or less. Prior art literature

[0004] Patent Document 1: Japanese Published Patent Application No. 2016-133604 The problem to be solved

[0005] Generally, dyes tend to have lower lightfastness than pigments, and there was room for further improvement regarding the lightfastness of films obtained using coloring compositions containing dyes.

[0006] As a result of the inventors examining the coloring composition described in Patent Document 1, it was found that even with this coloring composition, there is room for further improvement regarding the lightfastness of the film obtained after development.

[0007] Accordingly, the object of the present invention is to provide a coloring composition capable of forming a film with excellent light resistance. In addition, the object of the present invention is to provide a film, a color filter, a solid-state imaging element, and an image display device. means of solving the problem

[0008] The present invention provides the following.

[0009] <1> Colorant A containing a dye, and

[0010] Polymerization initiator B and,

[0011] Polymerizable compound C and,

[0012] A coloring composition comprising a compound d1 having an acidic group and a cationic group, and a salt of a relative anion d2 having a molecular weight of 50 or more, wherein the compound D has a weight average molecular weight of 2000 or more and a specific absorbance of 5 or less as represented by the formula (Aλ);

[0013] E 1 =A 1 / (c 1 ×l 1 )… (Aλ)

[0014] In the equation (Aλ), E 1 Silver represents the specific absorbance of compound D at the maximum absorption wavelength in the wavelength range of 400 to 700 nm, and

[0015] A 1 Silver represents the absorbance of compound D at the maximum absorption wavelength in the wavelength range of 400 to 700 nm, and

[0016] l 1 represents a cell length expressed in centimeters, and

[0017] c 1 represents the concentration of compound D in the solution, expressed in units of mg / ml.

[0018] <2> The cationic group of the above compound d1 is a quaternary ammonium cation, <1> Coloring composition described in

[0019] <3> The above counter anion d2 is an anion represented by any one of equations (BZ-1) to (BZ-8), <1> or <2> Coloring composition described in;

[0020] [Chemical Formula 1]

[0021]

[0022] In equation (BZ-1), R 111 Silver, -SO2-R 201 or -CO-R 201 Represents, and R 112 is, alkyl group, aryl group, -SO2-R 202 or -CO-R 202 Represents, and R 201 and R 202 Each independently represents a halogen atom, an alkyl group, or an aryl group, and R 111 and R 112 ...may combine to form a ring;

[0023] In formula (BZ-2), R 113 Silver, -SO2-R 203 or -CO-R 203 Represents, and R 114 and R 115 -SO2-R 204 , -CO-R 204 or represents cyanotype, R 203 and R 204 Each independently represents a halogen atom, an alkyl group, or an aryl group, and R 113 and, R 114 or R 115 It may combine to form a ring;

[0024] In formula (BZ-3), R 116 ~R 119 Each represents, independently, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a cyano group;

[0025] In formula (BZ-4), R 120 It represents an alkyl group or an aryl group;

[0026] In formula (BZ-5), R 121 It represents an alkyl group or an aryl group;

[0027] In formula (BZ-6), R 122 represents an alkyl group or an aryl group, and R 123 It represents silver, a hydrogen atom, an alkyl group, or an aryl group;

[0028] Among the formula (BZ-7), R 124 ~R 129 Each independently represents a halogen atom or a halogenated hydrocarbon group;

[0029] In formula (BZ-8), R 130 ~R 135 Each represents a halogen atom or a halogenated hydrocarbon group independently.

[0030] <4> The above counter anion d2 is a bis(fluoroalkylsulfonyl)imide anion, <1> or <2> Coloring composition described in

[0031] <5> The above compound D has a polymerizable group, <1> inside <4> A coloring composition described in any one of the following.

[0032] <6> The above polymerizable group is an ethylene unsaturated bond containing group, and

[0033] Compound D having an ethylenically unsaturated bond value of 0.7 mmol / g or higher, <5> Coloring composition described in

[0034] <7> The acid group of the above compound d1 is a carboxyl group, <1> inside <6> A coloring composition described in any one of the following.

[0035] <8> The above compound D having an acid value of 0.20 to 1.20 mmol / g, <1> inside <7> A coloring composition described in any one of the following.

[0036] <9> The above compound d1 is a polymer having a repeating unit d1-1 having an acid group and a repeating unit d1-2 having a cationic group, and

[0037] The above compound D forms a salt by coordinating the counter anion d2 to the cationic group of the above repeating unit d1-2, and

[0038] A salt structure formed by the above repeating unit d1-2 and the above counter-anion d2, wherein the ClogP value is -10.0 to 0.3, <1> inside <8> A coloring composition described in any one of the following.

[0039] <10> The above dye comprises a dye having a chemical structure including cations and anions, <1> inside <9> A coloring composition described in any one of the following.

[0040] <11> The above dye includes xanthen dye, <1> inside <10> A coloring composition described in any one of the following.

[0041] <12> The above dye comprises a dye polymer, <1> inside <11> A coloring composition described in any one of the following.

[0042] <13> The content of the polymerizable compound C in the total solid content of the above coloring composition is 5 to 30 mass%, <1> inside <12> A coloring composition described in any one of the following.

[0043] <14> The chloride ion concentration in the above coloring composition is 100 mass ppm or less, <1> inside <13> A coloring composition described in any one of the following.

[0044] <15> <1> inside <14> A film obtained using a coloring composition described in any one of the following.

[0045] <16> <15> A color filter having a membrane as described in

[0046] <17> <15> A solid-state imaging element having a film described in

[0047] <18> <15> Image display device having a film described in Effects of the invention

[0048] The present invention can provide a coloring composition capable of forming a film with excellent light resistance. In addition, the present invention can provide a film, a color filter, a solid-state imaging element, and an image display device using the coloring composition. Specific details for implementing the invention

[0049] The contents of the present invention will be described in detail below.

[0050] In this specification, "~" is used to mean including the values ​​described before and after it as lower and upper limits.

[0051] In the notation of groups (atomic groups) in this specification, notations that do not specify substitution or non-substitution include groups (atomic groups) that have substituents along with groups (atomic groups) that do not have substituents. For example, "alkyl group" includes not only alkyl groups that do not have substituents (non-substituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).

[0052] In this specification, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless specifically explained otherwise. In addition, light used for exposure may include active light or radiation such as emission spectra of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams.

[0053] In this specification, "(meth)acrylate" represents either acrylate or methacrylate, "(meth)acryl" represents either acrylic or methacryl, and "(meth)acryloyl" represents either acryloyl or methacryloyl.

[0054] In the present specification, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group in the structural formula.

[0055] In this specification, the weight average molecular weight and the number average molecular weight are polystyrene equivalent values ​​measured by the GPC (gel permeation chromatography) method.

[0056] In this specification, the term "total solid content" refers to the total mass of the components excluding the solvent from the total components of the composition.

[0057] In this specification, the term "pigment" refers to a color material that is difficult to dissolve in a solvent.

[0058] In this specification, the term "dyes" refers to a color material that is easily soluble in a solvent.

[0059] In this specification, the term "cation" means an atom having a static charge or a group of atoms having a static charge.

[0060] In this specification, the term anion means an atom having a negative charge or a group of atoms having a negative charge.

[0061] In this specification, symbols appended before or after a name (e.g., A, B, C, and D, etc.) are terms used to distinguish components and do not limit the type of components, the number of components, or the order of components.

[0062] In this specification, the term "process" includes not only independent processes but also cases where the desired function of the process is achieved, even if it cannot be clearly distinguished from other processes.

[0063] Coloring composition

[0064] The coloring composition of the present invention is,

[0065] Colorant A containing a dye, and

[0066] Polymerization initiator B and,

[0067] Polymerizable compound C and,

[0068] It is characterized by comprising a compound d1 having an acidic group and a cationic group, and a salt of a relative anion d2 having a molecular weight of 50 or more, wherein the compound D has a weight average molecular weight of 2000 or more and a specific absorbance of 5 or less as represented by the formula (Aλ).

[0069] The coloring composition of the present invention can form a film with excellent light resistance. Although the detailed reason for obtaining such an effect is unclear, it is presumed to be due to the following. Since the coloring composition of the present invention includes the aforementioned compound D, it is presumed that the association formation of dyes can be promoted by the aforementioned compound D during film formation. Furthermore, since compound D is a compound with a relatively large molecular weight, it is presumed that the film-forming components, such as polymerizable compound C, can be pseudo-crosslinked by compound D, thereby suppressing the leakage of compound D or dyes from the film during development. For this reason, it is presumed that a film with excellent light resistance could be formed by using the coloring composition of the present invention.

[0070] Furthermore, according to the coloring composition of the present invention, it is possible to form pixels with suppressed damage. Although the detailed reason for obtaining such an effect is unclear, it is presumed that since the coloring composition of the present invention includes the aforementioned compound D, film-forming components such as polymerizable compound C can be pseudo-crosslinked by the aforementioned compound D during film formation. For this reason, it is presumed that the coloring composition of the present invention can form a robust film upon exposure, and as a result, when developing and removing the unexposed portion, damage to the film in the exposed portion can be suppressed.

[0071] The coloring composition of the present invention can be preferably used as a coloring composition for color filters. More specifically, it can be preferably used as a coloring composition for forming pixels in a color filter. Examples of types of pixels in a color filter include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc. The coloring composition of the present invention can also be suitably used in the pixel configurations described in International Publication No. 2019 / 102887. Below, each component used in the coloring composition of the present invention will be described.

[0072] <<Colorant A>>

[0073] The coloring composition of the present invention contains a coloring agent A (hereinafter referred to as the coloring agent). Examples of coloring agents include pigments and dyes. It is preferable that the coloring agent included in the coloring composition of the present invention includes a dye.

[0074] -dyes-

[0075] The type of dye is not limited. Known dyes may be used as dyes. Examples include red dyes, blue dyes, green dyes, cyan dyes, magenta dyes, and yellow dyes. As one embodiment, an embodiment using at least one selected from cyan dyes, magenta dyes, and yellow dyes may be cited.

[0076] As a dye, it is preferable to be a compound having a pigment structure selected from triarylmethane pigment structure, xanthen pigment structure, anthraquinone pigment structure, cyanine pigment structure, squaryllium pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, subphthalocyanine pigment structure, azo pigment structure, pyrazolotriazole pigment structure, dipyromethen pigment structure, isoindoline pigment structure, thiazole pigment structure, benzimidazolone pigment structure, perinone pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, diiminium pigment structure, naphthalocyanine pigment structure, relene pigment structure, dibenzofuranone pigment structure, merosianine pigment structure, croconium pigment structure, and oxonol pigment structure, and triarylmethane pigment structure, xanthen pigment structure, anthraquinone pigment structure, cyanine pigment structure, squaryllium pigment structure, quinophthalone pigment It is more preferable that the compound has a pigment structure selected from the structure, phthalocyanine pigment structure, subphthalocyanine pigment structure, azo pigment structure, thiazole pigment structure, pyrazolotriazole pigment structure, and dipyromethen pigment structure; it is even more preferable that the compound has a pigment structure selected from the triarylmethane pigment structure, xanthen pigment structure, cyanine pigment structure, and squaryllium pigment structure; it is even more preferable that the compound has a triarylmethane pigment structure or a xanthen pigment structure; and it is particularly preferable that the compound has a xanthen pigment structure. That is, it is preferable that the dye is a xanthen dye.

[0077] The amount of dye dissolved in 100g of propylene glycol methyl ether acetate at 25℃ is preferably 0.01g or more, more preferably 0.5g or more, and more preferably 1g or more.

[0078] The dye used in the present invention is preferably a dye having a chemical structure including a cation and an anion. Hereinafter, the dye having a chemical structure including a cation and an anion is also referred to as dye A. In addition, the cation of dye A is referred to as "cation AX". + It is called ". Also, the anion of dye A is referred to as "anion AZ". - They say.

[0079] In dye A, the anion AZ - is, cation AX + It may exist outside of the molecule. "Anion AZ - is cation AX + "Exists outside the molecule" refers to the anion AZ - a, Cation AX + It is not bonded via a covalent bond, and the cation AX + It refers to the state in which it exists as an independent structural unit. Examples of the forms of dye A as described above include salts. Hereinafter, the anion existing outside the cation molecule is also referred to as the counter-anion. In dye A, the anion AZ - is, cation AX + It is desirable that it is bonded through a covalent bond. That is, the form of dye A is preferably an intramolecular salt (also called an amphoteric ion).

[0080] Anion AZ - As for the types, fluoride anion, chloride anion, bromine anion, iodide anion, cyanide ion, perchlorate anion, carboxylate anion, sulfonate anion, anion containing a phosphorus atom, imide anion, metade anion, borate anion, SbF6 -Examples include imide anions, metade anions, and borate anions, which are preferred, imide anions and metade anions are more preferred, and imide anions are more preferred due to their low nucleational properties. As an imide anion, bis(sulfonyl)imide anions are preferred. As a metade anion, tris(sulfonyl)mate anions are preferred. As a borate anion, tetraarylborate anions, tetracyanoborates, tetrafluoroborate anions, etc., may be examples.

[0081] Cation AX + Examples of types include cations having a xanthen pigment structure, cations having a triarylmethane pigment structure, cations having a cyanine pigment structure, and cations having a squaryllium pigment structure. Cation AX + It is preferable that the cation has a xanthen pigment structure or a triarylmethane pigment structure, and it is more preferable that the cation has a xanthen pigment structure because the effects of the present invention are more easily obtained.

[0082] AX cation of the xanthen pigment structure + Examples of dyes having [this] include compounds represented by the formula (XT-1).

[0083] [Chemical Formula 2]

[0084]

[0085] In equation (XT-1), R xt1 ~R xt4 Each independently represents a hydrogen atom, an alkyl group, or an aryl group, and R xt5 represents a substituent, m represents an integer from 0 to 5, and Z xt represents the counter-anion. Z xt If does not exist, R xt1 ~R xt5 At least one of them contains an anion.

[0086] R xt1 ~R xt4 The alkyl and aryl groups represented by may have substituents. Examples of substituents include the group represented as substituent T described later and polymerizable groups.

[0087] R xt5 Examples of substituents represented by include the group and polymerizable group described later as substituent T.

[0088] In equation (XT-1), Z xt represents a counter-anion. The counter-anions are fluoride anion, chloride anion, bromine anion, iodide anion, cyanide ion, perchlorate anion, carboxylate anion, sulfonate anion, anion containing a phosphorus atom, imide anion, metade anion, borate anion, SbF6 - Examples include imide anions, metade anions, and borate anions, which are preferred, imide anions and metade anions are more preferred, and imide anions are more preferred. As an imide anion, bis(sulfonyl)imide anions are preferred. As a metade anion, tris(sulfonyl)metide anions are preferred. As a borate anion, tetraarylborate anions, tetracyanoborates, tetrafluoroborate anions, etc., may be examples. The molecular weight of the relative anion is preferably 100 to 1000, and more preferably 200 to 500.

[0089] In equation (XT-1), R xt1 ~R xt5Where at least one of them comprises an anion, examples of the anion include carboxylate anions, sulfonate anions, anions containing a phosphorus atom, imide anions, metade anions, and borate anions; imide anions, metade anions, and borate anions are preferred, imide anions and metade anions are more preferred, and imide anions are more preferred. As for the imide anion, bis(sulfonyl)imide anions are preferred. As for the metade anion, tris(sulfonyl)metide anions are preferred. Specifically, R xt1 ~R xt5 It is preferable that at least one of them is a part structure represented by formula (AZ-1) or a part structure represented by formula (AZ-2), and more preferable that it is a part structure represented by formula (AZ-1).

[0090] [Chemical Formula 3]

[0091]

[0092] The dashed lines in the above formula represent bond loss with other atoms or atomic groups.

[0093] R xt1 ~R xt5 If at least one of them includes an anion, R xt1 ~R xt5 It is also desirable that at least one of them has a substituent represented by formula (P-1).

[0094] [Chemical Formula 4]

[0095]

[0096] In equation (P-1), L 1 Silver represents a single bond or a divalent linker, and it is preferably a single bond. L 1 Examples of the divalent linking groups represented by this include alkylene groups having 1 to 6 carbon atoms, arylene groups having 6 to 12 carbon atoms, -O-, -S-, or groups formed by combinations thereof. L 2represents -SO2- or -CO-. G represents a carbon atom or a nitrogen atom. n1 represents 2 if G is a carbon atom, and 1 if G is a nitrogen atom. R 6 It represents a silver, an alkyl group containing a fluorine atom, or an aryl group containing a fluorine atom. If n1 is 2, there are 2 Rs. 6 They may be the same or different. R 6 The number of carbon atoms in the alkyl group containing the fluorine atom represented here is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. R 6 The number of carbon atoms in the aryl group containing a fluorine atom is preferably 6 to 20, more preferably 6 to 14, and more preferably 6 to 10. The alkyl group containing a fluorine atom and the aryl group containing a fluorine atom may have additional substituents. Examples of substituents include the substituent T or polymerizable groups described later.

[0097] Cation AX of the triarylmethane dye structure + Examples of dyes having [this] include compounds represented by the formula (TP-1).

[0098] [Chemical Formula 5]

[0099]

[0100] In equation (TP-1), R tp1 ~R tp4 Each independently represents a hydrogen atom, an alkyl group, or an aryl group, and R tp5 is a hydrogen atom, an alkyl group, an aryl group, or NR tp9 R tp10 (R tp9 and R tp10 represents a hydrogen atom, an alkyl group, or an aryl group), and R tp6 , R tp7 and R tp8 Each represents a substituent independently, and

[0101] a, b, and c each independently represent integers from 0 to 4, and

[0102] If a, b, and c are 2 or more, R t p 6 Together, R tp7 Kiri and R tp8 They may each be connected to form a ring, and

[0103] Z tp represents the counter-anion, and Z tp If does not exist, R tp1 ~R tp8 At least one of them contains an anion.

[0104] R tp1 ~R tp5 , R tp9 and R tp10 The alkyl and aryl groups represented here may have substituents. Examples of substituents include the group represented as substituent T described later and polymerizable groups.

[0105] R tp6 , R tp7 and R tp8 The substituents represented here may include the group and polymerizable group, etc., which are represented as substituent T described later.

[0106] In equation (TP-1), Z tp represents the counter-anion. Z tp If does not exist, R tp1 ~R tp8 At least one of them includes an anion. As a counter anion, the counter anion described in the above-mentioned formula (XT-1) may be cited. Also, in formula (TP-1), R tp1 ~R tp8 In cases where at least one of them includes an anion, the anion may be the anion described above.

[0107] (Substituent T)

[0108] As substituents T, the following groups can be cited. Alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), aryl group (preferably an aryl group having 6 to 30 carbon atoms), amino group (preferably an amino group having 0 to 30 carbon atoms), alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), heteroaryloxy group, acyl group (preferably an acyl group having 1 to 30 carbon atoms), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), acyloxy group (preferably a carbon atom 2-30 acyloxy groups), acylamino groups (preferably acylamino groups having 2-30 carbon atoms), alkoxycarbonylamino groups (preferably alkoxycarbonylamino groups having 2-30 carbon atoms), aryloxycarbonylamino groups (preferably aryloxycarbonylamino groups having 7-30 carbon atoms), sulfamoyl groups (preferably sulfamoyl groups having 0-30 carbon atoms), carbamoyl groups (preferably carbamoyl groups having 1-30 carbon atoms), alkylthio groups (preferably alkylthio groups having 1-30 carbon atoms), arylthio groups (preferably arylthio groups having 6-30 carbon atoms), heteroarylthio groups (preferably 1-30 carbon atoms), alkylsulfonyl groups (preferably 1-30 carbon atoms), arylsulfonyl groups (preferably (6 to 30 carbon atoms), heteroarylsulfonyl group (preferably 1 to 30 carbon atoms), alkylsulfinyl group (preferably 1 to 30 carbon atoms), arylsulfinyl group (preferably 6 to 30 carbon atoms), heteroarylsulfinyl group (preferably 1 to 30 carbon atoms), ureido group (preferably 1 to 30 carbon atoms), hydroxyl group, carboxyl group, sulfo group, phosphate group, carboxylic acid amide group, sulfonic acid amide group, imidic acid group, mercapto group, halogen atom, cyano group, alkylsulfinyl group, arylsulfinyl group, hydrazino group, imino group, heteroaryl group (preferably 1 to 30 carbon atoms). These groups may have additional substituents if they are additionally substitutable groups.Examples of substituents include the group described as the aforementioned substituent T, polymerizable groups, etc.

[0109] Examples of polymerizable groups include ethylenically unsaturated bond-containing groups such as vinyl groups, allyl groups, (meth)acryloyl groups, epoxy groups, oxetaneyl groups, etc.

