WO2023008352A1

WO2023008352A1 - Coloring composition, film, optical filter, solid-state imaging device, image display device, and dye multimer

Info

Publication number: WO2023008352A1
Application number: PCT/JP2022/028563
Authority: WO
Inventors: 佑太奥秋; 祐一安原
Original assignee: 富士フイルム株式会社
Priority date: 2021-07-29
Filing date: 2022-07-25
Publication date: 2023-02-02
Also published as: JPWO2023008352A1; TW202307142A

Abstract

The present invention provides: a coloring composition comprising a dye multimer and a curable compound, the dye multimer including a dye structure having a structure a1, in which aromatic rings having hydroxy groups as substituents are bonded to each other via an azomethine group, or a structure a2, in which the structure a1 is coordinated to a metallic atom; a film; an optical filter; a solid-state imaging device; an image display device; and a dye multimer.

Description

Coloring composition, film, optical filter, solid-state imaging device, image display device, and dye multimer

The present invention relates to coloring compositions. The present invention also relates to a film, an optical filter, a solid-state imaging device, and an image display device using the colored composition. The present invention also relates to dye multimers.

In recent years, due to the spread of digital cameras, camera-equipped mobile phones, etc., the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has increased significantly. Color filters are used as key devices for displays and optical elements. A color filter usually comprises three primary color pixels of red, green and blue and serves to separate the transmitted light into the three primary colors.

The colored pixels of each color of the color filter are manufactured using a coloring composition containing a coloring agent. Patent Document 1 discloses a pigment composition for color filters containing a phthalocyanine-based pigment and an azomethine copper complex-based pigment, wherein the mass ratio of the phthalocyanine-based pigment to the azomethine copper complex-based pigment is 99.9/ A color filter pigment composition is described which is from 0.1 to 96.5/3.5.

WO2019/022051

In recent years, there has been a demand for further improvement in light resistance of films formed using coloring compositions containing coloring agents.

Here, in Patent Document 1, Color Index (C.I.) Pigment Yellow 129 is used as an azomethine copper complex-based pigment. C. I. Pigment Yellow 129 is a compound having the structure shown below. According to the studies of the present inventors, the film obtained using the composition containing the azomethine copper complex-based pigment described in the examples of Patent Document 1 cannot be said to have sufficient light resistance, and there is room for improvement. It turns out there is.

Therefore, an object of the present invention is to provide a coloring composition capable of forming a film with excellent light resistance. Another object of the present invention is to provide a film, an optical filter, a solid-state imaging device, an image display device, and a dye multimer.

According to the studies of the present inventors, the inventors have found that the above-mentioned objects can be achieved with the coloring composition described later, and have completed the present invention. Accordingly, the present invention provides the following.

<1> A coloring composition containing a pigment multimer and a curable compound,
The dye multimer has a structure a1 in which aromatic rings having hydroxy groups as substituents are bonded via an azomethine group, or a dye structure having a structure a2 in which the structure a1 is coordinated to a metal atom.
coloring composition.
<2> The dye multimer contains at least one repeating unit selected from repeating units represented by formula (A), repeating units represented by formula (B), and repeating units represented by formula (C). is a dye multimer containing repeating units, or
A dye multimer represented by formula (D),
The coloring composition according to <1>;

In formula (A), A ¹ represents a trivalent linking group,
L ¹ represents a single bond or a divalent linking group,
DyeI represents the above dye structure;

In formula (B), A ² represents a trivalent linking group,
L2 represents a single bond or a ^divalent linking group,
^DyeII represents the above dye structure having a group capable of forming an ionic bond or a coordinate bond with Y2,
Y ² represents a group capable of forming an ionic bond or coordinate bond with DyeII;

^In formula (C), L3 represents a single bond or a divalent linking group,
DyeIII represents the above dye structure,
m represents 0 or 1;

In formula (D), L ⁴ represents an (n+k)-valent linking group,
n represents an integer from 2 to 20,
k represents an integer from 0 to 20,
DyeIV represents the above dye structure,
^P4 represents a substituent,
Each of n DyeIV may be different,
When k is 2 or more, the plurality of P ⁴ may be different,
n+k represents an integer from 2 to 20;
<3> The dye structure represented by DyeI of formula (A) is a structure obtained by removing one hydrogen atom from the structure represented by formula (1), or a structure represented by formula (1) in a metal atom. A structure in which one hydrogen atom is removed from the coordinated structure,
The dye structure represented by DyeII of the above formula (B) is a structure represented by formula (1) or a structure in which the structure represented by formula (1) is coordinated to a metal atom,
The dye structure represented by DyeIII of the above formula (C) is a structure obtained by removing two hydrogen atoms from the structure represented by formula (1), or a structure represented by formula (1) coordinated to a metal atom. A structure obtained by removing two hydrogen atoms from the structure,
The dye structure represented by DyeIV of formula (D) is a structure obtained by removing one hydrogen atom from the structure represented by formula (1), or a structure represented by formula (1) coordinated to a metal atom. A structure in which one hydrogen atom is removed from the structure,
The coloring composition according to <2>;

In formula (1), R ¹ represents a hydrogen atom, an alkyl group or an aryl group,
X ² to X ⁹ each independently represents a nitrogen atom, CH or CR ^x ,
R ^x represents a substituent,
When adjacent two of X ² to X ⁹ are CR ^x , R ^x of two adjacent CR ^x may combine to form a ring,
In the case of DyeII of formula (B), at least one of X ² to X ⁹ has a group capable of forming an ionic bond or coordinate bond with Y ² as a substituent.
<4> The structure represented by the formula (1) is a structure represented by the formula (1-1) or a structure represented by the formula (1-2), <3> The colored composition according to ;

In formula (1-1), R ¹ represents a hydrogen atom, an alkyl group or an aryl group,
X ² to X ⁹ each independently represents a nitrogen atom, CH or CR ^x ,
R ^x represents a substituent,
When adjacent two of X ² to X ⁹ are CR ^x , R ^x of two adjacent CR ^x may combine to form a ring,
In the case of DyeII of formula (B), at least one of X ² to X ⁹ has a group capable of forming an ionic bond or coordinate bond with Y ² as a substituent;
However, formula (1-1) satisfies any of the following requirements 1 to 4;
Requirement 1 Adjacent two of X ³ to X ⁵ are CR ^x , and the R ^x 's of the two adjacent CR ^x 's are bonded to form a ring;
Requirement 2 X ² and X ³ are CR ^x , and R ^x of CR ^x represented by X ² and R ^x of CR ^x represented by X ³ combine to form a heterocyclic ring;
Requirement 3 Adjacent two of X ⁶ to X ⁹ are CR ^x , and the R ^x 's of the two adjacent CR ^x 's are bonded to form a ring;
Requirement 4 at least one of X ² and X ³ is CH and at least one of X ² to X ⁹ is CR ^x ;

In formula (1-2), R ¹ represents a hydrogen atom, an alkyl group or an aryl group,
R ² to R ¹¹ each independently represent a hydrogen atom or a substituent;
Adjacent two of R ² to R ¹¹ may combine to form a ring, and at least one of R ² to R ¹¹ is a substituent;
However, in the case of DyeII of formula (B), at least one of R ² to R ¹¹ has a group capable of ionic or coordinate bonding with Y ² as a substituent.
<5> Further, including a coloring agent other than the above-mentioned dye multimer,
The coloring composition according to any one of <1> to <4>, wherein the coloring agent contains a halogenated phthalocyanine pigment.
<6> A film obtained from the colored composition according to any one of <1> to <5>.
<7> An optical filter having the film according to <6>.
<8> A solid-state imaging device having the film according to <6>.
<9> An image display device comprising the film according to <6>.
<10> A dye polymer comprising a dye structure having a structure a1 in which aromatic rings having a hydroxy group as a substituent are bonded to each other through an azomethine group, or a structure a2 in which the structure a1 is coordinated to a metal atom. hand,
A dye multimer containing at least one repeating unit selected from repeating units represented by formula (A), repeating units represented by formula (B), and repeating units represented by formula (C), or , a dye multimer which is a dye multimer represented by the formula (D);