[0110] The dye (preferably dye A) is preferably a compound having polymerizable groups, for the reason that it is easy to obtain a film with high crosslinking density and excellent performance.

[0111] In addition, the dye (preferably dye A) is preferably a pigment polymer because it facilitates reducing the occurrence of residue during development. A pigment polymer is a pigment compound having two or more pigment structures in one molecule, and it is preferable to have three or more pigment structures. The upper limit is not particularly limited, but it may be 100 or less. The pigment structures in one molecule may be the same pigment structure or different pigment structures.

[0112] The weight-average molecular weight (Mw) of the pigment polymer is preferably 2,000 to 50,000. The lower limit is more preferably 3,000 or higher, and more preferably 6,000 or higher. The upper limit is more preferably 30,000 or lower, and more preferably 20,000 or lower.

[0113] Examples of the structures of pigment multimers include pigment multimers (A) to (D) described in paragraphs 0047 to 0103 of International Publication No. 2016 / 208524. As pigment multimers, it is preferable to have a pigment multimer having a repeating unit represented by formula (A) described below and a pigment multimer represented by formula (D) described below. Hereinafter, the pigment multimer having a repeating unit represented by formula (A) is also referred to as pigment multimer (A). In addition, the pigment multimer represented by formula (D) is also referred to as pigment multimer (D).

[0114] The pigment polymer (A) preferably comprises repeating units represented by formula (A). The proportion of repeating units represented by formula (A) is preferably 10 mass% or more of the total repeating units constituting the pigment polymer (A), more preferably 20 mass% or more, more preferably 30 mass% or more, and particularly preferably 50 mass% or more. The upper limit may be 100 mass% or less, or 95 mass% or less.

[0115] [Chemical Formula 6]

[0116]

[0117] In Equation (A), X 1 represents a trivalent connector, and L 1 represents a single bond or a divalent linker, and D 1 It represents the structure derived from pigment compounds.

[0118] X of Equation (A) 1 Examples of the trivalent linkers shown here include poly(meth)acrylic linkers, polyalkyleneimine linkers, polyester linkers, polyurethane linkers, polyurea linkers, polyamide linkers, polyether linkers, polystyrene linkers, etc., and it is preferable that the linker be a poly(meth)acrylic linker or a polyalkyleneimine linker, and more preferable that the linker be a poly(meth)acrylic linker.

[0119] L 1 represents a single bond or a divalent linker. L 1 Examples of the divalent linking groups represented by this include alkylene groups having 1 to 30 carbon atoms, arylene groups having 6 to 30 carbon atoms, heterocyclic groups, -CH=CH-, -O-, -S-, -C(=O)-, -COO-, -NR-, -CONR-, -OCO-, -SO-, -SO2-, and groups formed by linking two or more of these. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

[0120] The number of carbon atoms in the alkylene group is preferably 1 to 30. The upper limit is more preferably 25 or less, and more preferably 20 or less. The lower limit is more preferably 2 or more, and more preferably 3 or more. The alkylene group may be straight-chain, branched, or cyclic. The alkylene group may have a substituent or may be unsubstituted. Examples of substituents include the groups described in substituent group T.

[0121] The number of carbon atoms in the arylene group is preferably 6 to 20, and more preferably 6 to 12. The arylene group may have a substituent or may be unsubstituted. Examples of substituents include the group described in substituent group T.

[0122] The complex valence group is preferably a five-membered or six-membered ring. The heteroatoms of the complex valence group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms of the complex valence group is preferably 1 to 3. The complex valence group may have substituents or may be unsubstituted. Examples of substituents include the group described in substituent group T.

[0123] D 1 Examples of structures derived from the pigment compounds shown here include residues obtained by removing one or more hydrogen atoms from compounds having pigment structures selected from triarylmethane pigment structure, xanthen pigment structure, anthraquinone pigment structure, cyanine pigment structure, squaryllium pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, subphthalocyanine pigment structure, azo pigment structure, pyrazolotriazole pigment structure, dipyromethen pigment structure, isoindoline pigment structure, thiazole pigment structure, benzimidazolone pigment structure, perinone pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, diiminium pigment structure, naphthalocyanine pigment structure, relene pigment structure, dibenzofuranone pigment structure, merosianine pigment structure, croconium pigment structure, and oxonol pigment structure. D 1As for the structure derived from the pigment compound shown here, it is preferable that it be a structure derived from the compound represented by formula (XT-1) or a structure derived from the compound represented by formula (TP-1), and more preferable that it be a structure derived from the compound represented by formula (XT-1).

[0124] The pigment polymer (A) may include other repeating units in addition to the repeating unit represented by formula (A). The other repeating units may include functional groups such as polymerizable groups or acid groups, or they may not include these functional groups. Examples of polymerizable groups include ethylenically unsaturated bond-containing groups such as vinyl groups and (meth)acryloyl groups. Examples of acid groups include carboxyl groups, sulfonates, and phosphate groups.

[0125] The proportion of repeating units having polymerizable groups is preferably 0 to 50 mass% of the total repeating units constituting the pigment polymer (A). The lower limit is preferably 1 mass% or more, and more preferably 3 mass% or more. The upper limit is preferably 35 mass% or less, and more preferably 30 mass% or less.

[0126] The proportion of repeating units having acidic groups is preferably 0 to 50 mass% of the total repeating units constituting the pigment polymer (A). The lower limit is preferably 1 mass% or more, and more preferably 3 mass% or more. The upper limit is preferably 35 mass% or less, and more preferably 30 mass% or less.

[0127] The pigment polymer (D) is preferably represented by the formula (D).

[0128] [Chemical Formula 7]

[0129]

[0130] In equation (D), L 4 represents the (n+k) linker, and L 41 and L 42 Each independently represents a single bond or a divalent linker, and D 4represents the structure derived from the pigment compound, and P 4 represents a substituent; n represents 2–15, k represents 0–13, and n+k represents 2–15. n D 4 They may be different or identical. If k is 2 or greater, multiple P 4 They may be different from each other or identical.

[0131] n is preferably 2 to 14, more preferably 2 to 8, particularly preferably 2 to 7, and even more preferably 2 to 6. k is preferably 1 to 13, more preferably 1 to 10, even more preferably 1 to 8, particularly preferably 1 to 7, and even more preferably 1 to 6.

[0132] L 41 and L 42 Each represents, independently, a single bond or a divalent linker. Examples of divalent linkers include alkylene groups, arylene groups, -CH=CH-, -O-, -S-, -CO-, -COO-, -NR-, -CONR-, -OCO-, -SO-, -SO2-, and groups formed by linking two or more of these. Here, R represents, independently, a hydrogen atom, an alkyl group, or an aryl group. L 42 and L 43 It is preferable that each one independently contains -S-, and it is more preferable that it is -S-.

[0133] L 4 As a linker of the (n+k)valence represented by , a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms is included. As a linker of the (n+k)valence, the following structural units or a group composed of two or more of the following structural units combined (which may form a ring structure) may be examples. In the following formulas, * indicates a bond loss.

[0134] [Chemical Formula 8]

[0135]

[0136] Specific examples of (n+k) linkers include the linker described in paragraph 0084 of International Publication No. 2016 / 208524.

[0137] D 4 Examples of structures derived from pigment compounds represented by ga include residues obtained by removing one or more hydrogen atoms from compounds having pigment structures selected from triarylmethane pigment structure, xanthen pigment structure, anthraquinone pigment structure, cyanine pigment structure, squaryllium pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, subphthalocyanine pigment structure, azo pigment structure, pyrazolotriazole pigment structure, dipyromethen pigment structure, isoindoline pigment structure, thiazole pigment structure, benzimidazolone pigment structure, perinone pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, diiminium pigment structure, naphthalocyanine pigment structure, relene pigment structure, dibenzofuranone pigment structure, merosianine pigment structure, croconium pigment structure, and oxonol pigment structure. D 4 As for the structure derived from the pigment compound represented by, it is preferable that it be a structure derived from the compound represented by formula (XT-1) or a structure derived from the compound represented by formula (TP-1), and more preferable that it be a structure derived from the compound represented by formula (XT-1).

[0138] P 4 Examples of substituents represented by include acid groups, polymerizable groups, etc. Also, P 4 The substituent represented by α may be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound. When k is 2 or more, k P 4 It may be the same or different.

[0139] -Pigment-

[0140] The pigment may be either an inorganic pigment or an organic pigment, but it is preferable to be an organic pigment from the perspective of having many color variations, ease of dispersion, safety, etc.

[0141] Examples of organic pigments include phthalocyanine pigment, dioxazine pigment, quinacridone pigment, anthraquinone pigment, perylene pigment, azo pigment, azometaine pigment, azometaine pigment, diketopyrrolopyrrole pigment, pyrrrolopyrrole pigment, isoindolin pigment, quinophthalone pigment, triarylmethane pigment, xanthen pigment, cyanine pigment, quinoline pigment, pteridine pigment, etc.

[0142] The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, and more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and more preferably 100 nm or less. Furthermore, in this specification, the primary particle size of the pigment can be obtained from a photograph obtained by observing the primary particles of the pigment using a transmission electron microscope. Specifically, the projected area of ​​the primary particles of the pigment is determined, and the corresponding equivalent diameter is calculated as the primary particle size of the pigment. Also, the average primary particle size in the present invention is the arithmetic mean value of the primary particle sizes of 400 primary particles of the pigment. Furthermore, primary particles of the pigment refer to independent particles that are not aggregated.

[0143] The crystallite size of the pigment is preferably 0.1 to 50 nm, more preferably 0.5 to 30 nm, and more preferably 1 to 15 nm. The crystallite size can be obtained from the full width at half maximum of the diffraction angle peaks using an X-ray diffraction device and calculated using the Scherrer equation. The crystallite size of the pigment can be adjusted by known methods, such as adjusting manufacturing conditions or grinding after manufacturing.

[0144] The specific surface area of ​​pigments is 1–300 m² 2 It is desirable that it is / g. The lower limit is 10m 2 It is desirable that it be greater than / g, and 30m 2 It is more desirable to have at least / g. The upper limit is 250m 2 It is desirable that it be / g or less, and 200m 2 It is more desirable that it be less than / g. The value of the specific surface area can be measured according to DIN 66131: determination of the specific surface area of ​​solids by gas adsorption, based on the BET (Brunauer, Emmett and Teller) method.

[0145] The amount of pigment dissolved in 100g of propylene glycol methyl ether acetate at 25℃ is preferably less than 0.01g, more preferably less than 0.005g, and even more preferably less than 0.001g.

[0146] Examples of pigments include yellow pigments, orange pigments, red pigments, green pigments, purple pigments, and blue pigments.

[0147] Examples of red pigments include diketopyrrolopyrrole pigment, anthraquinone pigment, azo pigment, naphthol pigment, azomethane pigment, xanthen pigment, quinacridone pigment, perylene pigment, thioindigo pigment, etc., and it is preferable that it be diketopyrrolopyrrole pigment, anthraquinone pigment, or azo pigment, and more preferable that it be diketopyrrolopyrrole pigment. Specific examples of red pigments include CI (Color Index) pigment red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, Examples include 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, 297, etc. In addition, as a red pigment, the compound described in paragraph 0034 of International Publication No. 2022 / 085485 and the brominated diketopyrrolopyrrole compound described in Japanese Patent Publication No. 2020-085947 may also be used.

[0148] As for the red pigment, CI Pigment Red 122, 177, 224, 254, 255, 264, 269, and 272 are preferred, CI Pigment Red 254, 264, and 272 are more preferred, and CI Pigment Red 254 and 272 are even more preferred.

[0149] Examples of green pigments include phthalocyanine pigments and squaryllium pigments, and it is preferable that they be phthalocyanine pigments. Specific examples of green pigments include CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, 66, etc. Additionally, as a green pigment, zinc halide phthalocyanine pigments may be used, in which the number of halogen atoms per molecule is an average of 10 to 14, the number of bromine atoms is an average of 8 to 12, and the number of chlorine atoms is an average of 2 to 5. Specific examples include compounds described in International Publication No. 2015 / 118720. In addition, as a green colorant, compounds described in paragraph 0029 of International Publication No. 2022 / 085485, aluminum phthalocyanine compounds described in Japanese Publication No. 2020-070426, and diaryl methane compounds described in Japanese Publication No. 2020-504758 may also be used.

[0150] As for green pigments, CI Pigment Green 7, 36, 58, 62, and 63 are preferred, and CI Pigment Green 36 and 58 are more preferred.

[0151] Examples of orange pigments include diketopyrrolopyrrole pigments and azo pigments, and it is preferable that it be a diketopyrrolopyrrole pigment. Specific examples of orange pigments include CI pigment orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc.

[0152] Examples of yellow pigments include azo pigments, azometane pigments, isoindoline pigments, pteridine pigments, quinophthalone pigments, and perylene pigments, and it is preferable that it be an isoindoline pigment, a quinophthalone pigment, or an azo pigment. Specific examples of yellow pigments include CI pigment yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, Examples include 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236, etc.

[0153] In addition, as a yellow pigment, a nickel azobarbiturate complex having the following structure may be used.

[0154] [Chemical Formula 9]

[0155]

[0156] Examples of purple pigments include dioxazine pigment, quinacridone pigment, perylene pigment, thioindigo pigment, etc. Specific examples of purple pigments include CI pigment violet 1, 19, 23, 27, 32, 37, 42, 60, 61, etc.

[0157] Examples of blue pigments include phthalocyanine pigments and squaryllium pigments, and it is preferable that the pigment be a phthalocyanine pigment. Specific examples of blue pigments include CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc. In addition, aluminum phthalocyanine compounds having phosphorus atoms may be used as blue pigments. Specific examples include compounds described in paragraphs 0022 to 0030 of Japanese Patent Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Publication No. 2011-157478.

[0158] As a coloring agent, the triarylmethane dye polymer described in Korean Published Patent Application No. 10-2020-0028160, the xanthen compound described in Japanese Published Patent Application No. 2020-117638, the phthalocyanine compound described in International Published Patent Application No. 2020 / 174991, the isoindoline compound described in Japanese Published Patent Application No. 2020-160279 or their salts, the compound represented by Formula 1 described in Korean Published Patent Application No. 10-2020-0069442, the compound represented by Formula 1 described in Korean Published Patent Application No. 10-2020-0069730, the compound represented by Formula 1 described in Korean Published Patent Application No. 10-2020-0069070, and the compound represented by Formula 1 described in Korean Published Patent Application No. 10-2020-0069067 Compounds that appear, compounds represented by Formula 1 described in Korean Published Patent Application No. 10-2020-0069062, zinc halogenated phthalocyanine pigment described in Japanese Patent Publication No. 6809649, isoindoline compounds described in Japanese Published Patent Application No. 2020-180176, phenothiazine compounds described in Japanese Published Patent Application No. 2021-187913, zinc halogenated phthalocyanine described in International Published Patent No. 2022 / 004261, and zinc halogenated phthalocyanine described in International Published Patent No. 2021 / 250883 may be used. Other coloring agents may be rotaxanes, and the pigment backbone may be used in a cyclic structure of rotaxanes, may be used in a rod structure, or may be used in both structures.As other coloring agents, a quinophthalone compound represented by Formula 1 of Korean Published Patent Application No. 10-2020-0030759, a polymer dye disclosed in Korean Published Patent Application No. 10-2020-0061793, a coloring agent disclosed in Japanese Published Patent Application No. 2022-029701, an isoindoline compound disclosed in International Published Patent Application No. 2022 / 014635, an aluminum phthalocyanine compound disclosed in International Published Patent Application No. 2022 / 024926, a compound disclosed in Japanese Published Patent Application No. 2022-045895, a compound disclosed in International Published Patent Application No. 2022 / 050051, a compound disclosed in Japanese Published Patent Application No. 2020-090676, a compound disclosed in Japanese Published Patent Application No. 2020-055956, and Japanese Published Patent Application Compounds described in Patent No. 2021-031681, compounds described in Japanese Patent Publication No. 2022-056354, compounds described in U.S. Patent Application Publication No. 2021 / 0355327, compounds described in International Publication No. 2022 / 065357, compounds described in Japanese Patent Publication No. 2020-045436, compounds described in Korean Patent Publication No. 10-2021-0146726, compounds described in Japanese Patent Publication No. 2018-178039, compounds described in Chinese Patent Application Publication No. 113881244, compounds described in Chinese Patent Application Publication No. 113881245, compounds described in Chinese Patent Application Publication No. 113881246, compounds described in Japanese Patent Publication No. 2022-104822 Compounds, compounds described in Japanese Patent Publication No. 2022-096701, compounds described in Japanese Patent Publication No. 2020-023652, and green pigments described on pages 80-84 of the Journal of the Color Association (published in 2022) may also be used.

[0159] The content of the coloring agent in the total solid content of the coloring composition is preferably 40 mass% or more, more preferably 50 mass% or more, and more preferably 60 mass% or more. The upper limit is preferably 80 mass% or less, and more preferably 75 mass% or less.

[0160] The dye content in the total solid content of the coloring composition is preferably 5 mass% or more, more preferably 8 mass% or more, more preferably 10 mass% or more, and particularly preferably 15 mass% or more. The upper limit is preferably 80 mass% or less, more preferably 70 mass% or less, more preferably 60 mass% or less, even more preferably 50 mass% or less, particularly preferably 40 mass% or less, and most preferably 30 mass% or less. In addition, the dye content in the coloring agent included in the coloring composition is preferably 5 mass% or more, more preferably 10 mass% or more, more preferably 15 mass% or more, even more preferably 20 mass% or more, and particularly preferably 25 mass% or more. The upper limit may be 100 mass% or less, 90 mass% or less, 80 mass% or less, 70 mass% or less, 60 mass% or less, or 50 mass% or less.

[0161] When the coloring composition of the present invention includes a pigment as a coloring agent, the content of the pigment is preferably 10 to 1,000 parts by mass per 100 parts by mass of the dye. The lower limit is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, and more preferably 200 parts by mass or more. The upper limit is preferably 600 parts by mass or less, and more preferably 400 parts by mass or less.

[0162] <<Polymer initiator B>>

[0163] The coloring composition of the present invention contains polymerization initiator B (hereinafter referred to as the polymerization initiator). The polymerization initiator is preferably a photopolymerization initiator. There are no particular limitations on the photopolymerization initiator, and it can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light from the ultraviolet region to the visible region is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0164] Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine backbone, compounds having an oxadiazole backbone, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. The photopolymerization initiator is preferably, in terms of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a hexaarylbiimidazole compound, an onium compound, a benzothiasol compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, and a 3-aryl substituted coumarin compound, more preferably a compound selected from oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds, and even more preferably an oxime compound. In addition, as a photopolymerization initiator, the compound described in paragraphs 0065–0111 of Japanese Patent Publication No. 2014-130173, the compound described in Japanese Patent Publication No. 6301489, MATERIAL STAGE pp. 37–60, vol. 19, No.Peroxide-based photopolymerization initiator disclosed in 3, 2019, photopolymerization initiator disclosed in International Publication No. 2018 / 221177, photopolymerization initiator disclosed in International Publication No. 2018 / 110179, photopolymerization initiator disclosed in Japanese Published Patent Application No. 2019-043864, photopolymerization initiator disclosed in Japanese Published Patent Application No. 2019-044030, peroxide-based initiator disclosed in Japanese Published Patent Application No. 2019-167313, aminoacetophenone-based initiator having an oxazolidine group disclosed in Japanese Published Patent Application No. 2020-055992, oxime-based photopolymerization initiator disclosed in Japanese Published Patent Application No. 2013-190459, polymer disclosed in Japanese Published Patent Application No. 2020-172619, international The compound represented by Formula 1 described in Published Patent Application No. 2020 / 152120, the compound described in Japanese Published Patent Application No. 2021-181406, the photopolymerization initiator described in Japanese Published Patent Application No. 2022-013379, the compound represented by Formula (1) described in Japanese Published Patent Application No. 2022-015747, the fluorine-containing fluorene oxime ester-based photoinitiator described in Japanese Published Patent Application No. 2021-507058, the initiator described in Chinese Patent Application Published No. 110764367, the initiator described in Japanese Published Patent Application No. 2022-518535, the initiator described in International Published Patent Application No. 2021 / 175855, the compound described in Taiwan Patent Application Published No. 202200534, Japanese Published Patent Application Examples include compounds described in Patent Publication No. 2022-078550, compounds described in Korean Patent Publication No. 10-2017-0087330, and compounds described in International Publication No. 2022 / 075452.

[0165] Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.

[0166] Examples of commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Examples of commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV), and Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Examples of commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (both manufactured by BASF).