In formula (A), A ¹ represents a trivalent linking group,
L ¹ represents a single bond or a divalent linking group,
DyeI is a structure obtained by removing one hydrogen atom from the structure represented by formula (1), or a structure obtained by removing one hydrogen atom from a structure in which the structure represented by formula (1) is coordinated to a metal atom represents the dye structure of;

In formula (B), A ² represents a trivalent linking group,
L2 represents a single bond or a ^divalent linking group,
DyeII is the above dye structure having a group capable of forming an ionic bond or a coordinate bond with Y ² , the structure represented by formula (1), or the structure represented by formula (1) on a metal atom represents the dye structure of the coordinated structure,
Y ² represents a group capable of forming an ionic bond or coordinate bond with DyeII;

^In formula (C), L3 represents a single bond or a divalent linking group,
DyeIII is a structure obtained by removing two hydrogen atoms from the structure represented by formula (1), or a structure obtained by removing two hydrogen atoms from a structure in which the structure represented by formula (1) is coordinated to a metal atom represents the pigment structure of
m represents 0 or 1;

In formula (D), L ⁴ represents an (n+k)-valent linking group,
n represents an integer from 2 to 20,
k represents an integer from 0 to 20,
DyeIV is a structure obtained by removing one hydrogen atom from the structure represented by formula (1), or a structure obtained by removing one hydrogen atom from a structure in which the structure represented by formula (1) is coordinated to a metal atom represents the pigment structure of
^P4 represents a substituent,
Each of n DyeIV may be different,
When k is 2 or more, the plurality of P ⁴ may be different,
n+k represents an integer from 2 to 20;

In formula (1), R ¹ represents a hydrogen atom, an alkyl group or an aryl group,
X ² to X ⁹ each independently represents a nitrogen atom, CH or CR ^x ,
R ^x represents a substituent,
When adjacent two of X ² to X ⁹ are CR ^x , R ^x of two adjacent CR ^x may combine to form a ring,
In the case of DyeII of formula (B), at least one of X ² to X ⁹ has a group capable of forming an ionic bond or coordinate bond with Y ² as a substituent.
<11> The dye multimer according to <10>, wherein the structure represented by formula (1) is a structure represented by formula (1-1) or a structure represented by formula (1-2) ;

In formula (1-2), R ¹ represents a hydrogen atom, an alkyl group or an aryl group,
R ² to R ¹¹ each independently represent a hydrogen atom or a substituent;
Adjacent two of R ² to R ¹¹ may combine to form a ring, and at least one of R ² to R ¹¹ is a substituent;
However, in the case of DyeII of formula (B), at least one of R ² to R ¹¹ has a group capable of ionic or coordinate bonding with Y ² as a substituent.

According to the present invention, it is possible to provide a colored composition capable of forming a film with excellent light resistance. Also, a film, an optical filter, a solid-state imaging device, an image display device, and a dye multimer can be provided.

The contents of the present invention will be described in detail below.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth)acrylate" represents both or either acrylate and methacrylate, "(meth)acryl" represents both or either acrylic and methacrylic, and "(meth) ) acryloyl” refers to acryloyl and/or methacryloyl.
In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent.
As used herein, a pigment means a compound that is difficult to dissolve in a solvent.
As used herein, the term "process" includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .

<Coloring composition>
The coloring composition of the present invention is a coloring composition comprising a dye multimer and a curable compound,
The dye multimer contains a dye structure having a structure a1 in which aromatic rings having hydroxyl groups as substituents are bonded to each other via an azomethine group, or a structure a2 in which the structure a1 is coordinated to a metal atom. characterized by

According to the coloring composition of the present invention, a film with excellent light resistance can be formed. Although the detailed reason why such an effect is obtained is unknown, it is presumed to be due to the following. The dye multimer contained in the coloring composition of the present invention is a dye that is a compound in which aromatic rings having a hydroxy group as a substituent are bonded via an azomethine group, or the above-mentioned compound (hydroxy group is attached to a metal atom A compound in which aromatic rings having substituents are bonded via an azomethine group) is coordinated to polymerize a dye. It is presumed that by polymerizing such a dye, it has a certain degree of motility, and thus becomes more susceptible to heat inactivation. It is presumed that the easier the thermal deactivation, the shorter the lifetime in the excited state, and thus the improved light resistance.

In addition, the coloring composition of the present invention can also suppress the generation of development residues when pixels are formed by patterning by photolithography.

Further, the dye multimer contained in the coloring composition of the present invention has excellent dispersibility in the coloring composition, can suppress aggregation in the coloring composition, and the viscosity of the coloring composition changes over time. Change can also be suppressed. Therefore, the coloring composition of the present invention is also excellent in storage stability.

The coloring composition of the present invention is preferably used as a coloring composition for color filters or infrared transmission filters. More specifically, it can be preferably used as a coloring composition for forming color filter pixels or as a coloring composition for forming infrared transmission filters, and is more preferably used as a coloring composition for forming color filter pixels. Pixel types include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. Red pixels, green pixels, and yellow pixels are preferred. More preferably, it is a green pixel.

As an infrared transmission filter, the maximum transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1100 to 1300 nm. Filters satisfying spectral characteristics with a value of 70% or more (preferably 75% or more, more preferably 80% or more) are preferred. The infrared transmission filter is preferably a filter that satisfies any one of the following spectral characteristics (1) to (5).
(1): The maximum transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 800 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
(2): The maximum transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 900 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
(3): The maximum transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1000 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
(4): The maximum transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1100 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
(5): The maximum transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1200 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).

When a film having a thickness of 0.65 μm is formed using the coloring composition of the present invention, the wavelength at which the light transmittance of the film is 50% is preferably present in the wavelength range of 470 to 520 nm. More preferably in the wavelength range of 520 nm, even more preferably in the wavelength range of 480-520 nm. In particular, it is preferable that the wavelengths at which the light transmittance is 50% exist in both the wavelength range of 470 to 520 nm and the wavelength range of 575 to 625 nm. In this embodiment, the wavelength on the short wavelength side at which the light transmittance is 50% preferably exists in the wavelength range of 475 to 520 nm, more preferably in the wavelength range of 480 to 520 nm. Further, the wavelength on the long wavelength side at which the light transmittance is 50% preferably exists in the wavelength range of 580 to 620 nm, more preferably in the wavelength range of 585 to 615 nm. A coloring composition capable of forming a film having such spectral characteristics is preferably used as a coloring composition for forming green pixels of a color filter.

In addition, the colored composition of the present invention is preferably used for solid-state imaging devices. More specifically, it is preferably used as a coloring composition for optical filters used in solid-state imaging devices, and more preferably used as a coloring composition for color filters used in solid-state imaging devices.

The solid content concentration of the coloring composition of the present invention is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less.

Each component used in the coloring composition of the present invention will be described below.

<<Dye multimer (specific dye multimer)>>
The coloring composition of the present invention contains a dye multimer containing a dye structure (hereinafter also referred to as a specific dye structure), which will be described later. Hereinafter, a dye multimer containing a specific dye structure is also referred to as a specific dye multimer.

In this specification, the dye multimer means a compound having two or more dye structures in one molecule. The specific dye multimer has two or more specific dye structures in one molecule, preferably three or more, and more preferably four or more. The upper limit is not particularly limited, but may be 100 or less.

Next, the specific dye structure possessed by the specific dye multimer will be explained. The specific dye multimer has a structure a1 in which aromatic rings having hydroxyl groups as substituents are bonded to each other through an azomethine group, or a structure a2 in which the structure a1 described above is coordinated to a metal atom (specific dye structure structure).

The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. An aromatic hydrocarbon ring is preferable because it can further improve light resistance, residue suppression and storage stability. Moreover, each aromatic ring may further contain a substituent other than a hydroxy group. Substituents include the substituent T described later.

In the above structure a2, the metal atom coordinated by the above structure a1 includes a copper atom, a zinc atom, an iron atom, a titanium atom, an aluminum atom, a tin atom, a magnesium atom and a chromium atom. It is preferably a copper atom, more preferably a copper atom. A ligand may be further coordinated to the metal atom. Ligands include heterocyclic compounds (e.g., pyridine, pyrimidine, imidazole, pyrazole, triazole, tetrazole, quinoline, 1,10-phenanthroline, etc.), protic compounds (e.g., water, methanol, ethanol, etc.), amine compounds ( For example, triethylamine, N,N,N',N'-tetramethylenediamine, ethylenediaminetetraacetic acid N,N,N',N'',N''-pentamethyldiethylenetriamine, etc.), amide compounds (for example, N,N- dimethylacetamide, N-methylpyrrolidone, etc.), dimethylsulfoxide, sulfolane, nitrile compounds (eg, acetonitrile, etc.), and the like.