[0167] Examples of oxime compounds include the compound described in paragraph 0142 of International Publication No. 2022 / 085485, the compound described in Japanese Patent Publication No. 5430746, the compound described in Japanese Patent Publication No. 5647738, the compound represented by general formula (1) in Japanese Patent Publication No. 2021-173858 or the compound described in paragraphs 0022 to 0024, the compound represented by general formula (1) in Japanese Patent Publication No. 2021-170089 or the compound described in paragraphs 0117 to 0120. Specific examples of oxime compounds include 3-benzoyliminobutan-2-one, 3-acetoxyliminobutan-2-one, 3-propionyloxyliminobutan-2-one, 2-acetoxyliminopentan-3-one, 2-acetoxylimino-1-phenylpropan-1-one, 2-benzoylimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxylimino-1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propan-1,2-dione-2-(O-acetyloxime). Examples of commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, and Irgacure OXE04 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, and TR-PBG-327 (manufactured by TRONLY), and Adeka Optomer N-1919 (manufactured by ADEKA Inc., Photopolymerization Initiator 2 described in Japanese Patent Publication No. 2012-014052). Additionally, as for the oxime compound, it is preferable to use a compound that is non-colorable or a compound that is highly transparent and resistant to discoloration. Examples of commercially available products include Adeka Arcles NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Inc.).

[0168] As a photopolymerization initiator, oxime compounds having a fluorene ring, oxime compounds having a backbone in which at least one benzene ring of a carbazole ring becomes a naphthalene ring, oxime compounds having a fluorine atom, oxime compounds having a nitro group, oxime compounds having a benzofuran backbone, oxime compounds having a hydroxyl group substituent attached to a carbazole backbone, and compounds described in paragraphs 0143 to 0149 of International Publication No. 2022 / 085485 may be used.

[0169] Specific examples of oxime compounds preferably used in the present invention are shown below, but the present invention is not limited to these.

[0170] [Chemical Formula 10]

[0171]

[0172] [Chemical Formula 11]

[0173]

[0174] [Chemical Formula 12]

[0175]

[0176] The oxime compound is preferably a compound having a maximum absorption wavelength in the range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the range of 360 to 480 nm. Furthermore, regarding sensitivity, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar extinction coefficient of the compound can be measured using known methods. For example, it is preferable to measure at a concentration of 0.01 g / L using a spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate as the solvent.

[0177] As a photopolymerization initiator, a photoradical polymerization initiator with two or more functional groups may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so good sensitivity is obtained. In addition, when a compound with an asymmetric structure is used, crystallinity is reduced, solubility in solvents, etc. is improved, and it becomes difficult to precipitate over time, thereby improving the stability of the colored composition over time. Specific examples of photoradical polymerization initiators with two or more functional groups include the compound described in paragraph 0148 of International Publication No. 2022 / 065215.

[0178] The content of the polymerization initiator in the total solid content of the coloring composition is preferably 0.1 to 30 mass%. The lower limit is preferably 0.5 mass% or more, and more preferably 1 mass% or more. The upper limit is preferably 20 mass% or less, and more preferably 15 mass% or less. In the coloring composition of the present invention, only one type of polymerization initiator may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.

[0179] <<Polymerizable Compound C>>

[0180] The coloring composition of the present invention contains a polymerizable compound C (hereinafter referred to as the polymerizable compound). Examples of the polymerizable compound include a compound having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, etc. The polymerizable compound used in the present invention is preferably a radical polymerizable compound.

[0181] As for the polymerizable compound, it may be in any chemical form such as a monomer, prepolymer, or oligomer, but a monomer is preferred. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and more preferably 1500 or less. The lower limit is more preferably 150 or more, and more preferably 250 or more.

[0182] The polymerizable compound is preferably a compound containing three or more ethylenically unsaturated bond-containing groups, more preferably a compound containing three to 15 ethylenically unsaturated bond-containing groups, and more preferably a compound containing three to six ethylenically unsaturated bond-containing groups. In addition, the polymerizable compound is preferably a (meth)acrylate compound having 3 to 15 functions, and more preferably a (meth)acrylate compound having 3 to 6 functions. Specific examples of the polymerizable compound include compounds described in paragraphs 0075 to 0083 of International Publication No. 2022 / 065215.

[0183] As polymerizable compounds, dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds having a structure in which these (meth)acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues (for example, commercially available from Satomer Co., Ltd. It is desirable to have SR454, SR499). In addition, as polymerizable compounds, diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available as M-460; manufactured by Doa Gosei), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Doa Gosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Kagaku Co., Ltd.), 8UH-1006, 8UH-1012 (both manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Kagaku Co., Ltd.), etc. may also be used.

[0184] The content of the polymerizable compound in the total solid content of the coloring composition is preferably 1 to 35 mass%, and more preferably 5 to 30 mass%. The upper limit is preferably 25 mass% or less, and more preferably 20 mass% or less. The lower limit is preferably 8 mass% or more, and more preferably 10 mass% or more. The coloring composition of the present invention may contain only one type of polymerizable compound or two or more types. When two or more types of polymerizable compounds are included, it is preferable that their total amount falls within the above range.

[0185] <<Compound D>>

[0186] The coloring composition of the present invention comprises a compound d1 having an acidic group and a cationic group, and a salt of a relative anion d2 having a molecular weight of 50 or more, wherein the compound D has a weight average molecular weight of 2000 or more and a specific absorbance of 5 or less as represented by the formula (Aλ).

[0187] E 1 =A 1 / (c 1 ×l 1 )… (Aλ)

[0188] In the equation (Aλ), E 1 Silver represents the specific absorbance of compound D at the maximum absorption wavelength in the wavelength range of 400 to 700 nm, and

[0189] A 1 Silver represents the absorbance of compound D at the maximum absorption wavelength in the wavelength range of 400 to 700 nm, and

[0190] l 1 represents a cell length expressed in centimeters, and

[0191] c 1 represents the concentration of compound D in the solution, expressed in units of mg / ml.

[0192] The specific absorbance of compound D represented by formula (Aλ) is 5 or less, preferably 3 or less, and more preferably 1 or less. The specific absorbance represented by formula (Aλ) is an indicator of the degree to which compound D absorbs light in the visible range. The smaller the specific absorbance represented by formula (Aλ), the lower the absorption of light in the visible range. There is no lower limit for the specific absorbance. If a lower limit for the specific absorbance is established, the specific absorbance represented by formula (Aλ) may be determined within a range of 0.001 or more.

[0193] In the equation (Aλ), "A 1 The absorbance indicated by " is measured by the following method. A measurement sample is prepared using compound D and a solvent in which compound D is sufficiently dissolved. If compound D has sufficient solubility in methanol, methanol is used as the solvent. If compound D does not have sufficient solubility in methanol, cyclohexanone is used as the solvent. The absorbance of the above measurement sample at 25°C (room temperature) is measured using a cell with an optical path length of 1 cm.

[0194] The weight average molecular weight of compound D is 2000 or more, preferably 3000 or more, and more preferably 4000 or more. The upper limit is preferably 1000000 or less, more preferably 100000 or less, and more preferably 20000 or less.

[0195] The acid value of compound D is preferably 0.10 to 1.50 mmol / g, and more preferably 0.20 to 1.20 mmol / g from the perspective of development.

[0196] Compound D may have a polymerizable group. Examples of polymerizable groups include ethylene unsaturated bond-containing groups such as vinyl groups, allyl groups, and (meth)acryloyl groups, epoxy groups, and oxetanyl groups, and it is preferable that it be an ethylene unsaturated bond-containing group. When compound D has a polymerizable group, compound d1 may have a polymerizable group and counter-anion d2 may have a polymerizable group, but it is preferable that compound d1 have a polymerizable group because it can further improve curability.

[0197] The polymerizable group value of compound D is preferably 0.1 mmol / g or higher, more preferably 0.5 mmol / g or higher, more preferably 0.7 mmol / g or higher, even more preferably 1.0 mmol / g or higher, and particularly preferably 1.5 mmol / g or higher. The upper limit is preferably 5.0 mmol / g or lower, more preferably 4.0 mmol / g or lower, and more preferably 3.0 mmol / g or lower.

[0198] When the polymerizable group of compound D is an ethylene unsaturated bond containing group, the ethylene unsaturated bond containing group of compound D (hereinafter also referred to as C=C) is preferably 0.1 mmol / g or more, more preferably 0.5 mmol / g or more, more preferably 0.7 mmol / g or more, even more preferably 1.0 mmol / g or more, and particularly preferably 1.5 mmol / g or more. The upper limit is preferably 5.0 mmol / g or less, more preferably 4.0 mmol / g or less, and more preferably 3.0 mmol / g or less.

[0199] The polymerizable group number of compound D is a numerical value representing the molar amount of the polymerizable group per 1g of solid content of compound D. If the polymerizable group number can be calculated from the structural formula of compound D, the value calculated from the structural formula is used. In addition, if it cannot be calculated from the structural formula but can be calculated from the raw material used in the synthesis of compound D, the value calculated from the input raw material is used. Furthermore, regarding the polymerizable group number of compound D, if it cannot be calculated from the raw material used in the synthesis of compound D, the value measured by the hydrolysis method is used. Specifically, component (a) of the polymerizable group region is extracted from compound D by alkali treatment, its content is measured by high-speed liquid chromatography (HPLC), and calculated from the following formula. In addition, if the above component (a) cannot be extracted from compound D by alkali treatment, the value measured by the NMR method (nuclear magnetic resonance) is used.

[0200] Polymerizable group of Compound D [mmol / g] = (Content of Component (a) [ppm] / Molecular weight of Component (a) [g / mol]) / (Weight of Compound D [g] × (Solid content of Compound D [mass%] / 100) × 10)

[0201] The amount of compound D dissolved in 100g of 1-methoxy-2-propanol at 25℃ is preferably 0.1g or more, more preferably 0.5g or more, and more preferably 1g or more.

[0202] The amount of compound D dissolved in 100g of cyclohexanone at 25℃ is preferably 0.1g or more, more preferably 0.5g or more, and more preferably 1g or more.

[0203] Specific examples of compound D include compounds AP-1 to AP-20 shown in the examples described below.

[0204] (Compound d1)

[0205] In compound D, the above-described compound d1, which forms a salt with the counter-anion d2, is a compound having an acidic group and a cationic group.

[0206] The weight average molecular weight of compound d1 is preferably 2000 or more, more preferably 3000 or more, and more preferably 4000 or more. The upper limit is preferably 1000000 or less, more preferably 100000 or less, and more preferably 20000 or less.

[0207] Examples of acid groups in compound d1 include carboxyl groups, phosphate groups, sulfonyl groups, and phenolic hydroxyl groups, and it is preferable that it be a carboxyl group for the reason that it can suppress the occurrence of developing residues.

[0208] The acid value of compound d1 is preferably 0.10 to 1.50 mmol / g, and more preferably 0.20 to 1.20 mmol / g.

[0209] Examples of cationic groups of compound d1 include quaternary ammonium cations, pyridium cations, and imidazolium cations, and it is preferable that it be a quaternary ammonium cation. As for the quaternary ammonium cation, it is preferable that it be a group represented by formula (Cat-1).

[0210] [Chemical Formula 13]

[0211]

[0212] During the meal, R cat1 ~R cat3 Each represents an alkyl group or an aryl group independently, and * represents a bonding hand.

[0213] R cat1 ~R cat3 The number of carbon atoms in the alkyl group represented here is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. R cat1 ~R cat3 The alkyl group represented here is preferably a straight chain or branched, and more preferably a straight chain.

[0214] R cat1 ~R cat3 The number of carbon atoms in the aryl group shown here is preferably 6 to 20, and more preferably 6 to 12.

[0215] R cat1 ~R cat3 It is preferable that each is independently an alkyl group. R cat1 and R cat2 It is preferable that each is independently an alkyl group having 1 to 5 carbon atoms, more preferable that it is an alkyl group having 1 to 3 carbon atoms, more preferable that it is a methyl or ethyl group, and particularly preferable that it is a methyl group. R cat3 It is preferable that the silver be an alkyl group having 1 to 10 carbon atoms, more preferable that it be an alkyl group having 1 to 5 carbon atoms, more preferable that it be an alkyl group having 1 to 3 carbon atoms, more preferably that it be a methyl group or an ethyl group, and particularly preferable that it be a methyl group.

[0216] The cationic group value of compound d1 is preferably 0.1 to 3.0 mmol / g, and more preferably 0.2 to 1.5 mmol / g for the reason that it can improve the light resistance of the resulting film.

[0217] Compound d1 may have a polymerizable group. Examples of polymerizable groups include ethylene unsaturated bond-containing groups such as vinyl groups, allyl groups, (meth)acryloyl groups, epoxy groups, oxetanyl groups, etc., and it is preferable that it be an ethylene unsaturated bond-containing group.

[0218] When compound d1 has a polymerizable group, the polymerizable group of compound d1 is preferably 0.1 mmol / g or more, more preferably 0.5 mmol / g or more, more preferably 0.7 mmol / g or more, even more preferably 1.0 mmol / g or more, and particularly preferably 1.5 mmol / g or more. The upper limit is preferably 5.0 mmol / g or less, more preferably 4.0 mmol / g or less, and more preferably 3.0 mmol / g or less.

[0219] When the polymerizable group of compound d1 is an ethylene unsaturated bond-containing group, the C=C value of compound d1 is preferably 0.1 mmol / g or higher, more preferably 0.5 mmol / g or higher, more preferably 0.7 mmol / g or higher, even more preferably 1.0 mmol / g or higher, and particularly preferably 1.5 mmol / g or higher. The upper limit is preferably 5.0 mmol / g or lower, more preferably 4.0 mmol / g or lower, and more preferably 3.0 mmol / g or lower.

[0220] It is preferable that compound d1 be a polymer having a repeating unit d1-1 having an acid group and a repeating unit d1-2 having a cationic group.

[0221] When compound d1 is a polymer having a repeating unit d1-1 having an acid group and a repeating unit d1-2 having a cationic group, it is preferable that compound D forms a salt by coordinating a counter anion d2 to the cationic group of repeating unit d1-2. Furthermore, the ClogP value of the salt structure formed by repeating unit d1-2 and the counter anion d2 is preferably -10.0 to 0.3, more preferably -5.0 to 0, and even more preferably -3.0 to -1.0, for the reason that it can improve the light resistance of the resulting film.

[0222] In addition, the CLogP value is the calculated value of LogP, which is the common logarithm of the 1-octanol / water partition coefficient P. In this specification, the CLogP value is a value obtained by estimating using ChemDrawProfessional ver. 20.1.1.125 (manufactured by PerkinElmer).

[0223] Here, when compound D is a polymer of the following structure, the ClogP value of the salt structure formed by the repeating unit d1-2 and the counter anion d2 described above is the ClogP value of the structure of the region enclosed by the dashed line of the polymer of the following structure. Also, the ClogP value of the structure of the region enclosed by the dashed line is -1.24.

[0224] [Chemical Formula 14]

[0225]

[0226] As a repeating unit d1-1 having a repeating unit, the repeating unit represented by equation (d1-1) can be cited.

[0227] [Chemical Formula 15]

[0228]

[0229] During the meal, A d10 represents a trivalent connector, and L d10 represents a single bond or a divalent linker, and R d10 It indicates acidity.

[0230] A d10 Examples of the trivalent linkers shown here include poly(meth)acrylic linkers, polyalkyleneimine linkers, polyester linkers, polyurethane linkers, polyurea linkers, polyamide linkers, polyether linkers, polystyrene linkers, etc., and it is preferable that the linker be a poly(meth)acrylic linker or a polyalkyleneimine linker, and more preferable that the linker be a poly(meth)acrylic linker.

[0231] L d10As the divalent linking group represented by this, an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, OCO-, -CONR x1 Examples include -, -S- and combinations of two or more of these groups. R x1 It represents silver, hydrogen atoms, alkyl groups, or aryl groups.

[0232] The above alkylene and arylene groups may have substituents. Examples of substituents include hydroxyl groups, alkoxy groups, acyl groups, polymerizable groups, etc.

[0233] The content of repeating unit d1-1 having an acid group in compound d1 is preferably 0.1 to 40 mass%. The upper limit is preferably 35 mass% or less, more preferably 30 mass% or less, more preferably 20 mass% or less, and even more preferably 10 mass% or less. The lower limit is preferably 1 mass% or more, and more preferably 3 mass% or more.

[0234] As a repeating unit d1-2 having a cationic group, the repeating unit represented by equation (d1-2) can be cited.

[0235] [Chemical Formula 16]

[0236]

[0237] During the meal, A d20 represents a trivalent connector, and L d20 represents a single bond or a divalent linker, and R d20 It represents a cationic group.

[0238] A d20Examples of the trivalent linkers shown here include poly(meth)acrylic linkers, polyalkyleneimine linkers, polyester linkers, polyurethane linkers, polyurea linkers, polyamide linkers, polyether linkers, polystyrene linkers, etc., and it is preferable that the linker be a poly(meth)acrylic linker or a polyalkyleneimine linker, and more preferable that the linker be a poly(meth)acrylic linker.

[0239] L d20 As the divalent linking group represented by this, an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, OCO-, -CONR x2 Examples include -, -S- and combinations of two or more of these groups. R x2 represents a hydrogen atom, an alkyl group, or an aryl group.

[0240] The above alkylene and arylene groups may have substituents. Examples of substituents include hydroxyl groups, alkoxy groups, acyl groups, polymerizable groups, etc.

[0241] The content of repeating unit d1-2 having a cationic group in compound d1 is preferably 0.1 to 70 mass%. The upper limit is preferably 60 mass% or less, more preferably 55 mass% or less, more preferably 50 mass% or less, even more preferably 40 mass% or less, and even more preferably 30 mass% or less. The lower limit is preferably 1 mass% or more, more preferably 5 mass% or more, and even more preferably 10 mass% or more.

[0242] Compound d1 may further include repeating units d1-3 having polymerizable groups. Examples of repeating units d1-3 having polymerizable groups include the repeating unit represented by formula (d1-3).

[0243] [Chemical Formula 17]

[0244]

[0245] During the meal, A d30 represents a trivalent connector, and L d30 represents a single bond or a divalent linker, and R d30 It represents a polymerizable group.

[0246] A d30 Examples of the trivalent linkers shown here include poly(meth)acrylic linkers, polyalkyleneimine linkers, polyester linkers, polyurethane linkers, polyurea linkers, polyamide linkers, polyether linkers, polystyrene linkers, etc., and it is preferable that the linker be a poly(meth)acrylic linker or a polyalkyleneimine linker, and more preferable that the linker be a poly(meth)acrylic linker.

[0247] L d30 As the divalent linking group represented by this, an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, OCO-, -CONR x3 Examples include -, -S- and combinations of two or more of these groups. R x3 It represents silver, hydrogen atoms, alkyl groups, or aryl groups.

[0248] The above alkylene and arylene groups may have substituents. Examples of substituents include hydroxyl groups, alkoxy groups, acyl groups, etc.

[0249] When compound d1 contains repeating unit d1-3 having a polymerizable group, the content of repeating unit d1-3 having a polymerizable group in compound d1 is preferably 1 to 95 mass%. The upper limit is preferably 90 mass% or less, and more preferably 80 mass% or less. The lower limit is preferably 10 mass% or more, more preferably 20 mass% or more, and more preferably 40 mass% or more.

[0250] Compound d1 may have additional repeating units other than the aforementioned units d1-1 to d1-3.

[0251] (Relative anion d2)

[0252] In compound D, the counter anion d2 that forms a salt with the specific cation described above is an anion with a molecular weight of 50 or more.

[0253] Examples of the counter anion d2 include imide anions, metade anions, borate anions, sulfonate anions, carboxylate anions, phosphate anions, and anions containing phosphorus or antimony atoms; it is preferable that the imide anion be one that can further improve the lightfastness of the resulting film. Furthermore, it is more preferable that the imide anion be a bis(fluoroalkylsulfonyl)imide anion.

[0254] The molecular weight of the counter anion d2 is 50 or more, preferably 51 to 900, more preferably 100 to 600, and more preferably 150 to 400.

[0255] The counter anion d2 may have a polymerizable group. Examples of polymerizable groups include ethylene unsaturated bond-containing groups such as vinyl groups, allyl groups, (meth)acryloyl groups, epoxy groups, oxetanyl groups, etc., and it is preferable that it be an ethylene unsaturated bond-containing group.

[0256] The counter anion d2 is preferably an anion represented by any one of formulas (BZ-1) to (BZ-8), and is preferably an anion represented by formula (BZ-1) for the reason that it can further improve the light resistance of the resulting film.

[0257] [Chemical Formula 18]

[0258]

[0259] In equation (BZ-1), R 111 Silver, -SO2-R 201 or -CO-R201 Represents, and R 112 is, alkyl group, aryl group, -SO2-R 202 or -CO-R 202 Represents, and R 201 and R 202 Each independently represents a halogen atom, an alkyl group, or an aryl group, and R 111 and R 112 It may combine to form a ring.

[0260] R 112 , R 201 and R 202 The number of carbon atoms in the alkyl group represented by is preferably 1 to 10, and more preferably 1 to 6. R 112 , R 201 and R 202 The alkyl group represented by is preferably an alkyl group having a halogen atom as a substituent, and more preferably an alkyl group having a fluorine atom as a substituent.

[0261] R 112 , R 201 and R 202 The number of carbon atoms in the aryl group represented by is preferably 6 to 20, and more preferably 6 to 12. R 112 , R 201 and R 202 The aryl group represented by is preferably an aryl group having a halogen atom as a substituent, and more preferably an aryl group having a fluorine atom as a substituent.

[0262] R 201 and R 202 Examples of the halogen atoms represented by fluorine atoms, chlorine atoms, and bromine atoms may be fluorine atoms, and it is preferable that it be a fluorine atom.

[0263] In equation (BZ-1), R 111 and R 112 They may combine to form a ring. It is preferable that the formed ring be a 5-membered ring or a 6-membered ring.

[0264] R of equation (BZ-1) 111 -SO2-R201 and R 112 -SO2-R 202 It is desirable that... Also, R 201 and R 202 It is preferable that each is independently a fluorine atom, an alkyl group having a fluorine atom as a substituent, or an aryl group having a fluorine atom as a substituent, more preferable that it is a fluorine atom or an alkyl group having a fluorine atom as a substituent, and even more preferable that it is an alkyl group having a fluorine atom as a substituent.

[0265] In formula (BZ-2), R 113 Silver, -SO2-R 203 or -CO-R 203 Represents, and R 114 and R 115 -SO2-R 204 , -CO-R 204 or represents cyanotype, R 203 and R 204 Each independently represents a halogen atom, an alkyl group, or an aryl group, and R 113 and, R 114 or R 115 It may combine to form a ring.

[0266] R 203 and R 204 The number of carbon atoms in the alkyl group represented by is preferably 1 to 10, and more preferably 1 to 6. R 203 and R 204 The alkyl group represented by is preferably an alkyl group having a halogen atom as a substituent, and more preferably an alkyl group having a fluorine atom as a substituent.

[0267] R 203 and R 204 The number of carbon atoms in the aryl group represented by is preferably 6 to 20, and more preferably 6 to 12. R 203 and R 204 The aryl group represented by is preferably an aryl group having a halogen atom as a substituent, and more preferably an aryl group having a fluorine atom as a substituent.

[0268] R 203 and R 204 Examples of the halogen atoms represented by fluorine atoms, chlorine atoms, and bromine atoms may be fluorine atoms, and it is preferable that it be a fluorine atom.

[0269] In equation (BZ-2), R 113 and, R 114 or R 115 They may combine to form a ring. It is preferable that the formed ring be a 5-membered ring or a 6-membered ring.

[0270] In equation (BZ-2), R 113 Silver, -SO2-R 203 It is desirable that R 114 and R 115 -SO2-R 204 or -CO-R 204 It is desirable that -SO2-R 204 It is more desirable that... Also, R 203 and R 204 It is preferable that each is independently a fluorine atom, an alkyl group having a fluorine atom as a substituent, or an aryl group having a fluorine atom as a substituent, more preferable that it is a fluorine atom or an alkyl group having a fluorine atom as a substituent, and even more preferable that it is an alkyl group having a fluorine atom as a substituent.

[0271] In formula (BZ-3), R 116 ~R 119 Each represents, independently, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a cyano group. Examples of halogen atoms include fluorine atoms, chlorine atoms, and bromine atoms, and it is preferable that it be a fluorine atom. The alkyl group, aryl group, alkoxy group, and aryloxy group may have substituents or may be unsubstituted. If it has substituents, it is preferable that it be a halogen atom or an alkyl group substituted with a halogen atom, and more preferable that it be a fluorine atom or an alkyl group substituted with a fluorine atom.

[0272] In equation (BZ-3), R 116 ~R 119 Preferably, at least one of them is a cyano group, a fluorine atom, an alkyl group having a fluorine atom as a substituent, an aryl group having a fluorine atom as a substituent, or an aryl group having an alkyl group substituted with a fluorine atom as a substituent, and R 116 ~R 119 It is more preferable that all of them are cyano groups, fluorine atoms, alkyl groups having fluorine atoms as substituents, or aryl groups having fluorine atoms as substituents, and it is more preferable that they are fluorine atoms.

[0273] In formula (BZ-4), R 120 It represents a silver, alkyl group, or aryl group. R 120 The number of carbon atoms in the alkyl group represented here is preferably 1 to 10, and more preferably 1 to 6. R 120 The alkyl group represented here may have a substituent. Examples of substituents include halogen atoms, alkoxy groups, aryl groups, aryloxy groups, acyl groups, acyloxy groups, etc. R 120 The number of carbon atoms in the aryl group represented here is preferably 6 to 20, and more preferably 6 to 12. R 120 The aryl group represented here may have a substituent. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, acyl groups, acyloxy groups, etc.

[0274] In formula (BZ-5), R 121 It represents a silver, alkyl group, or aryl group. R 121 The number of carbon atoms in the alkyl group represented here is preferably 1 to 10, and more preferably 1 to 6. R 121 The alkyl group represented here may have a substituent. Examples of substituents include halogen atoms, alkoxy groups, aryl groups, aryloxy groups, acyl groups, acyloxy groups, etc. R 121 The number of carbon atoms in the aryl group represented here is preferably 6 to 20, and more preferably 6 to 12. R 121The aryl group represented here may have a substituent. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, acyl groups, acyloxy groups, etc.

[0275] In formula (BZ-6), R 122 represents an alkyl group or an aryl group, and R 123 It represents silver, a hydrogen atom, an alkyl group, or an aryl group. R 122 and R 123 The number of carbon atoms in the alkyl group represented here is preferably 1 to 10, and more preferably 1 to 6. R 122 and R 123 The alkyl group represented here may have a substituent. Examples of substituents include halogen atoms, alkoxy groups, aryl groups, aryloxy groups, acyl groups, acyloxy groups, etc. R 122 and R 123 The number of carbon atoms in the aryl group represented here is preferably 6 to 20, and more preferably 6 to 12. R 122 and R 123 The aryl group represented here may have a substituent. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, acyl groups, acyloxy groups, etc.

[0276] Among the formula (BZ-7), R 124 ~R 129 represents, respectively, a halogen atom or a halogenated hydrocarbon group. R 124 ~R 129 Examples of the halogen atoms represented by R include fluorine atoms, chlorine atoms, and bromine atoms, and it is preferable that it be a fluorine atom. 124 ~R 129 The halogenated hydrocarbon group represented by is preferably an alkyl group having a halogen atom as a substituent, and more preferably an alkyl group having a fluorine atom as a substituent. The number of carbon atoms in the halogenated hydrocarbon group is preferably 1 to 10, and more preferably 1 to 6.

[0277] In formula (BZ-8), R 130~R 135 represents, respectively, a halogen atom or a halogenated hydrocarbon group. R 130 ~R 135 Examples of the halogen atoms represented by R include fluorine atoms, chlorine atoms, and bromine atoms, and it is preferable that it be a fluorine atom. 130 ~R 135 The halogenated hydrocarbon group represented by is preferably an alkyl group having a halogen atom as a substituent, and more preferably an alkyl group having a fluorine atom as a substituent. The number of carbon atoms in the halogenated hydrocarbon group is preferably 1 to 10, and more preferably 1 to 6.

[0278] Specific examples of the counter anion d2 include anions having the structure shown below.

[0279] [Chemical Formula 19]

[0280]

[0281] [Chemical Formula 20]

[0282]

[0283] Also, SbF6 - , (CF3)3PF3 - , (C2F5)2PF4 - , (C2F5)3PF3 - , [(CF3)2CF]2PF4 - , [(CF3)2CF]3PF3, (n-C3F7)2PF4 - , (n-C3F7)3PF3 - , (n-C4F9)3PF3 - , (C2F5)(CF3)2PF3 - , [(CF3)2CFCF2]2PF4 - , [(CF3)2CFCF2]3PF3, (n-C4F9)2PF4 - , (n-C4F9)3PF3 - , (C2F4H)(CF3)2PF3 - , (C2F3H2)3PF3 - , (C2F5)(CF3)2PF3 -, (CF3)4B - , (CF3)3BF - , (CF3)2BF2 - , (CF3)BF3 - , (C2F5)4B - , (C2F5)3BF - , (C2F5)BF3 - , (C2F5)2BF2 - , (CF3)(C2F5)2BF - , (CF3C6H4)4B - , (C6F5)2BF2 - , (C6F5)BF3 - , (C6H3F2)4B - , B(CN)F3 - , B(CN)2F2 - , B(CN)3F - , (CF3)3B(CN) - , (CF3)2B(CN)2 - , (C2F5)3B(CN) - , (C2F5)2B(CN)2 - , (n-C3F7)3B(CN) - , (n-C4F9)3B(CN) - , (n-C4F9)2B(CN)2 - , (n-C6F 13 )3B(CN) - , (CHF2)3B(CN) - , (CHF2)2B(CN)2 - , (CH2CF3)3B(CN) - , (CH2CF3)2B(CN)2 - , (CH2C2F5)3B(CN) - , (CH2C2F5)2B(CN)2 - , (CH2CH2C3F7)2B(CN)2 - , (n-C3F7CH2)2B(CN)2 - , (C6H5)3B(CN) - , and anions of the following structures can be cited as specific examples.

[0284] [Chemical Formula 21]

[0285]

[0286] [Chemical Formula 22]

[0287]

[0288] [Chemical Formula 23]

[0289]

[0290] The content of compound D in the total solid content of the coloring composition is preferably 1 to 60 mass%. The upper limit is preferably 50 mass% or less, and more preferably 40 mass% or less. The lower limit is preferably 3 mass% or more, and more preferably 6 mass% or more. When the content of compound D is within the above range, the effects of the present invention are exhibited more significantly.

[0291] The content of compound D is preferably 5 to 1,000 parts by mass per 100 parts by mass of dye. The upper limit is preferably 600 parts by mass or less, and more preferably 300 parts by mass or less. The lower limit is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more. When the content of compound D is within the above range, the effects of the present invention are exhibited more significantly.

[0292] Suzy

[0293] The coloring composition of the present invention preferably contains a resin in addition to the compound D described above. The resin is incorporated, for example, for the purpose of dispersing particles such as pigments within the coloring composition or for use as a binder. Furthermore, a resin used primarily to disperse particles such as pigments is also referred to as a dispersant. However, such uses of the resin are merely examples, and it may be used for purposes other than such uses.

[0294] The weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.

[0295] Examples of resins include (meth)acrylic resin, epoxy resin, (meth)acrylamide resin, n·thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, siloxane resin, etc. In addition, as a resin, the resin described in paragraphs 0091–0099 of International Publication No. 2022 / 065215, the block polyisocyanate resin described in Japanese Published Patent Application No. 2016-222891, the resin described in Japanese Published Patent Application No. 2020-122052, the resin described in Japanese Published Patent Application No. 2020-111656, the resin described in Japanese Published Patent Application No. 2020-139021, the resin comprising a constituent unit having a ring structure in the main chain and a constituent unit having a biphenyl group in the side chain described in Japanese Published Patent Application No. 2017-138503, the resin described in paragraphs 0199–0233 of Japanese Published Patent Application No. 2020-186373, the alkali-soluble resin described in Japanese Published Patent Application No. 2020-186325, and Korea A resin represented by Formula 1 described in Korean Patent Publication No. 10-2020-0078339, a copolymer containing epoxy groups and acid groups described in International Patent Publication No. 2022 / 030445, and a compound described in Japanese Patent Publication No. 2018-135514 may also be used.

[0296] As for the resin, it is preferable to use a resin having acid groups. A resin having acid groups can be used as an alkali-soluble resin. Examples of acid groups include carboxyl groups, phosphate groups, sulfonyl groups, phenolic hydroxyl groups, etc.

[0297] The acid value of the resin having acid groups is preferably 30 to 500 mg KOH / g. The lower limit is more preferably 40 mg KOH / g or higher, and particularly preferably 50 mg KOH / g or higher. The upper limit is more preferably 400 mg KOH / g or lower, more preferably 300 mg KOH / g or lower, and particularly preferably 200 mg KOH / g or lower. The weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, and more preferably 5,000 to 50,000. In addition, the number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.

[0298] A resin having acid groups preferably comprises repeating units having acid groups in side chains, and more preferably comprises 5 to 70 mol% of the total repeating units of the resin. The upper limit of the content of repeating units having acid groups in side chains is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of repeating units having acid groups in side chains is preferably 10 mol% or more, and more preferably 20 mol% or more.

[0299] Regarding resins having acid groups, reference may be made to paragraphs 0558–0571 of Japanese Patent Publication No. 2012-208494 (paragraphs 0685–0700 of the corresponding U.S. Patent Application Publication No. 2012 / 0235099) and paragraphs 0076–0099 of Japanese Patent Publication No. 2012-198408, the contents of which are incorporated by reference into this specification. In addition, commercially available resins having acid groups may be used. In addition, regarding the method of introducing acid groups into the resin, there are no particular limitations, but for example, the method described in Japanese Patent Publication No. 6349629 may be cited. In addition, as a method of introducing acid groups into the resin, a method of introducing acid groups by reacting an acid anhydride with a hydroxyl group generated by the ring-opening reaction of an epoxy group may also be cited.

[0300] The coloring composition of the present invention preferably comprises a resin having basic groups. The resin having basic groups is preferably a resin comprising repeating units having basic groups in side chains, more preferably a copolymer having repeating units having basic groups in side chains and repeating units not having basic groups, and even more preferably a block copolymer having repeating units having basic groups in side chains and repeating units not having basic groups. The resin having basic groups may also be used as a dispersant. The amine value of the resin having basic groups is preferably 5 to 300 mgKOH / g. The lower limit is preferably 10 mgKOH / g or higher, and more preferably 20 mgKOH / g or higher. The upper limit is preferably 200 mgKOH / g or lower, and more preferably 100 mgKOH / g or lower.

[0301] Commercially available resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (all manufactured by Big Chem), Solspers 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, Examples include 38500, 39000, 53095, 56000, 7100 (all manufactured by Nihon Lubrizol Co., Ltd.), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF Co., Ltd.). Additionally, for resins having basic groups, block copolymer (B) described in paragraphs 0063 to 0112 of Japanese Patent Publication No. 2014-219665, block copolymer A1 described in paragraphs 0046 to 0076 of Japanese Patent Publication No. 2018-156021, and vinyl resin having basic groups described in paragraphs 0150 to 0153 of Japanese Patent Publication No. 2019-184763 may be used, and the contents thereof are incorporated herein by reference.

[0302] It is also preferable that the coloring composition of the present invention comprises, respectively, a resin having acidic groups and a resin having basic groups. According to this embodiment, the storage stability of the coloring composition can be further improved. When a resin having acidic groups and a resin having basic groups are used in combination, the content of the resin having basic groups is preferably 20 to 500 parts by mass per 100 parts by mass of the resin having acidic groups, more preferably 30 to 300 parts by mass, and even more preferably 50 to 200 parts by mass.

[0303] As for the resin, it is also desirable to use a resin having an aromatic carboxyl group. In the resin having an aromatic carboxyl group, the aromatic carboxyl group may be included in the main chain of the repeating unit or in the side chain of the repeating unit. It is preferable that the aromatic carboxyl group be included in the main chain of the repeating unit. Furthermore, in this specification, an aromatic carboxyl group is a group having a structure in which one or more carboxyl groups are attached to an aromatic ring. In the aromatic carboxyl group, the number of carboxyl groups attached to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2. Examples of resins having an aromatic carboxyl group include the resins described in paragraphs 0082 to 0107 of International Publication No. 2021 / 166858.

[0304] The coloring composition of the present invention preferably contains a resin as a dispersant. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, an acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups. As an acidic dispersant (acidic resin), a resin in which the amount of acid groups is 70 mol% or more when the total amount of acid groups and basic groups is 100 mol% is preferred. The acid groups of the acidic dispersant (acidic resin) are preferably carboxyl groups. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH / g. Furthermore, a basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups. As a basic dispersant (basic resin), a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol% is preferred. The basic group of the basic dispersant is preferably an amino group.

[0305] It is also preferable that the resin used as a dispersant be a graft resin. For details of the graft resin, reference may be made to paragraphs 0025 to 0094 of Japanese Patent Publication No. 2012-255128, and the contents thereof are incorporated herein by reference.

[0306] It is also preferable that the resin used as a dispersant be a resin having aromatic carboxyl groups. Examples of resins having aromatic carboxyl groups include those described above.

[0307] The resin used as a dispersant is preferably a polyimine-based dispersant that includes a nitrogen atom in at least one of the main chain and the side chain. As a polyimine-based dispersant, a resin having a main chain having a partial structure with functional groups having a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and also having a basic nitrogen atom in at least one of the main chain and the side chain, is preferred. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom that exhibits basicity. For polyimine-based dispersants, reference may be made to paragraphs 0102 to 0166 of Japanese Patent Publication No. 2012-255128, and the contents thereof are incorporated herein by reference.

[0308] It is also preferable that the resin used as a dispersant be a resin having a structure in which a plurality of polymer chains are bonded to the core portion. Examples of such resins include dendrimers (including star-shaped polymers). In addition, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Publication No. 2013-043962.

[0309] The resin used as a dispersant is preferably a resin comprising repeating units having ethylenically unsaturated bond-containing groups in the side chains. The content of repeating units having ethylenically unsaturated bond-containing groups in the side chains is preferably 10 mol% or more of the total repeating units of the resin, more preferably 10 to 80 mol%, and even more preferably 20 to 70 mol%.

[0310] As a dispersant, the resin described in Japanese Patent Publication No. 2018-087939, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent Publication No. 6432077, polyethyleneimine having polyester side chains described in International Patent Publication No. 2016 / 104803, block copolymer described in International Patent Publication No. 2019 / 125940, block polymer having acrylamide structural units described in Japanese Patent Publication No. 2020-066687, block polymer having acrylamide structural units described in Japanese Patent Publication No. 2020-066688, and the dispersant described in International Patent Publication No. 2016 / 104803 may be used.

[0311] Dispersants are also available as commercially available products, and specific examples thereof include the DISPERBYK series from BYK Chemie, the SOLSPERSE series from Nippon Lubrizol, the Efka series from BASF, and the Azisper series from Ajinomoto Fine Techno Co., Ltd. In addition, the product described in paragraph 0129 of Japanese Patent Publication No. 2012-137564 and the product described in paragraph 0235 of Japanese Patent Publication No. 2017-194662 may also be used as a dispersant.

[0312] The resin content in the total solid content of the coloring composition is preferably 50 mass% or less, more preferably 40 mass% or less, more preferably 35 mass% or less, and even more preferably 30 mass% or less. The lower limit can be 0 mass% or more, 1 mass% or more, or 2 mass% or more.

[0313] In addition, the content of the resin having acid groups (alkali-soluble resin) in the total solid content of the coloring composition is preferably 50 mass% or less, more preferably 40 mass% or less, more preferably 35 mass% or less, and even more preferably 30 mass% or less. The lower limit can be 0 mass% or more, 1 mass% or more, or 2 mass% or more.

[0314] In addition, the content of the resin having acid groups (alkali-soluble resin) in the total amount of resin is preferably 30 mass% or more, more preferably 50 mass% or more, more preferably 70 mass% or more, and particularly preferably 80 mass% or more, for the reason that excellent developability is easily obtained. The upper limit may be 100 mass%, 95 mass%, or 90 mass% or less. The coloring composition of the present invention may contain only one type of resin or may contain two or more types. When two or more types of resin are included, it is preferable that their total amount be within the above range.