The specific dye structure preferably has the above structure a2 because it can further improve light resistance, residue suppression and storage stability, and further improve heat resistance.

The specific dye structure is a structure derived from a compound having a structure represented by formula (1) (hereinafter, also referred to as compound A1), or a compound in which compound A1 is coordinated to a metal atom (hereinafter, also referred to as compound A2). It is preferably a structure derived from

In formula (1), R ¹ represents a hydrogen atom, an alkyl group or an aryl group,
X ² to X ⁹ each independently represents a nitrogen atom, CH or CR ^x ,
R ^x represents a substituent,
When two adjacent CR ^x 's among X ² to X ⁹ are CR x's, the R ^x 's of the two adjacent CR ^x 's may combine to form a ring.

The number of carbon atoms in the alkyl group represented by R ¹ in formula (1) is preferably 1-30, more preferably 1-15, and even more preferably 1-8. The alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear. The alkyl group may have a substituent. Substituents include the substituent T described later.
The aryl group represented by R ¹ in formula (1) preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms. The aryl group may have a substituent. Substituents include the substituent T described later.
R ¹ in formula (1) is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

X ² to X ⁹ in formula (1) each independently represent a nitrogen atom, CH or CR ^x , and R ^x represents a substituent. Substituents represented by R ^x include substituents T described later. The substituent represented by R ^x is preferably a group containing a heteroatom, more preferably a specific functional group A described later. Preferably, X ² to X ⁹ in formula (1) are each independently CH or CR ^x . Further, at least one of X ² to X ⁹ in formula (1) is CR ^x , and R ^x is a group containing a heteroatom (preferably is also preferably a specific functional group A) described later.

Specific functional groups A include a nitro group, a cyano group, -NR ¹⁰¹ R ¹⁰² , -OR ¹⁰³ , -SR ¹⁰⁴ , -COOR ¹⁰⁵ , -OCOR ¹⁰⁶ , -SO ₂ R ¹⁰⁷ , -SO ₂ NR ¹⁰⁸ R ¹⁰⁹ , - SO ₂ OR ¹¹⁰ , —CONR ¹¹¹ R ¹¹² and —NR ¹¹³ COR ¹¹⁴ , preferably a nitro group, a cyano group, —NR ¹⁰¹ R ¹⁰² , —OR ¹⁰³ , —SR ¹⁰⁴ and —COOR ¹⁰⁵ , — NR ¹⁰¹ R ¹⁰² and -OR ¹⁰³ are more preferred. R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom, an alkyl group or an aryl group, R ¹⁰¹ and R ¹⁰² may combine to form a ring, and R ¹⁰³ to R ¹¹⁴ each independently , represents an alkyl group or an aryl group.

The number of carbon atoms in the alkyl group represented by R ¹⁰¹ to R ¹¹⁴ is preferably 1-10, more preferably 1-5, still more preferably 1-3, and particularly preferably 1 or 2. The alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear. The alkyl group may have a substituent. Substituents include the substituent T described later. The alkyl groups represented by R ¹⁰¹ to R ¹¹⁴ are preferably methyl groups or ethyl groups.
The aryl group represented by R ¹⁰¹ to R ¹¹⁴ preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms. The aryl group may have a substituent. Substituents include the substituent T described later.

R ¹⁰¹ and R ¹⁰² are each independently preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group. R ¹⁰³ to R ¹¹⁴ are each independently preferably an alkyl group, more preferably a methyl group or an ethyl group.

When adjacent two of X ² to X ⁹ in formula (1) are CR ^x , the R ^x 's of the two adjacent CR ^x 's may combine to form a ring. The ring formed may be a hydrocarbon ring or a hetero ring. Further, the hydrocarbon ring may be an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring. Heteroatoms contained in the heterocycle include nitrogen, sulfur and oxygen atoms. The heterocycle is preferably a 5- or 6-membered ring. Specific examples of the ring to be formed include a benzene ring, a hydrocarbon ring such as a naphthalene ring, a pyrrole ring, a furan ring, a thiophene ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, an imidazoline ring, pyridazine ring, pyrimidine ring, pyrazine ring, indole ring, isoindole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, benzotriazole ring, purine ring, quinoline ring, isoquinoline ring, quinazoline ring, quinoxaline ring, cinnoline ring, Heterocycles such as pteridine ring, pyrrolidine ring, piperidine ring, tetrahydrofuran ring, tetrahydropyran ring, tetrahydrothiophene ring, and tetrahydrothiopyran ring are included. The ring thus formed may further have a substituent. Substituents include the substituent T described later. The substituent is preferably a group containing a heteroatom, more preferably the specific functional group A described above.

Examples of the above-mentioned substituent T include the following groups. Halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (preferably alkyl group having 1 to 30 carbon atoms), alkenyl group (preferably alkenyl group having 2 to 30 carbon atoms), alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an aryl group having 6 to 30 carbon atoms), a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms), an amino group (preferably amino group having 0 to 30 carbon atoms), alkoxy group (preferably alkoxy group having 1 to 30 carbon atoms), aryloxy group (preferably aryloxy group having 6 to 30 carbon atoms), heterocyclic oxy group (preferably carbon 1 to 30 heterocyclic oxy groups), acyl groups (preferably acyl groups having 2 to 30 carbon atoms), alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 30 carbon atoms), aryloxycarbonyl groups (preferably aryloxycarbonyl group having 7 to 30 carbon atoms), heterocyclicoxycarbonyl group (preferably heterocyclicoxycarbonyl group having 2 to 30 carbon atoms), acyloxy group (preferably acyloxy group having 2 to 30 carbon atoms), acylamino group (preferably acylamino group having 2 to 30 carbon atoms), aminocarbonylamino group (preferably aminocarbonylamino group having 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably alkoxycarbonylamino group having 2 to 30 carbon atoms) , aryloxycarbonylamino group (preferably aryloxycarbonylamino group having 7 to 30 carbon atoms), sulfamoyl group (preferably sulfamoyl group having 0 to 30 carbon atoms), sulfamoylamino group (preferably 0 to 30 carbon atoms sulfamoylamino group), carbamoyl group (preferably carbamoyl group having 1 to 30 carbon atoms), alkylthio group (preferably alkylthio group having 1 to 30 carbon atoms), arylthio group (preferably arylthio group having 6 to 30 carbon atoms) group), heterocyclicthio group (preferably heterocyclicthio group having 1 to 30 carbon atoms), alkylsulfonyl group (preferably alkylsulfonyl group having 1 to 30 carbon atoms), alkylsulfonylamino group (preferably having 1 to 30 alkylsulfonylamino groups), arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 30 carbon atoms), arylsulfonylamino groups (preferably arylsulfonylamino groups having 6 to 30 carbon atoms), heterocyclic sulfonyl groups (preferably is a C1-C30 heterocyclic sulfonyl group), a heterocyclic sulfonylamino group (preferably a heterocyclic sulfonylamino group having 1 to 30 carbon atoms), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 30 carbon atoms), an arylsulfinyl group (preferably a arylsulfinyl group of 6 to 30), heterocyclic sulfinyl group (preferably heterocyclic sulfinyl group of 1 to 30 carbon atoms), ureido group (preferably ureido group of 1 to 30 carbon atoms), hydroxy group, nitro group, carboxy group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imide group, phosphino group, mercapto group, cyano group, alkylsulfino group, arylsulfino group, arylazo group, heterocyclic azo group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, hydrazino group, imino group. These groups may further have substituents if they are substitutable groups.

Compound A1 is preferably a compound represented by formula (1-1) or a compound represented by formula (1-2).