[0315] <<Compounds having cyclic ether groups>>

[0316] The coloring composition of the present invention may contain a compound having a cyclic ether group. Examples of cyclic ether groups include epoxy groups, oxetaneyl groups, etc. Preferably, the compound having a cyclic ether group is a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of epoxy compounds include compounds having one or more epoxy groups within one molecule, and compounds having two or more epoxy groups are preferred. Preferably, the epoxy compound is a compound having 1 to 100 epoxy groups within one molecule. The upper limit of epoxy groups included in the epoxy compound may be, for example, 10 or fewer, or 5 or fewer. The lower limit of epoxy groups included in the epoxy compound is preferably 2 or more. As compounds having cyclic ether groups, compounds described in paragraphs 0034 to 0036 of Japanese Patent Publication No. 2013-011869, paragraphs 0147 to 0156 of Japanese Patent Publication No. 2014-043556, paragraphs 0085 to 0092 of Japanese Patent Publication No. 2014-089408, compounds described in Japanese Patent Publication No. 2017-179172, xanthen-type epoxy resin described in Japanese Patent Publication No. 2021-195421, and xanthen-type epoxy resin described in Japanese Patent Publication No. 2021-195422 may be used.

[0317] A compound having a cyclic ether group may be a low molecular weight compound (e.g., molecular weight less than 2,000, furthermore, molecular weight less than 1,000) or a macromolecule (e.g., molecular weight 1,000 or more; in the case of a polymer, weight average molecular weight 1,000 or more). The weight average molecular weight of a compound having an epoxy group is preferably 200 to 100,000, and more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5,000 or less, and even more preferably 3,000 or less.

[0318] Examples of commercially available compounds having cyclic ether groups include EHPE3150 (manufactured by Daicel Inc.), EPICLON N-695 (manufactured by DIC Inc.), Mapruf G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (all manufactured by Nichiyu Inc., epoxy group-containing polymers).

[0319] The content of a compound having a cyclic ether group in the total solid content of the coloring composition is preferably 0.1 to 20 mass%. The lower limit is preferably 0.5 mass% or more, and more preferably 1 mass% or more. The upper limit is preferably 15 mass% or less, and more preferably 10 mass% or less. Only one type of compound having a cyclic ether group may be used, or two or more types may be used. If two or more types are used, it is preferable that their total amount falls within the above range.

[0320] <<Pigment Derivatives>>

[0321] The coloring composition of the present invention may contain a pigment derivative. Examples of pigment derivatives include compounds having at least one structure selected from the group consisting of a pigment structure and a triazine structure, and an acidic or basic group.

[0322] Examples of the above pigment structures include quinoline pigment structure, benzimidazoleone pigment structure, benzisoindole pigment structure, benzothiazol pigment structure, iminium pigment structure, squaryllium pigment structure, croconium pigment structure, oxonol pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrrole pigment structure, azo pigment structure, azometain pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, anthraquinone pigment structure, quinacridone pigment structure, dioxazine pigment structure, perinone pigment structure, perylene pigment structure, thiazine indigo pigment structure, thioindigo pigment structure, isoindolin pigment structure, isoindolinone pigment structure, quinophthalone pigment structure, disthiol pigment structure, triarylmethane pigment structure, pyromethene pigment structure, etc.

[0323] Examples of acid groups possessed by pigment derivatives include carboxyl groups, sulfo groups, phosphate groups, boronic acid groups, imidic acid groups, and salts thereof. As atoms or atomic groups constituting the salt, alkali metal ions (Li + , Na + , K + Alkaline earth metal ions (Ca, etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ Examples include ammonium ions, imidazolium ions, pyridinium ions, phosphonium ions, etc. As for imidic acid groups, -SO2NHSO2R X1 , -CONHSO2R X2 , -CONHCOR X3 or -SO2NHCOR X4 It is desirable, and -SO2NHSO2R X1 , -CONHSO2R X2 , or -SO2NHCOR X4 is more desirable, and -SO2NHSO2R X1 or -CONHSO2R X2 is more desirable. R X1 ~R X4 represents, respectively, an alkyl group or an aryl group. R X1 ~R X4The alkyl and aryl groups represented by α may have substituents. As substituents, halogen atoms are preferred, and fluorine atoms are more preferred. R X1 ~R X4 Each is preferably, independently, an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and more preferably an alkyl group containing a fluorine atom. The number of carbon atoms in the alkyl group containing a fluorine atom is preferably 1 to 10, more preferably 1 to 5, and more preferably 1 to 3. The number of carbon atoms in the aryl group containing a fluorine atom is preferably 6 to 20, more preferably 6 to 12, and more preferably 6.

[0324] Basic groups of pigment derivatives include amino groups, pyridinyl groups and their salts, ammonium salts, and phthalimidemethyl groups. Atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, phenoxide ions, etc.

[0325] As for the amino group, -NR x11 R x12 Examples include groups that appear as and cyclic amino groups.

[0326] -NR x11 R x12 In the group represented as, R x11 and R x12Each of the elements independently represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably an alkyl group. That is, the amino group is preferably a dialkylamino group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and more preferably 1 to 3. The alkyl group may be straight-chain, branched, or cyclic, but is preferably straight-chain or branched, and more preferably straight-chain. The alkyl group may have a substituent. Examples of substituents include the aforementioned substituent T. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and more preferably 6 to 12. The aryl group may have a substituent. Examples of substituents include the aforementioned substituent T.

[0327] Examples of cyclic amino groups include pyrrolidine, piperidine, piperazine, and morpholine groups. These groups may have additional substituents.

[0328] As for the pigment derivative, a pigment derivative with excellent visible transparency (hereinafter also referred to as a transparent pigment derivative) may be used. The maximum value (εmax) of the molar extinction coefficient of the transparent pigment derivative in the wavelength range of 400 to 700 nm is 3000 L·mol -1 ·cm -1 It is preferable that it be less than or equal to 1000 L·mol -1 ·cm -1 It is more preferable that it be less than or equal to 100 L·mol -1 ·cm -1 It is more desirable that it be less than or equal to. The lower limit of εmax is, for example, 1 L·mol -1 ·cm -1 That is all, 10L·mol -1 ·cm -1 It is okay if it is more than that.

[0329] Specific examples of pigment derivatives include compounds described in the examples below, compounds described in paragraph 0124 of International Publication No. 2022 / 085485, benzimidazoleone compounds or their salts described in Japanese Patent Publication No. 2018-168244, and compounds having an isoindoline skeleton described in General Formula (1) of Japanese Patent Publication No. 6996282.

[0330] When the coloring composition of the present invention contains a pigment derivative, the content of the pigment derivative in the total solid content of the coloring composition is preferably 0.3 to 20 mass%. The lower limit is preferably 0.6 mass% or more, and more preferably 0.9 mass% or more. The upper limit is preferably 15 mass% or less, more preferably 12.5 mass% or less, and more preferably 10 mass% or less. In addition, the content of the pigment derivative is preferably 1 to 30 mass parts per 100 mass parts of pigment. The lower limit is preferably 2 mass parts or more, and more preferably 3 mass parts or more. The upper limit is preferably 25 mass parts or less, more preferably 20 mass parts or less, and more preferably 15 mass parts or less. The coloring composition of the present invention may contain only one type of pigment derivative or may contain two or more types. In the case of including two or more types of pigment derivatives, it is desirable that their total amount be within the above range.

[0331] Silane Coupling Agent

[0332] The coloring composition of the present invention may contain a silane coupling agent. As a silane coupling agent, a silane compound having a hydrolyzable group may be used, and it is preferable that the silane compound has a hydrolyzable group and other functional groups. A hydrolyzable group refers to a substituent that is directly connected to a silicon atom and can generate a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of hydrolyzable groups include a halogen atom, an alkoxy group, an acyloxy group, etc., and an alkoxy group is preferred. That is, a silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, examples of functional groups other than hydrolyzable groups include a vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group, isocyanate group, phenyl group, etc., and amino group, (meth)acryloyl group, and epoxy group are preferred. Specific examples of silane coupling agents include the compound described in paragraph 0177 of International Publication No. 2022 / 085485 and the compound described in Japanese Patent Publication No. 2019-183020. The content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.01 to 15.0 mass%, and more preferably 0.05 to 10.0 mass%. The silane coupling agent may be of only one type or two or more types. In the case of two or more types, it is preferable that the total amount be within the above range.

[0333] <<Solvent>>

[0334] The coloring composition of the present invention preferably contains a solvent. Examples of solvents include organic solvents. Basically, there are no particular restrictions on the type of solvent as long as it satisfies the solubility of each component and the coating properties of the composition. Examples of organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents, etc. For details regarding these, reference may be made to paragraph 0223 of International Publication No. 2015 / 166779, the contents of which are incorporated herein by reference. In addition, ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups may also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples include 3-methoxy-N,N-dimethylpropaneamide, 3-butoxy-N,N-dimethylpropaneamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma-butyrolactone, sulforaine, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol and 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropyl alcohol, etc.However, aromatic hydrocarbons used as organic solvents (benzene, toluene, xylene, ethylbenzene, etc.) may be reduced for reasons such as environmental considerations (for example, with respect to the total amount of organic solvents, it may be reduced to 50 mass ppm (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less).

[0335] In the present invention, it is preferable to use an organic solvent with a low metal content. The metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent at the mass ppt (parts per trillion) level may be used, and such organic solvents are provided, for example, by Toyo Kosei Co., Ltd. (Kagaku Kogyo Nippo, November 13, 2015).

[0336] Methods for removing impurities such as metals from organic solvents include, for example, distillation (such as molecular distillation or thin-film distillation) or filtration using a filter. Regarding the filter hole diameter of the filter used for filtration, it is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0337] Organic solvents may contain isomers (compounds with the same number of atoms but different structures). In addition, isomers may contain only one type or multiple types.

[0338] It is preferable that the content of peroxide in the organic solvent be 0.8 mmol / L or less, and it is more preferable that it substantially does not contain peroxide.

[0339] The content of the solvent in the coloring composition is preferably 10 to 95 mass%, more preferably 20 to 90 mass%, and even more preferably 30 to 90 mass%.

[0340] In addition, from the perspective of environmental regulation, it is desirable that the coloring composition of the present invention substantially does not contain environmentally regulated substances. Furthermore, in the present invention, "substantially does not contain environmentally regulated substances" means that the content of environmentally regulated substances in the coloring composition is 50 mass ppm or less, which is preferably 30 mass ppm or less, more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Examples of environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are registered as environmentally regulated substances based on the REACH (Registration Evaluation Authorization and Restriction of CHemicals) rules, the PRTR (Pollutant Release and Transfer Register) method, and VOC (Volatile Organic Compounds) regulations, and their usage amounts and handling methods are strictly regulated. These compounds may be used as solvents when manufacturing individual components used in coloring compositions, or may be incorporated into the coloring composition as residual solvents. From the perspective of human safety and environmental considerations, it is desirable to reduce these substances as much as possible. As a method for reducing environmentally regulated substances, one can reduce them by heating or depressurizing the system to raise the boiling point above that of the environmentally regulated substance and then distilling and removing the substance from the system. Furthermore, when distilling and removing small amounts of environmentally regulated substances, it is useful to co-boil with a solvent having a boiling point equivalent to that of the solvent in question to increase efficiency. Additionally, if the system contains compounds capable of radical polymerization, polymerization inhibitors may be added to prevent the radical polymerization reaction from proceeding and causing cross-linking between molecules during vacuum distillation, thereby allowing for vacuum distillation removal.These distillation removal methods may be any of the following stages: the raw material stage, the product stage resulting from the reaction of the raw material (e.g., a resin solution or a polyfunctional monomer solution after polymerization), or the stage of a coloring composition produced by mixing these compounds.

[0341] Polymerization Inhibitor

[0342] The coloring composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salt, cerium 1 salt, etc.). Among these, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the coloring composition is preferably 0.0001 to 5 mass%. The polymerization inhibitor may be of only one type or of two or more types. In the case of two or more types, the total amount is preferably within the above range.

[0343] <<Surfactant>>

[0344] The coloring composition of the present invention may contain a surfactant. As a surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants may be used. It is preferable that the surfactant be a silicone-based surfactant or a fluorine-based surfactant, and it is more preferable that it be a silicone-based surfactant. Regarding surfactants, reference may be made to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, and the contents thereof are incorporated herein by reference.

[0345] As a fluorine-based surfactant, compounds described in paragraphs 0167 to 0173 of International Publication No. 2022 / 085485 may be used.

[0346] Examples of nonionic surfactants include the compound described in paragraph 0174 of International Publication No. 2022 / 085485.

[0347] Examples of silicone-based surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (all manufactured by Dow Toray Corporation), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (all manufactured by Bic Chem), etc. there is.

[0348] In addition, compounds with the following structure may be used as silicone-based surfactants.

[0349] [Chemical Formula 24]

[0350]

[0351] The content of the surfactant in the total solid content of the coloring composition is preferably 0.001 mass% to 5.0 mass%, and more preferably 0.005 to 3.0 mass%. The surfactant may be of only one type or two or more types. In the case of two or more types, it is preferable that the total amount be within the above range.

[0352] UV absorber

[0353] The coloring composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, dibenzoyl compounds, etc. Specific examples of such compounds may include the compound described in paragraph 0179 of International Publication No. 2022 / 085485, the reactive triazine ultraviolet absorber described in Japanese Patent Publication No. 2021-178918, the ultraviolet absorber described in Japanese Patent Publication No. 2022-007884, and the compound described in Korean Patent Publication No. 10-2022-0014454. The content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.01 to 10 mass%, and more preferably 0.01 to 5 mass%. In the present invention, only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount be within the above range.

[0354] <<Antioxidant>>

[0355] The coloring composition of the present invention may contain an antioxidant. Examples of antioxidants include phenol compounds, phosphite ester compounds, thioether compounds, etc. As phenol compounds, any phenol compound known as a phenolic antioxidant may be used. Preferred phenol compounds include hindered phenol compounds. Compounds having a substituent at a site (orthosite) adjacent to a phenolic hydroxyl group are preferred. As the substituents mentioned above, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. In addition, compounds having a phenol group and a phosphite ester group within the same molecule are also preferred as antioxidants. Furthermore, phosphorus-based antioxidants may also be suitably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosperfin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosperfin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphite. Examples of commercially available antioxidants include Adekastav AO-20, Adekastav AO-30, Adekastav AO-40, Adekastav AO-50, Adekastav AO-50F, Adekastav AO-60, Adekastav AO-60G, Adekastav AO-80, and Adekastav AO-330 (all manufactured by ADEKA Inc.). Additionally, as antioxidants, compounds described in paragraphs 0023 to 0048 of Japanese Patent Publication No. 6268967, compounds described in International Publication No. 2017 / 006600, compounds described in International Publication No. 2017 / 164024, and compounds described in Korean Patent Publication No. 10-2019-0059371 may be used. The content of the antioxidant in the total solid content of the coloring composition is preferably 0.01 to 20 mass%, and more preferably 0.3 to 15 mass%.Only one type of antioxidant may be used, or two or more types may be used. If two or more types are used, it is desirable that the total amount be within the above range.

[0356] <<Curing Accelerator>>

[0357] The coloring composition of the present invention may include a curing accelerator. Examples of curing accelerators include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds, etc. Specific examples of curing accelerators include the compound described in paragraph 0164 of International Publication No. 2022 / 085485 and the compound described in Japanese Patent Publication No. 2021-181406. The content of the curing accelerator in the total solid content of the coloring composition is preferably 0.3 to 8.9 mass%, and more preferably 0.8 to 6.4 mass%.

[0358] Other ingredients

[0359] The coloring composition of the present invention may, if necessary, contain sensitizers, plasticizers, and other additives (e.g., conductive particles, fillers, defoaming agents, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately including these components, properties such as film properties can be adjusted. These components may be compounds described in paragraph 0182 of International Publication No. 2022 / 085485.

[0360] The coloring composition of the present invention may contain a metal oxide to adjust the refractive index of the resulting film. Examples of metal oxides include TiO2, ZrO2, Al2O3, SiO2, etc. The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. In addition, in this case, the core portion may be hollow.

[0361] The coloring composition of the present invention may include a light resistance improver. Examples of light resistance improvers include the compound described in paragraph 0183 of International Publication No. 2022 / 085485.

[0362] It is also preferable that the coloring composition of the present invention substantially does not contain terephthalic acid esters. Here, "substantially does not contain" means that the content of terephthalic acid esters is 1,000 ppb by mass or less of the total amount of the coloring composition, more preferably 100 ppb by mass or less, and particularly preferably zero.

[0363] In terms of environmental regulations, it is preferable that the coloring composition of the present invention has a melamine content of 10,000 ppm by mass or less.

[0364] The coloring composition of the present invention preferably has a metal content of 100 ppm by mass or less in the glass, and more preferably 50 ppm by mass or less. In addition, the halogen content of the glass is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less.

[0365] In addition, it is preferable that the chloride ion concentration in the coloring composition be 100 mass ppm or less, and more preferable that it be 50 mass ppm or less.

[0366] Methods for reducing metals or halogens in glass within a coloring composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with ion-exchange resin.

[0367] From the perspective of environmental regulations, the use of perfluoroalkylsulfonic acids and their salts, and perfluoroalkylcarboxylic acids and their salts, may be restricted. In the coloring composition of the present invention, when reducing the content of the above compounds, the content of perfluoroalkylsulfonic acids (particularly perfluoroalkylsulfonic acids having 6 to 8 carbon atoms in the perfluoroalkyl group) and their salts, and perfluoroalkylcarboxylic acids (particularly perfluoroalkylcarboxylic acids having 6 to 8 carbon atoms in the perfluoroalkyl group) and their salts is preferably in the range of 0.01 ppb to 1,000 ppb with respect to the total solid content of the coloring composition, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb. The coloring composition of the present invention may not substantially contain perfluoroalkylsulfonic acids and their salts, and perfluoroalkylcarboxylic acids and their salts. For example, by using compounds that can substitute perfluoroalkylsulfonic acid and its salts, and compounds that can substitute perfluoroalkylcarboxylic acid and its salts, a coloring composition that substantially does not contain perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts may be selected. As compounds that can substitute for regulated compounds, for example, compounds excluded from regulation based on differences in the number of carbon atoms in the perfluoroalkyl group may be cited. However, the foregoing does not prevent the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts. The coloring composition of the present invention may contain perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts, to the maximum allowable extent.

[0368] The moisture content of the coloring composition of the present invention is typically 3 mass% or less, preferably 0.01 to 1.5 mass%, and more preferably in the range of 0.1 to 1.0 mass%. The moisture content can be measured by the Karl Fischer method.

[0369] The coloring composition of the present invention can be used by adjusting the viscosity for purposes such as adjusting the film surface shape (flatness, etc.) and adjusting the film thickness. The viscosity value can be appropriately selected as needed, but for example, 0.3 mPa·s to 50 mPa·s at 25°C is preferred, and 0.5 mPa·s to 20 mPa·s is more preferred. As a method for measuring viscosity, for example, a cone plate type viscometer can be used and measured under conditions where the temperature is adjusted to 25°C.

[0370] <<Container>>

[0371] As for the container for the coloring composition, there are no particular limitations, and a known container may be used. In addition, as the container, the container described in paragraph 0187 of International Publication No. 2022 / 085485 may be used.

[0372] Method for preparing a coloring composition

[0373] The coloring composition of the present invention can be prepared by mixing the above-described components. When preparing the coloring composition, the coloring composition may be prepared by simultaneously dissolving and / or dispersing all components in a solvent, or, if necessary, each component may be prepared into two or more appropriate solutions or dispersions and mixed at the time of use (application) to prepare the coloring composition.

[0374] In addition, when preparing a coloring composition, it is desirable to include a process for dispersing pigments. In the process for dispersing pigments, mechanical forces used for pigment dispersion include compression, pressing, impact, shearing, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flotjet mixers, high-pressure wet atomization, and ultrasonic dispersion. Furthermore, when grinding pigments in a sand mill (bead mill), it is desirable to process under conditions that increase grinding efficiency by using beads with a small diameter or increasing the bead filling ratio. Additionally, it is desirable to remove coarse particles after the grinding process by means of filtration or centrifugation. In addition, the process and disperser for dispersing pigments may suitably be used as described in “The Great Collection of Dispersion Technology, published by Joho Kiko Co., Ltd., July 15, 2005,” “Comprehensive Data Collection on Practical Applications of Dispersion Technology Centered on Suspension (Solid / Liquid Dispersion System), published by Keiei Kaihatsu Center Publishing Department, October 10, 1978,” and paragraph 0022 of Japanese Patent Publication No. 2015-157893. In addition, in the process for dispersing pigments, particle refinement treatment may be performed using a salt milling process. For materials, equipment, and processing conditions used in the salt milling process, reference may be made to the descriptions in, for example, Japanese Patent Publication No. 2015-194521 and Japanese Patent Publication No. 2012-046629.

[0375] When preparing a coloring composition, it is desirable to filter the coloring composition with a filter for purposes such as removing foreign substances or reducing defects. Examples of the types of filters and filtration methods used for filtration include the filters and filtration methods described in paragraphs 0196 to 0199 of International Publication No. 2022 / 085485.

[0376] <Cut>

[0377] The film of the present invention is a film obtained from the coloring composition of the present invention described above. The film of the present invention can be used in color filters, etc. Specifically, it can be preferably used as a coloring layer (pixel) of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc. The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and more preferably 0.3 μm or more.

[0378] Color Filter

[0379] Next, the color filter of the present invention will be described. The color filter of the present invention has the film of the present invention described above. More preferably, the film of the present invention is used as a pixel of the color filter. The color filter of the present invention can be used for solid-state imaging devices such as CCDs (charge coupling devices) or CMOS (complementary metal oxide semiconductors) or image display devices.

[0380] In the color filter of the present invention, the film thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and more preferably 0.3 μm or more.

[0381] It is preferable that the width of the pixels included in the color filter be 0.5 to 20.0 μm. The lower limit is preferably 1.0 μm or more, and more preferably 2.0 μm or more. The upper limit is preferably 15.0 μm or less, and more preferably 10.0 μm or less. In addition, the Young's modulus of the pixels is preferably 0.5 to 20 GPa, and more preferably 2.5 to 15 GPa.

[0382] It is desirable that each pixel included in the color filter possesses high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although no lower limit is specified, it is desirable, for example, to be 0.1 nm or more. The surface roughness of the pixel can be measured, for example, using a Veeco Dimension 3100 AFM (Atomic Force Microscope). In addition, the contact angle of water on the pixel can be set to an appropriately desirable value, but typically ranges from 50 to 110°. The contact angle can be measured, for example, using a contact angle meter CV-DT Type A (manufactured by Kyowa Kaimen Chemical Co., Ltd.). Furthermore, it is desirable that the volume resistivity of the pixel be high. Specifically, the volume resistivity of the pixel is 10 9 It is desirable that it be Ω·cm or greater, and 10 11 It is more desirable for it to be Ω·cm or greater. An upper limit is not specified, but for example, 10 14 It is desirable that it be Ω·cm or less. The volume resistivity of the pixel can be measured, for example, using an ultra-high resistance meter 5410 (manufactured by Advantest).

[0383] In the case of a color filter, a protective layer may be provided on the surface of the film of the present invention. By providing a protective layer, various functions such as oxygen blocking, low reflection, hydrophobicity, and shielding of light of specific wavelengths (ultraviolet, near-infrared, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. Methods for forming the protective layer include a method of forming it by applying a resin composition dissolved in an organic solvent, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. Examples of components constituting the protective layer include (meth)acrylic resin, n·thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluoropolymer resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al2O3, Mo, SiO2, Si2N4, etc., and two or more of these components may be included. For example, in the case of a protective layer intended for oxygen barrier, it is preferable that the protective layer includes polyol resin, SiO2, and Si2N4. In addition, for a protective layer intended for low reflection, it is preferable that the protective layer comprises (meth)acrylic resin and fluoropolymer resin.

[0384] When forming a protective layer by applying a resin composition, known methods such as spin coating, casting, screen printing, and inkjet methods may be used as the method of applying the resin composition. The organic solvent included in the resin composition may be a known organic solvent (e.g., propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.). When forming the protective layer by chemical vapor deposition, known chemical vapor deposition methods (thermal chemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) may be used as the chemical vapor deposition method.

[0385] The protective layer may, if necessary, contain additives such as organic or inorganic microparticles, absorbers of light of a specific wavelength (e.g., ultraviolet, near-infrared, etc.), refractive index modifiers, antioxidants, adhesives, and surfactants. Examples of organic or inorganic microparticles include polymer microparticles (e.g., silicone resin microparticles, polystyrene microparticles, melamine resin microparticles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, etc. Known absorbers may be used as absorbers of light of a specific wavelength. The content of these additives can be appropriately adjusted, but is preferably 0.1 to 70 mass% with respect to the total mass of the protective layer, and more preferably 1 to 60 mass%.

[0386] In addition, as a protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Publication No. 2017-151176 may be used.

[0387] Method for manufacturing color filters

[0388] Next, a method for manufacturing a color filter using the coloring composition of the present invention will be described. The method for manufacturing a color filter preferably comprises a process of forming a coloring composition layer on a support using the coloring composition of the present invention, a process of exposing the coloring composition layer to light in a pattern, and a process of developing and removing unexposed portions of the coloring composition layer to form a pattern (pixel). If necessary, a process of baking the coloring composition layer (pre-baking process) and a process of baking the developed pattern (pixel) (post-baking process) may also be provided.

[0389] In the process of forming a coloring composition layer, a coloring composition layer is formed on a support using the coloring composition of the present invention. The support is not particularly limited and can be appropriately selected according to the application. Examples include a glass substrate and a silicon substrate, and a silicon substrate is preferred. Furthermore, a charge coupling device (CCD), a complementary metal-oxide-semiconductor (CMOS), a transparent conductive film, etc., may be formed on the silicon substrate. Additionally, a black matrix is ​​formed on the silicon substrate to isolate each pixel. Furthermore, an underlayer may be provided on the silicon substrate to improve adhesion with the upper layer, prevent material diffusion, or flatten the substrate surface. The surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. It is also preferably 30 to 80° when measured with water.

[0390] Known methods may be used as the method for applying the coloring composition. Examples include drop casting; slit coating; spraying; roll coating; spin coating; fluid coating; slit and spin; pre-wetting (e.g., the method described in Japanese Patent Publication No. 2009-145395); various printing methods such as inkjet (e.g., on-demand, piezo, thermal), nozzlejet, etc., flexographic printing, screen printing, gravure printing, inversion offset printing, metal mask printing, etc.; transfer methods using molds, etc.; nanoimprinting methods, etc. In addition, the application method described in paragraph 0207 of International Patent Publication No. 2022 / 085485 may also be used.

[0391] The colored composition layer formed on the support may be dried (pre-baked). If the film is manufactured by a low-temperature process, pre-baking is not required. If pre-baking is performed, the pre-baking temperature is preferably 150°C or lower, more preferably 120°C or lower, and more preferably 110°C or lower. The lower limit may be, for example, 50°C or higher, or 80°C or higher. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and more preferably 80 to 220 seconds. Pre-baking may be performed using a hot plate, an oven, etc.

[0392] Next, the colored composition layer is exposed in a pattern (exposure process). For example, the colored composition layer can be exposed in a pattern by using a stepper exposure machine or a scanner exposure machine, etc., and exposing it through a mask having a predetermined mask pattern. By doing so, the exposed portion can be cured.

[0393] Examples of radiation (light) that can be used during exposure include g-rays and i-rays. Additionally, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) may be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), with KrF rays (wavelength 248 nm) being preferred. Furthermore, a light source with a long wavelength of 300 nm or more may also be used. As a light source, an electrodeless ultraviolet lamp system or a hybrid curing of ultraviolet and infrared rays may be used.

[0394] Additionally, during exposure, light may be irradiated continuously or pulsed (pulse exposure). Furthermore, pulse exposure is an exposure method in which light is irradiated and paused repeatedly in short cycles (e.g., at the millisecond level or less).

[0395] The irradiation dose (exposure dose) is, for example, 0.03 to 2.5 J / cm² 2 It is desirable, and 0.05~1.0 J / cm 2 It is more preferable. The oxygen concentration during exposure can be appropriately selected, and in addition to performing the procedure under atmospheric conditions, exposure may be performed, for example, under a low-oxygen atmosphere where the oxygen concentration is 19 volume% or less (e.g., 15 volume%, 5 volume%, or substantially oxygen-free), or under a high-oxygen atmosphere where the oxygen concentration exceeds 21 volume% (e.g., 22 volume%, 30 volume%, or 50 volume%). Furthermore, the exposure intensity can be appropriately set, typically 1000 W / m² 2 ~100,000 W / m² 2 (For example, 5000W / m² 2 , 15000W / m 2 , or, 35,000W / m² 2 It can be selected from the range. Oxygen concentration and exposure illuminance may be appropriately combined; for example, oxygen concentration 10 volume% and illuminance 10,000 W / m² 2, oxygen concentration 35 volume% and illuminance 20,000 W / m² 2 It can be done with the back.

[0396] Next, the unexposed portion of the coloring composition layer is developed and removed to form a pattern (pixel). The development and removal of the unexposed portion of the coloring composition layer can be performed using a developer solution. As a result, the coloring composition layer of the unexposed portion in the exposure process is dissolved into the developer solution, leaving only the photocured portion. The temperature of the developer solution is, for example, preferably 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, to improve residue removal, the process of shaking off the developer solution every 60 seconds and supplying a fresh developer solution may be repeated several more times.

[0397] Examples of developing solutions include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used. As for the developing solution and the cleaning (rinsing) method after development, the developing solution or cleaning method described in paragraph 0214 of International Publication No. 2022 / 085485 may be used.

[0398] After development and drying, it is preferable to perform additional exposure treatment or heat treatment (post-baking). Additional exposure treatment or post-baking is a curing treatment performed after development to ensure complete curing. For example, the heating temperature for post-baking is preferably 100 to 300°C, and more preferably 200 to 270°C. Post-baking can be performed on the film after development in a continuous or batch manner using heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater to achieve the above conditions. When performing additional exposure treatment, it is preferable that the light used for exposure be light with a wavelength of 400 nm or less. In addition, the additional exposure treatment may be performed by the method described in Korean Published Patent Application No. 10-2017-0122130.

[0399] Solid-state imaging sensor

[0400] The solid-state imaging element of the present invention has the film of the present invention described above. As for the configuration of the solid-state imaging element, there are no particular limitations as long as it is a configuration that has the film of the present invention and functions as a solid-state imaging element, but for example, the following configuration may be cited.

[0401] The device has a configuration having a plurality of photodiodes constituting a light-receiving area of ​​a solid-state imaging element (CCD (charge-coupled device) image sensor, CMOS (complementary metal-oxide-semiconductor) image sensor, etc.) on a substrate and a transmission electrode made of polysilicon, etc., a light-shielding film having only the light-receiving portion of the photodiode open on the photodiode and the transmission electrode, a device protection film made of silicon nitride, etc. formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and a color filter on the device protection film. In addition, the device protection film may have a light-collecting means (e.g., a micro lens, etc.; hereinafter the same) on the side closer to the substrate, or a configuration in which the light-collecting means is formed on the color filter. Furthermore, the color filter may have a structure in which each colored pixel is embedded in a space partitioned, for example, in a grid shape by a partition wall. In this case, it is preferable that the partition wall has a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include the devices described in Japanese Patent Publication No. 2012-227478, Japanese Patent Publication No. 2014-179577, and International Patent Publication No. 2018 / 043654. Additionally, as shown in Japanese Patent Publication No. 2019-211559, light resistance may be improved by providing an ultraviolet absorption layer within the structure of the solid-state imaging element. An imaging device equipped with the solid-state imaging element of the present invention can be used for digital cameras or electronic devices having imaging functions (such as mobile phones), as well as for automotive cameras or surveillance cameras.

[0402] Image display device

[0403] The image display device of the present invention has the film of the present invention described above. Examples of image display devices include liquid crystal display devices and organic electroluminescence display devices. Definitions of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (by Akio Sasaki, published by Kogyo Chosakai Co., Ltd., 1990) and "Display Devices" (by Sumiaki Ibuki, published by Sangyo Tosho Co., Ltd., 1st year of the Heisei era). In addition, liquid crystal display devices are described, for example, in "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd., 1994). There are no particular limitations on the liquid crystal display devices to which the present invention can be applied, and, for example, it can be applied to various types of liquid crystal display devices described in the above "Next-Generation Liquid Crystal Display Technology."

[0404] Examples

[0405] The present invention will be explained in more detail below with reference to examples. The materials, usage amounts, ratios, processing details, processing procedures, etc., shown in the following examples may be appropriately modified without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In addition, in the structural formulas shown below, Me is a methyl group, Et is an ethyl group, and i-Pr is an isopropyl group.

[0406] <Example of Compound Synthesis>

[0407] (Example of synthesis of ammonium monomer 1)

[0408] 14.3 g of N-(2-(methacryloyloxy)ethyl)-N,N-dimethylbutane-1-amium chloride and 15 g of water were added to a beaker and mixed. 20.0 g of potassium bis((perfluoroethyl)sulfonyl)amide and 200 g of water were added to a 3-neck flask, and the mixture was stirred at room temperature for 30 minutes using a stirring blade and a three-way motor. After confirming complete dissolution, N-(2-(methacryloyloxy)ethyl)-N,N-dimethylbutane-1-amium chloride prepared separately was added dropwise over 10 minutes. After stirring for 1 hour, 100 mL of butyl acetate was added and stirred for 30 minutes. The liquids were transferred using a separatory funnel and left to stand for 5 minutes; after this, the lower organic layer was removed, and the upper aqueous layer was discarded. The organic layer was returned to the separatory funnel, and 100 mL of water was added and shaken. After standing for 5 minutes, the lower organic layer was transferred to a 500 mL volumetric flask. 5 mg of (4-hydroxy-2,2,6,6-tetramethylpiperazine-1-yloxy) radical (OH-TEMPO) was added, and the solvent was distilled off using a rotary evaporator at 10 torr and 40°C for 1 hour. 0.5 g of the obtained ammonium monomer 1 was weighed, and after vacuum drying at 130°C for 2 hours, the remaining weight was 99.9%, and the remaining butyl acetate measured by gas chromatography was 0.1 mass%. The amount of potassium detected by inductively coupled plasma emission spectroscopy (ICP-OES) was 600 ppm. For 1 g of the sample, titration was performed using a 0.01 N silver nitrate aqueous solution, and the residual Cl amount was 20 ppm. The residual moisture amount measured with a Karl Fischer moisture meter was 200 ppm.

[0409] (Example of synthesis of ammonium monomer 2)

[0410] Two beakers were prepared by adding 19.5 g of methacloylcholine chloride and 80 g of water to each beaker. 20.0 g of potassium bis((trifluoromethyl)sulfonyl)amide and 200 g of water were added to a 3-neck flask, and the mixture was stirred at room temperature for 30 minutes using a stirring blade and a 3-one motor. After confirming complete dissolution, a separately prepared aqueous solution of methacloylcholine chloride was added dropwise over 10 minutes. After stirring for 1 hour, 100 mL of ethyl acetate was added, and the mixture was stirred for 30 minutes. The liquid was transferred using a separatory funnel and left to stand for 5 minutes; afterward, the lower organic layer was removed, and the upper aqueous layer was discarded. The organic layer was returned to the 3-neck flask, and a separately prepared aqueous solution of methacloylcholine chloride was added dropwise over 10 minutes while stirring. After stirring for 30 minutes, the liquid was transferred to a separatory funnel and left to stand for 5 minutes. The lower organic layer was removed, and the upper aqueous layer was discarded. The organic layer was returned to the separatory funnel, 100 mL of water was added, and the mixture was shaken. After standing for 5 minutes, the lower organic layer was transferred to a 500 mL volumetric flask. 5 mg of OH-TEMPO was added, and the solvent was distilled off using a rotary evaporator at 20 torr and 40°C for 1 hour. 0.5 g of the obtained ammonium monomer 2 was weighed, and after vacuum drying at 130°C for 2 hours, the remaining weight was 99.8%, and the remaining ethyl acetate measured by gas chromatography was 0.1 mass%. The amount of potassium detected by ICP-OES was 800 ppm. For 1 g of the sample, titration was performed using a 0.01 N silver nitrate aqueous solution, and the residual Cl amount was 35 ppm. The residual moisture amount measured with a Karl Fischer moisture meter was 800 ppm.

[0411] (Example of synthesis of ammonium monomer 3)

[0412] Two beakers were prepared by adding 32.1 g of methacloylcholine chloride and 80 g of water to each beaker. 20.0 g of sodium p-toluenesulfonate and 200 g of water were added to a 3-neck flask, and the mixture was stirred at room temperature for 30 minutes using a stirring blade and a 3-one motor. After confirming complete dissolution, a separately prepared aqueous solution of methacloylcholine chloride was added dropwise over 10 minutes. After stirring for 1 hour, 100 mL of dichloromethane was added and stirred for 30 minutes. The liquids were transferred using a separatory funnel and left to stand for 5 minutes; afterward, the lower organic layer was removed, and the upper aqueous layer was discarded. The organic layer was returned to the 3-neck flask, and a separately prepared aqueous solution of methacloylcholine chloride was added dropwise over 10 minutes while stirring. After stirring for 30 minutes, the liquid was transferred to a separatory funnel and left to stand for 5 minutes. The lower organic layer was removed, and the upper aqueous layer was discarded. The organic layer was returned to the separatory funnel, 100 mL of water was added, and the mixture was shaken. After standing for 5 minutes, the lower organic layer was transferred to a 500 mL volumetric flask. 5 mg of OH-TEMPO was added, and the solvent was distilled off using a rotary evaporator at 10 torr and 40°C for 1 hour. 0.5 g of the obtained ammonium monomer 3 was weighed, and after vacuum drying at 130°C for 2 hours, the remaining weight was 99.9%. The amount of sodium detected by ICP-OES measurement was 500 ppm. When titrated with a 0.01 N silver nitrate aqueous solution on 1 g of the sample, the remaining amount of Cl was 30 ppm. The residual moisture content measured with a Karl Fischer moisture meter was 100 ppm.

[0413] (Example of synthesis of ammonium monomer 4)

[0414] 29.1 g of n-butyl p-toluenesulfonic acid, 60 g of 1-methoxy-2-propanol, and 5 mg of OH-TEMPO were added to a 3-neck flask and stirred at room temperature for 5 minutes using a stirring blade and a 3-one motor. Subsequently, 20 g of 2-(dimethylamino)ethyl methacrylate was added dropwise over 5 minutes. The temperature was raised to 100°C, and the reaction was completed by heating and stirring for 5 hours. The completion of the reaction was confirmed by NMR by the disappearance of the peaks of the raw materials, n-butyl p-toluenesulfonic acid and 2-(dimethylamino)ethyl methacrylate. 0.5 g of the obtained ammonium monomer solution was weighed, and the remaining weight after vacuum drying at 110°C for 2 hours was 45.1%.

[0415] [Chemical Formula 25]

[0416]

[0417] (Example of synthesis of compound AP-1)

[0418] 26.7 g of 1-methoxy-2-propanol was added to a 3-neck flask, a stirring blade, a nitrogen inlet tube, a condenser, and a thermometer were set, nitrogen was flowed at 20 mL / min, and the mixture was heated and stirred at 200 rpm until the internal temperature reached 80 degrees. To this, 10.6 g of ammonium monomer 1, 9.6 g of light ester HO-MS(N) (manufactured by Kyoei Chemicals Co., Ltd.), 2.7 g of methyl methacrylate, 0.67 g of 1-dodecanethiol, 0.38 g of V-601 (manufactured by Fujifilm Wako Junyaku Co., Ltd.), and 26.7 g of 1-methoxy-2-propanol were dissolved and added dropwise over 2 hours. After heating and stirring at 80°C for 2 hours, the temperature was raised to 90°C and heated and stirred for another 2 hours. After cooling to room temperature, the mixture was stirred under atmospheric conditions for 5 minutes. 3.7 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 0.058 g of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO), 1.5 g of Parmin DM2098 (manufactured by Kao Chemical Co., Ltd.), and 11.5 g of 1-methoxy-2-propanol were added, and the mixture was heated and stirred at 90°C for 40 hours to obtain a solution containing compound AP-1. The acid value calculated by titrating 0.5 g of the above solution with a 1N KOH aqueous solution was 0.87 mmol / g, and the remaining weight after weighing 0.5 g of the above solution and vacuum drying at 130°C for 2 hours was 30.2%. The kinematic viscosity was 2.00 cSt when the concentration was adjusted to 0.030 g / mL using 1-methoxy-2-propanol and measured with a Uberode (manufactured by Shibata Chemical Co., Ltd.) with a viscometer constant of 0.005. When measured in the same way using 1-methoxy-2-propanol as the solvent, the kinematic viscosity was 1.63 cSt. The weight-average molecular weight measured using GPC (hexafluoro-2-propanol eluent, Toso TSKgel SuperAW3000 column, and polyethylene glycol as the molecular weight standard) was 8000.

[0419] (Example of synthesis of compound AP-2)

[0420] 22.0 g of 1-methoxy-2-propanol was added to a 3-neck flask, and a stirring blade, nitrogen inlet tube, condenser, and thermometer were set. Nitrogen was flowed at 20 mL / min, and the mixture was heated and stirred at 200 rpm until the internal temperature reached 80 degrees. To this, 4.4 g of ammonium monomer 2, 3.8 g of methacrylic acid, 9.8 g of benzyl methacrylate, 1.11 g of 1-dodecanethiol (manufactured by Fujifilm Wako Junyaku Co., Ltd.), 0.63 g of V-601 (manufactured by Fujifilm Wako Junyaku Co., Ltd.), and 22.0 g of 1-methoxy-2-propanol were dissolved and added dropwise over 2 hours. After heating and stirring at 80°C for 2 hours, the temperature was raised to 90°C and heated and stirred for another 2 hours. After cooling to room temperature, the mixture was stirred under atmospheric conditions for 5 minutes. 3.8g of 4HBAGE (Mitsubishi Chemical), 0.05g of TEMPO, 0.48g of Permin DM2098 (Kao Chemical), and 11.5g of 1-methoxy-2-propanol were added, and the mixture was heated and stirred at 90°C for 40 hours to obtain a solution containing compound AP-2. The acid value calculated by titrating 0.5g of the solution with a 1N KOH aqueous solution was 1.16 mmol / g, and the remaining weight after weighing 0.5g of the solution and vacuum drying at 130°C for 2 hours was 30.5%. The kinematic viscosity was 1.92 cSt when the concentration was adjusted to 0.030 g / mL using 1-methoxy-2-propanol and measured with a Uberode (manufactured by Shibata Chemical Co., Ltd.) with a viscometer constant of 0.005. The kinematic viscosity was 1.63 cSt when measured in the same way using 1-methoxy-2-propanol as the solvent. The weight-average molecular weight measured by GPC (hexafluoro-2-propanol eluent, TSKgel SuperAW3000 column, polyethylene glycol as molecular weight standard) was 4000.

[0421] (Example of synthesis of compound AP-3)

[0422] A solution containing compound AP-3 was obtained by synthesizing it in the same way, except for changing the monomer amount from compound AP-2. The acid value calculated by titrating 0.5 g of the solution with a 1N KOH aqueous solution was 1.14 mmol / g, and the remaining weight after weighing 0.5 g of the solution and vacuum drying it at 130°C for 2 hours was 30.1%. The kinematic viscosity was 1.97 cSt when the concentration was adjusted to 0.030 g / mL using 1-methoxy-2-propanol and measured with a Uberode (manufactured by Shibata Chemical Co., Ltd.) with a viscometer constant of 0.005. The kinematic viscosity was 1.63 cSt when measured in the same way using 1-methoxy-2-propanol as the solvent. The weight-average molecular weight measured using GPC (hexafluoro-2-propanol eluent, TSKgel SuperAW3000 column, polyethylene glycol as molecular weight standard) was 7000.

[0423] (Example of synthesis of compound AP-4)

[0424] A solution containing compound AP-4 was obtained by synthesizing it in the same manner, except that the monomer species and amount were changed from compound AP-2. The acid value calculated by titrating 0.5 g of the solution with a 1N KOH aqueous solution was 0.46 mmol / g, and the remaining weight after weighing 0.5 g of the solution and vacuum drying it at 130°C for 2 hours was 30.8%. The kinematic viscosity was 2.18 cSt when the concentration was adjusted to 0.030 g / mL using 1-methoxy-2-propanol and measured with a Uberode (manufactured by Shibata Chemical Co., Ltd.) with a viscometer constant of 0.005. The kinematic viscosity was 1.63 cSt when measured in the same way using 1-methoxy-2-propanol as the solvent. The weight average molecular weight measured using GPC (hexafluoro-2-propanol eluent, TSKgel SuperAW3000 column, polyethylene glycol as molecular weight standard) was 20,000.

[0425] (Example of synthesis of compound AP-5)

[0426] A solution containing compound AP-5 was obtained by synthesizing it in the same manner, except that the monomer species and amount were changed from compound AP-2. Additionally, ammonium monomer 3 was used as the ammonium monomer. The acid value calculated by titrating 0.5 g of the above solution with a 1N KOH aqueous solution was 1.12 mmol / g, and the remaining weight after weighing 0.5 g of the above solution and vacuum drying it at 130°C for 2 hours was 30.8%. The kinematic viscosity was 2.10 cSt when the concentration was adjusted to 0.030 g / mL using 1-methoxy-2-propanol and measured with a Uberode (manufactured by Shibata Chemical Co., Ltd.) with a viscometer constant of 0.005. The kinematic viscosity was 1.63 cSt when measured in the same way using 1-methoxy-2-propanol as the solvent. The weight-average molecular weight measured using GPC (hexafluoro-2-propanol eluent, TSKgel SuperAW3000 column, polyethylene glycol as molecular weight standard) was 16,000.

[0427] (Synthesization example of compounds AP-6~AP-21, BP-1)

[0428] Compounds AP-6~AP-20 and BP-1 were synthesized by the same method as above.

[0429] The structures of compounds AP-1 to AP-21 and BP-1 are as follows. In addition, in the structural formulas shown below, the numbers indicated for the main chain are mass ratios, and the numbers indicated for the side chains are the number of repeating units.

[0430] (Example of synthesis of compound AP-22)

[0431] A solution containing compound AP-22 was obtained by synthesizing in the same manner, except for changing the monomer amount from compound AP-2. Additionally, ammonium monomer 3 was used as the ammonium monomer. The acid value calculated by titrating 0.5 g of the above solution with a 1N KOH aqueous solution was 0.53 mmol / g, and the remaining weight after weighing 0.5 g of the above solution and vacuum drying at 130°C for 2 hours was 29.8%. The concentration was adjusted to 0.030 g / ml using 1-methoxy-2-propanol, and the kinematic viscosity measured with a Uberode (manufactured by Shibata Chemical Co., Ltd.) with a viscometer constant of 0.005 was 1.97 cSt. When measured in the same way with 1-methoxy-2-propanol solvent, the kinematic viscosity was 1.63 cSt. The weight-average molecular weight measured using GPC (hexafluoro-2-propanol eluent, TSKgel SuperAW3000 column, polyethylene glycol as molecular weight standard) was 7000.

[0432] The specific absorbance of each compound represented by the following formula (Aλ) was all 5 or less. The specific absorbance of each compound was measured using 1-methoxy-2-propanol as the solvent.

[0433] Compounds AP-1 to AP-22 are salts of compound d1 having an acidic and cationic group and a counter-anion d2 having a molecular weight of 50 or more, and are compounds with a weight average molecular weight of 2000 or more and a specific absorbance of 5 or less represented by the following formula (Aλ). Compound BP-1 is a comparative compound.

[0434] E 1 =A 1 / (c 1 ×l 1 )… (Aλ)

[0435] E 1 : Specific absorbance of a compound at the maximum absorption wavelength in the wavelength range of 400–700 nm

[0436] A 1 : Absorbance of a compound at the maximum absorption wavelength in the wavelength range of 400–700 nm

[0437] l 1 : Cell length expressed in cm

[0438] c 1 : Concentration of a compound in a solution, expressed in units of mg / ml

[0439] The weight average molecular weight, C=C value (a group containing an ethylenically unsaturated bond), acid value, and ClogP value of the region enclosed by the dotted line for each compound are listed in accordance with the table below. Additionally, the ClogP value of the region enclosed by the dotted line was calculated based on the monomer structure prior to polymerization. Furthermore, the cationic group at the region corresponding to compound d1 constituting compound D is also listed in the table below.

[0440] [Chemical Formula 26]

[0441]

[0442] [Chemical Formula 27]

[0443]

[0444] [Chemical Formula 28]

[0445]

[0446] [Chemical Formula 29]

[0447]

[0448] [Chemical Formula 30]

[0449]

[0450] [Chemical Formula 31]

[0451]

[0452] [Chemical Formula 32]

[0453]

[0454] [Chemical Formula 33]

[0455]

[0456] [Table 1]

[0457]

[0458] <Preparation of Dispersion>

[0459] After mixing the raw materials listed in the table below, 230 parts by mass of zirconia beads with a diameter of 0.3 mm were added, and a dispersion treatment was performed for 5 hours using a paint shaker. Next, the dispersion was obtained by separating the zirconia beads by filtration. In addition, the solid content concentration (mass%) and pigment concentration (mass%) of the dispersion are listed together in the table.

[0460] [Table 2]

[0461]

[0462] The details of the materials indicated by abbreviations in the table above are as follows.

[0463] (Pigment)

[0464] PG-1: CI Pigment Blue 15:6

[0465] PG-2: CI Pigment Red 254

[0466] PG-3: CI Pigment Yellow 139

[0467] PG-4: CI Pigment Yellow 150

[0468] PG-5: CI Pigment Violet 23

[0469] PG-6: CI Pigment Green 36

[0470] (derivative)

[0471] PS-1: BYK-SYNERGIST 2100 (BYK)

[0472] PS-2: BYK-SYNERGIST 2105 (BYK company)

[0473] PS-3~PS-9: Compounds with the following structures

[0474] [Chemical Formula 34]

[0475]

[0476] [Chemical Formula 35]

[0477]

[0478] (Dispersant)

[0479] D-1: DISPERBYK-161 (Big Chemistry)

[0480] D-2: 30 mass% propylene glycol monomethyl ether acetate solution of the resin having the following structure (the values ​​indicated on the main chain are molar ratios. The weight-average molecular weight of the resin is 11,000)

[0481] [Chemical Formula 36]

[0482]

[0483] D-3: 30 mass% propylene glycol monomethyl ether acetate solution of a resin having the following structure (the numbers indicated for the main chain are molar ratios, and the numbers indicated for the side chains are the number of repeating units. The weight-average molecular weight of the resin is 7,000.)

[0484] [Chemical Formula 37]

[0485]

[0486] D-4: 30 mass% propylene glycol monomethyl ether acetate solution of FlySurf A215C (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

[0487] (solvent)

[0488] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0489] S-3: 1-Methoxy-2-Propanol (PGME)

[0490] <Preparation of Coloring Composition>

[0491] A coloring composition was obtained by mixing raw materials other than the solvent listed in the table below, 0.0007 parts by mass of a polymerization inhibitor (p-methoxyphenol), and 0.05 parts by mass of a silicone-based surfactant (Shin-Etsu Kagaku Kogyo, KF-6000), and then adding the solvent listed in the table below so that the solid content concentration becomes 12% by mass. In addition, in the table, the amount of the solvent other than the solvent is in parts by mass based on the solid content conversion value, and the solvent ratio is a mass ratio.

[0492] [Table 3]

[0493]

[0494] [Table 4]

[0495]

[0496] [Table 5]

[0497]

[0498] [Table 6]

[0499]

[0500] [Table 7]

[0501]

[0502] [Table 8]

[0503]

[0504] [Table 9]

[0505]

[0506] [Table 10]

[0507]

[0508] [Table 11]

[0509]

[0510] [Table 12]

[0511]

[0512] [Table 13]

[0513]

[0514] [Table 14]

[0515]

[0516] The details of the materials indicated by abbreviations in the table above are as follows.

[0517] (Dispersion)

[0518] Dispersions 1~9: The aforementioned dispersions 1~9

[0519] (Dye solution)

[0520] A-1: Cyclohexanone solution (solids concentration: 12.3 mass%) of a dye of the following structure (xanthen dye, weight-average molecular weight: 7000, m: 3, n: 3).

[0521] [Chemical Formula 38]

[0522]

[0523] A-2: Cyclohexanone solution of a dye of the following structure (xanthen dye, molecular weight: 704.24) (solids concentration: 12.3 mass%)

[0524] [Chemical Formula 39]

[0525]

[0526] A-3: Cyclohexanone solution (solids concentration: 12.3 mass%) of a dye of the following structure (xanthen dye, weight average molecular weight: 10,000).

[0527] [Chemical Formula 40]

[0528]

[0529] A-4: Cyclohexanone solution (solids concentration: 12.3 mass%) of a dye of the following structure (xanthen dye, molecular weight: 1,115.28).

[0530] [Chemical Formula 41]

[0531]

[0532] A-5: Cyclohexanone solution (solids concentration: 12.3 mass%) of a dye of the following structure (molecular weight: 1,165.32).

[0533] [Chemical Formula 42]

[0534]

[0535] A-6: Cyclohexanone solution (solids concentration: 12.3 mass%) of a dye of the following structure (molecular weight: 774.97).

[0536] [Chemical Formula 43]

[0537]

[0538] A-7: Cyclohexanone solution (solids concentration: 12.3 mass%) of a dye of the following structure (molecular weight: 410.52).

[0539] [Chemical Formula 44]

[0540]

[0541] A-8: Cyclohexanone solution of CI Acid Red 289 (xanthen dye, molecular weight: 676.73) (solids concentration: 12.3 mass%)

[0542] A-9: Cyclohexanone solution (solids concentration: 12.3 mass%) of a colored polymer (xanthen dye, weight average molecular weight: 9000) having the following structure

[0543] [Chemical Formula 45]

[0544]

[0545] A-10: Cyclohexanone solution (solids concentration: 12.3 mass%) of a dye of the following structure (molecular weight: 324.42).

[0546] [Chemical Formula 46]

[0547]

[0548] A-11: Cyclohexanone solution (solids concentration: 12.3 mass%) of a dye of the following structure (molecular weight: 374.33).

[0549] [Chemical Formula 47]

[0550]

[0551] A-20: Cyclohexanone solution of Acid Green 27 (solids concentration: 12.3 mass%)

[0552] A-21: Cyclohexanone solution of Acid yellow 23 (solids concentration: 12.3 mass%)

[0553] A-22: Cyclohexanone solution of Solvent Blue 25 (solids concentration: 12.3 mass%)

[0554] A-23: Cyclohexanone solution of Acid Red 52 (solids concentration: 12.3 mass%)

[0555] A-24: Cyclohexanone solution of dye of the following structure (solid content: 12.3 mass%)

[0556] [Chemical Formula 48]

[0557]

[0558] A-25: Cyclohexanone solution of dye of the following structure (solid content: 12.3 mass%)

[0559] [Chemical Formula 49]

[0560]

[0561] A-26: Cyclohexanone solution of dye of the following structure (solid content: 12.3 mass%)

[0562] [Chemical Formula 50]

[0563]

[0564] A-27: Cyclohexanone solution of dye of the following structure (solid content: 12.3 mass%)

[0565] A-28: Cyclohexanone solution of dye of the following structure (solid content: 12.3 mass%)

[0566] A-29: Cyclohexanone solution of dye of the following structure (solid content: 12.3 mass%)

[0567] [Chemical Formula 51]

[0568]

[0569] (Specific compound)

[0570] AP-1~AP-22: The aforementioned compounds AP-1~AP-22

[0571] BP-1: The aforementioned compound BP-1

[0572] (profit)

[0573] P-1: 30 mass% propylene glycol monomethyl ether acetate solution of a resin having the following structure (the numbers indicated on the main chain are the molar ratios of the repeating units. The weight-average molecular weight of the resin is 11,000.)

[0574] [Chemical Formula 52]

[0575]

[0576] P-2: 40 mass% propylene glycol monomethyl ether acetate solution of a resin having the following structure (the numbers indicated on the main chain are the molar ratios of the repeating units. The weight-average molecular weight of the resin is 11,000.)

[0577] [Chemical Formula 53]

[0578]

[0579] P-3: A 30 mass% propylene glycol monomethyl ether acetate solution of a resin having the following structure (the numbers indicated for the main chain are the molar ratio of repeating units, and the numbers indicated for the side chains are the number of repeating units. The weight-average molecular weight of the resin is 11,000.)

[0580] [Chemical Formula 54]

[0581]

[0582] P-4: 40 mass% propylene glycol monomethyl ether acetate solution of a resin having the following structure (the numbers indicated on the main chain are the molar ratios of the repeating units. The weight-average molecular weight of the resin is 11,000.)

[0583] [Chemical Formula 55]

[0584]

[0585] (polymerizable compound)

[0586] M-1: KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, Nippon Kayaku Co., Ltd.)

[0587] M-2, M-3: Compounds with the following structures

[0588] [Chemical Formula 56]

[0589]

[0590] (Photopolymerization initiator)

[0591] I-1~I-8: Compounds with the following structures

[0592] [Chemical Formula 57]

[0593]

[0594] (Additives)

[0595] E-1: Compound of the following structure (UV absorber)

[0596] E-2: Compounds of the following structure (weight average molecular weight 3500, compounds having cyclic ether groups)

[0597] E-3: Compounds of the following structure (weight average molecular weight 2300, compounds having cyclic ether groups)

[0598] E-4: Compounds with the following structure (silane coupling agents)

[0599] E-5: Compounds with the following structure (silane coupling agents)

[0600] E-6: Compounds with the following structure (silane coupling agents)

[0601] E-7: Compounds of the following structure (antioxidants)

[0602] E-8: Lithium bis(trifluoromethanesulfonyl)imide

[0603] E-9: Sodium p-toluenesulfonate

[0604] E-10: Compounds of the following structure (polyfunctional thiol compounds)

[0605] E-11: Compounds of the following structure (polyfunctional thiol compounds)

[0606] [Chemical Formula 58]

[0607]

[0608] <Performance Evaluation>

[0609] <<Evaluation of Examples 1–69 and Comparative Examples 1–3>>

[0610] (Evaluation of lightfastness)

[0611] Each coloring composition was applied onto a glass substrate by the spin coating method and heat-treated (pre-baked) at 120°C for 120 seconds using a hot plate. The obtained film was exposed using an i-line stepper exposure device FPA-3000i5+ (Canon Corporation) through a mask with a square dot pattern having a side length of 1.0 μm. Specifically, light with a wavelength of 365 nm was applied to the film at 1000 mJ / cm² 2 The glass substrate having the exposed film formed thereon was placed on a horizontal rotating table of a spin shower developer (DW-30 type, Chemitronics Co., Ltd.), and subsequently, a colored pattern was formed by performing puddle development at 23°C for 60 seconds using a 60% diluted solution of CD-2000 (Fujifilm Electronics Materials Co., Ltd.). The glass substrate with the formed colored pattern was fixed to the horizontal rotating table using a vacuum chuck method, and next, while rotating the silicon wafer at a rotation speed of 50 rpm using a rotating device, pure water was supplied in a shower form from a spray nozzle above the center of rotation to perform a rinsing treatment, followed by spray drying. By performing a heat treatment (post-bake) for 300 seconds using a hot plate at 200°C, a colored pattern (pixel) with a thickness of 0.6 μm was formed.

[0612] For the obtained pixels, the light transmittance (transmittance) in the wavelength range of 400 to 700 nm was measured using an MCPD-3000 manufactured by Otsuka Denshi Co., Ltd. Next, the pixels produced above were irradiated with 100,000 Lux of light for 2,000 hours using a light tolerance tester (Super Xenon Weather Meter SX75, manufactured by Suga Shikenki Co., Ltd.) (total irradiation amount 200 million Luxhr). The transmittance of the pixels after light irradiation was measured, and the light tolerance was evaluated according to the following criteria.

[0613] -metewand-

[0614] A: The cumulative value of the transmittance of the pixel at a wavelength of 400~700nm after light irradiation is 98% or more of the cumulative value of the transmittance of the pixel at a wavelength of 400~700nm before light irradiation.

[0615] B: The integrated value of the transmittance of the pixel at a wavelength of 400~700nm after light irradiation is 94% or more and less than 98% of the integrated value of the pixel at a wavelength of 400~700nm before light irradiation.

[0616] C: The cumulative value of the transmittance of the pixel at a wavelength of 400~700nm after light irradiation is 90% or more and less than 94% of the cumulative value of the transmittance of the pixel at a wavelength of 400~700nm before light irradiation.

[0617] D: The cumulative value of the transmittance of the colored pixel at a wavelength of 400~700nm after light irradiation is less than 90% of the cumulative value of the transmittance of the pixel at a wavelength of 400~700nm before light irradiation.

[0618] (Evaluation of sensitivity (exposure sensitivity))

[0619] Each coloring composition was applied onto a silicon wafer by spin coating and dried (pre-baked) at 100°C for 120 seconds using a hot plate to form a composition layer with a thickness of 0.60 μm.

[0620] Next, the composition layer was exposed by irradiating light of wavelength 365 nm with a specific exposure amount using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.) through a mask pattern in which a square non-mask portion with a side of 1.0 μm was arranged in an area of ​​4 mm × 3 mm.

[0621] Next, a silicon wafer having a composition layer formed after exposure was placed on a horizontal rotating table of a spin shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.) and puddle developed at 23°C for 60 seconds using a developer (CD-2000, manufactured by Fujifilm Electronics Materials Co., Ltd.). Then, while rotating the silicon wafer at a rotation speed of 50 rpm, a rinsing treatment was performed by supplying pure water in a shower form from an ejection nozzle above the center of rotation, and then spray-dried to form a pattern (pixel).

[0622] The pattern obtained was observed while varying the specific exposure amount, and the minimum exposure amount that resolves a square pattern with a side length of 1.0 μm was determined and evaluated according to the following evaluation criteria. The smaller the minimum exposure amount, the better the exposure sensitivity of the composition.

[0623] -metewand-

[0624] A: The above minimum exposure amount is 100 mJ / cm² 2 It was less than

[0625] B: The above minimum exposure amount is 100 or more and 200 mJ / cm² 2 It was less than

[0626] C: The above minimum exposure amount is 200 or more and 500 mJ / cm² 2 It was less than

[0627] D: The above minimum exposure amount is 500 or more and 1000 mJ / cm² 2 It was less than

[0628] E: The above minimum exposure amount is 1000 mJ / cm² 2 That was all.

[0629] (Evaluation of Phenomenality)

[0630] CT-4000L (Fujifilm Electronics Materials, Inc.) was applied to an 8-inch (20.32 cm) silicon wafer by the spin coating method to achieve a thickness of 0.1 μm after post-baking, and an undercoating layer was formed by heating at 220°C for 300 seconds using a hot plate, thereby obtaining a silicon wafer (support) with an attached undercoating layer. Each coloring composition was applied by the spin coating method to achieve a thickness of 0.6 μm after post-baking, and then heated at 100°C for 2 minutes using a hot plate. The obtained film was exposed to light using an i-line stepper exposure device FPA-3000i5+ (Canon Corporation) through a mask with a square dot pattern having a side length of 1.0 μm. Specifically, light with a wavelength of 365 nm was applied to the film at a pressure of 1000 mJ / cm² 2 The silicon wafer having the exposed film formed thereon was placed on a horizontal rotating table of a spin shower developer (DW-30 type, Chemitronics Co., Ltd.), and subsequently, a colored pattern was formed on the silicon wafer by performing puddle development at 23°C for 60 seconds using a 60% diluted solution of CD-2000 (Fujifilm Electronics Materials Co., Ltd.). The silicon wafer with the formed colored pattern was fixed to the horizontal rotating table using a vacuum chuck method, and then, while rotating the silicon wafer at a rotation speed of 50 rpm using a rotating device, pure water was supplied in a shower form from a spray nozzle above the center of rotation to perform a rinsing treatment, followed by spray drying. A colored pattern (pixel) was formed by performing a heat treatment (post-bake) for 300 seconds using a hot plate at 200°C. A silicon wafer with pixels formed thereon was observed using a scanning electron microscope (SEM) (magnification: 10,000x), and the development was evaluated according to the following evaluation criteria.

[0631] -metewand-

[0632] A: No residue was found outside the area where the coloring pattern was formed (unexposed area).

[0633] B: Very slight residue was observed outside the area where the coloring pattern was formed (unexposed area), but it was not to the extent of causing practical problems.

[0634] C: Slight residue was observed outside the area where the coloring pattern was formed (unexposed area), but it was not to the extent of causing practical problems.

[0635] D: Significant residue was observed outside the area where the coloring pattern was formed (unexposed area).

[0636] (Evaluation of preservation stability)

[0637] The initial viscosity (V0) of each coloring composition was measured using "RE-85L" manufactured by Toki Sangyo Co., Ltd. Next, the viscosity (V1) of each coloring composition was measured after standing at 45°C for 7 days. Based on the following formula, the viscosity increase rate (%) of the coloring composition after standing was calculated, and storage stability was evaluated. The smaller the value of the viscosity increase rate (%), the better the storage stability. The viscosity of the coloring composition was measured with the temperature adjusted to 25°C.

[0638] Viscosity increase rate (%) = [(Viscosity after settling (V1) - Initial viscosity (V0)) / Initial viscosity (V0)] × 100

[0639] (Assessment of damage)

[0640] Pixels (coloring patterns) produced for the evaluation of phenotype were observed at a magnification of 40,000x using a transmission electron microscope, and the occurrence rate of voids in the pixels (number of pixels with voids inside the pixel / number of observed pixels) was calculated, and damage was evaluated according to the following criteria. In addition, the occurrence rate of voids was calculated by randomly selecting 20 cross-sections and observing the presence or absence of voids in 10 pixels for each cross-section, thereby observing a total of 200 boundaries.

[0641] Occurrence rate = Number of pixels with internal voids / Number of observed pixels

[0642] -metewand-

[0643] 5: The occurrence rate of voids was 0.

[0644] 4: The void occurrence rate was greater than 0 and less than or equal to 0.1.

[0645] 3: The void occurrence rate was greater than 0.1 and less than or equal to 0.2.

[0646] 2: The void occurrence rate was greater than 0.2 and less than or equal to 0.5.

[0647] 1: The void occurrence rate was greater than 0.5 and less than or equal to 1.0.

[0648] <<Evaluation of Examples 301–310 and Comparative Examples 301–303>>

[0649] (Evaluation of sensitivity)

[0650] CT-4000L (Fujifilm Electronics Materials, Inc.) was applied to an 8-inch (20.32 cm) silicon wafer by a spin coat method to achieve a thickness of 0.1 μm after post-baking, and an undercoating layer was formed by heating at 220°C for 300 seconds using a hot plate, thereby obtaining a silicon wafer (support) with an attached undercoating layer. Each coloring composition was applied using a spin coater, and subsequently, heating (pre-baking) was performed at 100°C for 120 seconds using a hot plate to obtain a film with a thickness of 0.45 μm. Subsequently, regarding the film, light with a wavelength of 248 nm (KrF line) was exposed through a patterned mask (0.5 μm × 0.5 μm) using a KrF scanner exposure machine at an illuminance of 35,000 W / m² 2 , exposure rate 20 mJ / cm² 2 Exposure was performed by irradiating under the conditions. Subsequently, for the film after exposure, a shower development was performed at 23°C for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) as the developer. After that, the film was rinsed with a spin shower using pure water, and a colored pattern (pixel) was formed by post-baking at 230°C for 2 minutes.

[0651] exposure rate 200 mJ / cm² 2 Up to 10 mJ / cm² 2 By varying the exposure amount to form a pixel with a line width of 0.7 μm, the sensitivity was evaluated based on the following evaluation criteria.

[0652] -metewand-

[0653] A: The above exposure amount is 60 mJ / cm² 2 This was the case.

[0654] B: The above exposure amount is 60 mJ / cm² 2 Exceeding 100 mJ / cm² 2 This was the case.

[0655] C: The above exposure amount is 100 mJ / cm² 2 Exceeding 150 mJ / cm² 2 This was the case.

[0656] D: The above exposure amount is 150 mJ / cm² 2 Exceeding 200 mJ / cm² 2 This was the case.

[0657] E: The above exposure amount is 200 mJ / cm² 2 That was all.

[0658] (Evaluation of adhesion and phenomenality)

[0659] exposure rate of 100 mJ / cm² 2 Pixels (patterns) were formed in the same manner as the sensitivity evaluation, except for the setting. The obtained pixels were observed at a magnification of 20,000x using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Tech Corp.). The number of peeled pixels was measured out of the total number of pixels (1071 × 1071) formed in a part of the observed image area, and adhesion was evaluated based on the following evaluation criteria.

[0660] -metewand-

[0661] A: The number of peeled pixels was 10 or less.

[0662] B: The number of peeled pixels was greater than 10 and less than or equal to 20.

[0663] C: The number of peeled pixels was greater than 20 and less than or equal to 50.

[0664] D: The number of peeled pixels was greater than 50 and less than or equal to 200.

[0665] E: The number of peeled pixels exceeded 200.

[0666] In addition, the image obtained by the scanning electron microscope was evaluated for its potential based on the following evaluation criteria.

[0667] -metewand-

[0668] A: The linearity of the pixels was excellent, and there was very little residue between pixels.

[0669] B: Pixel linearity was excellent, and there was little residue between pixels.

[0670] C: Pixel linearity was slightly poor, but there was little residue between pixels.

[0671] D: The linearity of the pixels was poor, and there was a lot of residue between pixels.

[0672] E: Due to an excessive amount of residue, pixels were not formed, and the spaces between pixels could not be identified.

[0673] (Evaluation of lightfastness)

[0674] Each coloring composition was applied onto a glass substrate by a spin coating method, and subsequently, heat treatment (pre-baking) was performed at 120°C for 120 seconds using a hot plate. The obtained film was exposed to light with a wavelength of 248 nm (KrF line) through a patterned mask (0.5 μm × 0.5 μm) using a KrF scanner exposure machine at an illuminance of 35,000 W / m² 2 , exposure amount 100 mJ / cm² 2Exposure was performed by irradiating under the conditions. A glass substrate having the exposed film formed thereon was placed on a horizontal rotating table of a spin shower developer (DW-30 type, Chemitronics Co., Ltd.), and subsequently, a colored pattern was formed on the glass substrate by performing puddle development at 23°C for 60 seconds using a 60% diluted solution of CD-2000 (Fujifilm Electronics Materials Co., Ltd.). The glass substrate with the formed colored pattern was fixed to the horizontal rotating table using a vacuum chuck method, and next, while rotating the silicon wafer at a rotation speed of 50 rpm using a rotating device, pure water was supplied in a shower form from a spray nozzle above the center of rotation to perform a rinsing treatment, followed by spray drying. A colored pattern (pixel) with a thickness of 0.45 μm was formed by performing a heat treatment (post-bake) for 300 seconds using a hot plate at 200°C.

[0675] For the obtained pixels, the light transmittance (transmittance) in the wavelength range of 400 to 700 nm was measured using an MCPD-3000 manufactured by Otsuka Denshi Co., Ltd. Next, the pixels produced above were irradiated with 100,000 Lux of light for 2,000 hours using a light tolerance tester (Super Xenon Weather Meter SX75, manufactured by Suga Shikenki Co., Ltd.) (total irradiation amount 200 million Luxhr). The transmittance of the pixels after light irradiation was measured, and the light tolerance was evaluated according to the following criteria.

[0676] -metewand-

[0677] A: The cumulative value of the transmittance of the pixel at a wavelength of 400~700nm after light irradiation is 98% or more of the cumulative value of the transmittance of the pixel at a wavelength of 400~700nm before light irradiation.

[0678] B: The integrated value of the transmittance of the pixel at a wavelength of 400~700nm after light irradiation is 94% or more and less than 98% of the integrated value of the pixel at a wavelength of 400~700nm before light irradiation.

[0679] C: The cumulative value of the transmittance of the pixel at a wavelength of 400~700nm after light irradiation is 90% or more and less than 94% of the cumulative value of the transmittance of the pixel at a wavelength of 400~700nm before light irradiation.

[0680] D: The cumulative value of the transmittance of the pixel at a wavelength of 400~700nm after light irradiation is less than 90% of the cumulative value of the transmittance of the pixel at a wavelength of 400~700nm before light irradiation.

[0681] [Table 15]

[0682]

[0683] [Table 16]

[0684]

[0685] [Table 17]

[0686]

[0687] As shown in the table above, the light resistance evaluation of the example was better than that of the comparative example.

[0688] <Examples 501–510>

[0689] A green composition was applied to a silicon wafer by the spin coating method so that the film thickness after deposition was 1.0 μm. Subsequently, it was heated at 100°C for 2 minutes using a hot plate. Then, using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Corporation), at 1,000 mJ / cm² 2The material was exposed through a mask with a square dot pattern having sides of 2 μm. Subsequently, a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) was used, and puddle development was performed at 23°C for 60 seconds. Afterward, the material was rinsed with a spin shower and further washed with pure water. Subsequently, the green composition was patterned on the silicon wafer by heating at 200°C for 5 minutes using a hot plate. The red composition and the blue composition were patterned sequentially in the same manner to form red, green, and blue colored patterns (Bayer patterns). In Examples 501 to 510, the colored compositions prepared in Examples 1 to 10, respectively, were used as the blue composition. Examples 501 to 510 correspond to the examples in which the colored compositions prepared in Examples 1 to 10, respectively, were used as the blue composition. The Green composition and Red composition used in Examples 501 to 510 will be described later. In addition, a Bayer pattern is a pattern formed by repeating a 2×2 array of color filter elements having one red element, two green elements, and one blue element, as disclosed in U.S. Patent Publication No. 3,971,065. The obtained color filter was introduced into a solid-state imaging element according to a known method. By using the coloring compositions prepared in Examples 1 to 10, a solid-state imaging element having suitable image recognition capabilities and lightfastness was obtained.

[0690] The Green composition and Red composition used in Examples 501 to 510 are as follows.

[0691] [Green Composition]

[0692] The following ingredients were mixed and stirred, and then filtered through a nylon filter (manufactured by Nihon Pole Co., Ltd.) with a hole diameter of 0.45 μm to prepare a Green composition.

[0693] Green pigment dispersion: 73.7 parts by mass

[0694] Resin 4 (40 mass% PGMEA solution): 0.3 mass parts

[0695] Polymerizable compound 1: 1.2 parts by mass

[0696] Photopolymerization initiator 1: 0.6 parts by mass

[0697] Surfactant 1: 4.2 parts by mass

[0698] UV absorber 1: 0.5 parts by mass

[0699] PGMEA: 19.5 parts by mass

[0700] [Red Composition]

[0701] The following ingredients were mixed and stirred, and then filtered through a nylon filter (manufactured by Nihon Pole Co., Ltd.) with a hole diameter of 0.45 μm to prepare a Red composition.

[0702] Red pigment dispersion: 51.7 parts by mass

[0703] Resin 4 (40 mass% PGMEA solution): 0.6 mass parts

[0704] Polymerizable compound 4: 0.6 parts by mass

[0705] Photopolymerization initiator 1: 0.3 parts by mass

[0706] Surfactant 1: 4.2 parts by mass

[0707] PGMEA: 42.6 parts by mass

[0708] The raw materials used in the Green composition and the Red composition are as follows.

[0709] Green pigment dispersion

[0710] A pigment dispersion was prepared by mixing and dispersing a mixture consisting of 6.4 parts by mass of CI Pigment Green 36, 5.3 parts by mass of CI Pigment Yellow 150, 5.2 parts by mass of a dispersant (DISPERBYK-161, BYK-Chemie), and 83.1 parts by mass of PGMEA using a bead mill (zirconia beads 0.3 mm diameter) for 3 hours. Subsequently, a high-pressure disperser NANO-3000-10 equipped with a vacuum reduction mechanism (Nippon BI Co., Ltd.) was used at 2000 kg / cm² 2 A dispersion treatment was performed under pressure at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a green pigment dispersion.

[0711] · Red pigment dispersion

[0712] A mixture comprising 9.6 parts by mass of CI Pigment Red 254, 4.3 parts by mass of CI Pigment Yellow 139, 6.8 parts by mass of a dispersant (DISPERBYK-161, BYK Chemie), and 79.3 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.3 mm diameter) to prepare a pigment dispersion. Subsequently, a dispersion treatment was performed using a high-pressure disperser NANO-3000-10 (Nippon BI Co., Ltd.) equipped with a vacuum reduction mechanism at a flow rate of 500 g / min under a pressure of 2,000 kg / cm³. This dispersion treatment was repeated 10 times to obtain a red pigment dispersion.

[0713] · Polymerizable Compound 1: KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, Nippon Kayaku Co., Ltd.)

[0714] · Polymerizable compound 4: Compound of the following structure

[0715] [Chemical Formula 59]

[0716]

[0717] · Resin 4: Resin having the following structure (the numbers noted in the main chain are the molar ratios of repeating units. The weight-average molecular weight of the resin is 11,000, and the acid value is 70 mgKOH / g.)

[0718] [Chemical Formula 60]

[0719]

[0720] · Photopolymerization Initiator 1: Irgacure OXE01 (BASF)

[0721] · Surfactant 1: 1 mass% PGMEA solution of the following mixture (weight average molecular weight 14,000). In the following formulas, the units of % (62% and 38%) representing the ratio of repeating units are mass%.

[0722] [Chemical Formula 61]

[0723]

[0724] · UV absorber 1 (UV-503, manufactured by Daito Chemical Co., Ltd.)

[0725] The same effect is obtained even if some or all of the resin, polymerizable compound, photopolymerization initiator, and solvent used in the coloring composition of the example are replaced with the materials described in this specification.

Claims

Claim 1 A coloring composition comprising a coloring agent A containing a dye, a polymerization initiator B, a polymerizable compound C, a compound d1 having an acidic group and a cationic group, and a salt of a relative anion d2 having a molecular weight of 50 or more, wherein the compound D has a weight average molecular weight of 2000 or more and a specific absorbance of 5 or less as represented by the formula (Aλ); E 1 =A 1 / (c 1 ×l 1 )… (Aλ)Equation (Aλ), among, E 1 E represents the specific absorbance of compound D at the maximum absorption wavelength in the wavelength range of 400–700 nm, and A 1 ... represents the absorbance of compound D at the maximum absorption wavelength in the wavelength range of 400–700 nm, and l 1 represents the cell length expressed in cm, and c 1 represents the concentration of compound D in the solution, expressed in units of mg / ml. Claim 2 A coloring composition according to claim 1, wherein the cationic group of the compound d1 is a quaternary ammonium cation. Claim 3 A coloring composition according to claim 1 or claim 2, wherein the counter anion d2 is an anion represented by any one of formulas (BZ-1) to (BZ-8); [Chemical Formula 1] In equation (BZ-1), R 111 Silver, -SO2-R 201 or -CO-R 201 Represents, and R 112 is, alkyl group, aryl group, -SO2-R 202 or -CO-R 202 Represents, and R 201 and R 202 Each independently represents a halogen atom, an alkyl group, or an aryl group, and R 111 and R 112 ... may combine to form a ring; in formula (BZ-2), R 113 Silver, -SO2-R 203 or -CO-R 203 Represents, and R 114 and R 115 -SO2-R 204 , -CO-R 204 or represents cyanotype, R 203 and R 204 Each independently represents a halogen atom, an alkyl group, or an aryl group, and R 113 and, R 114 or R 115 may combine to form a ring; in formula (BZ-3), R 116 ~R 119 Each represents, independently, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a cyano group; in formula (BZ-4), R 120 Silver represents an alkyl group or an aryl group; in formula (BZ-5), R 121 Silver represents an alkyl group or an aryl group; in formula (BZ-6), R 122 represents an alkyl group or an aryl group, and R 123 Silver represents a hydrogen atom, an alkyl group, or an aryl group; in formula (BZ-7), R 124 ~R 129 represents, respectively, a halogen atom or a halogenated hydrocarbon group; in formula (BZ-8), R 130 ~R 135 Each represents a halogen atom or a halogenated hydrocarbon group independently. Claim 4 A coloring composition according to claim 1 or claim 2, wherein the counter anion d2 is a bis(fluoroalkylsulfonyl)imide anion. Claim 5 A coloring composition according to claim 1 or claim 2, wherein compound D has a polymerizable group. Claim 6 A coloring composition according to claim 5, wherein the polymerizable group is an ethylene unsaturated bond containing group, and the ethylene unsaturated bond value of compound D is 0.7 mmol / g or higher. Claim 7 A coloring composition according to claim 1 or claim 2, wherein the acid group of the compound d1 is a carboxyl group. Claim 8 A coloring composition according to claim 1 or claim 2, wherein the acid value of compound D is 0.20 to 1.20 mmol / g. Claim 9 A coloring composition according to claim 1 or claim 2, wherein the compound d1 is a polymer having a repeating unit d1-1 having an acid group and a repeating unit d1-2 having a cationic group, and the compound D is a salt formed by the counter anion d2 coordinating to the cationic group of the repeating unit d1-2, and the ClogP value of the salt structure formed by the repeating unit d1-2 and the counter anion d2 is -10.0 to 0.

3. Claim 10 A coloring composition according to claim 1 or claim 2, wherein the dye comprises a dye having a chemical structure including a cation and an anion. Claim 11 A coloring composition according to claim 1 or claim 2, wherein the dye comprises a xanthen dye. Claim 12 A coloring composition according to claim 1 or claim 2, wherein the dye comprises a dye polymer. Claim 13 A coloring composition according to claim 1 or claim 2, wherein the content of the polymerizable compound C in the total solid content of the coloring composition is 5 to 30 mass%. Claim 14 A coloring composition according to claim 1 or claim 2, wherein the chloride ion concentration in the coloring composition is 100 mass ppm or less. Claim 15 A film obtained using the coloring composition described in claim 1 or claim 2. Claim 16 A color filter having a membrane as described in claim 15. Claim 17 A solid-state imaging element having a film as described in claim 15. Claim 18 An image display device having a film as described in claim 15.

Images