In formula (1-1), R ¹ represents a hydrogen atom, an alkyl group or an aryl group,
X ² to X ⁹ each independently represents a nitrogen atom, CH or CR ^x ,
R ^x represents a substituent,
When two adjacent CR ^x 's among X ² to X ⁹ are CR x's, the R ^x 's of the two adjacent CR ^x 's may combine to form a ring.
However, formula (1-1) satisfies any one of requirements 1 to 4 below.
Requirement 1 Adjacent two of X ³ to X ⁵ are CR ^x , and the R ^x 's of the two adjacent CR ^x 's are bonded to form a ring;
Requirement 2 X ² and X ³ are CR ^x , and R ^x of CR ^x represented by X ² and R ^x of CR ^x represented by X ³ combine to form a heterocyclic ring;
Requirement 3 Adjacent two of X ⁶ to X ⁹ are CR ^x , and the R ^x 's of the two adjacent CR ^x 's are bonded to form a ring;
Requirement 4 At least one of X ² and X ³ is CH, and at least one of X ² to X ⁹ is CR ^x .

In formula (1-2), R ¹ represents a hydrogen atom, an alkyl group or an aryl group,
R ² to R ¹¹ each independently represent a hydrogen atom or a substituent;
Adjacent two of R ² to R ¹¹ may combine to form a ring, and at least one of R ² to R ¹¹ is a substituent.

First, the compound represented by formula (1-1) will be described.
R ¹ in formula (1-1) has the same definition as R ¹ in formula (1). Further, details of X ² to X ⁹ in formula (1-1) are the same as X ² to X ⁹ in formula (1). However, formula (1-1) satisfies any one of requirements 1 to 4 described above.

Requirement 1 is that adjacent two of X ³ to X ⁵ are CR ^x , and the R ^x 's of the two adjacent CR ^x 's are bonded to form a ring. Examples of the ring formed by bonding R ^x together include the rings described above, preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The ring formed by combining R ^x may further have a substituent. Examples of the substituent include the substituent T described above. The substituent is preferably a group containing a heteroatom, more preferably the specific functional group A described above.

As a specific example of Requirement 1, X ³ and X ⁴ are each independently CR ^x , and R ^x of CR ^x represented by X ³ and R ^x of CR ^x represented by X ⁴ combine to form a ring and X ⁴ and X ⁵ are each independently CR ^x , and R ^x of CR ^x represented by X ⁴ and R ^x of CR ^x represented by X ⁵ combine to form a ring. aspects.

In Requirement 1, it is also preferred that at least one of X ⁶ to X ⁹ is CR ^x and R ^x is a heteroatom-containing group (preferably, the specific functional group A described above).

Requirement 2 is that X ² and X ³ are CR ^x , and R ^x of CR ^x represented by X ² and R ^x of CR ^x represented by X ³ combine to form a heterocyclic ring. is. The heterocycles formed by combining R ^x include the heterocycles described above. The hetero ring formed by combining R ^x may further have a substituent. Examples of the substituent include the substituent T described above. The substituent is preferably a group containing a heteroatom, more preferably the specific functional group A described above.

In Requirement 2, it is also preferred that at least one of X ⁶ to X ⁹ is CR ^x and R ^x is a heteroatom-containing group (preferably the specific functional group A described above).

Requirement 3 is that adjacent two of X ⁶ to X ⁹ are CR ^x , and the R ^x 's of the two adjacent CR ^x 's are bonded to form a ring. Examples of the ring formed by bonding R ^x together include the rings described above, preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The ring formed by combining R ^x may further have a substituent. Examples of the substituent include the substituent T described above. The substituent is preferably a group containing a heteroatom, more preferably the specific functional group A described above.

As a specific example of requirement 3, X ⁶ and X ⁷ are each independently CR ^x , and R ^x of CR ^x represented by X ⁶ and R ^x of CR ^x represented by X ⁷ combine to form a ring and X ⁷ and X ⁸ are each independently CR ^x , and R ^x of CR ^x represented by X ⁷ and R ^x of CR ^x represented by X ⁸ combine to form a ring. Examples include embodiments in which X ⁸ and X ⁹ are each independently CR ^x , and R ^x of CR ^x represented by X ⁸ and R ^x of CR ^x represented by X ⁹ combine to form a ring. X ⁶ and X ⁷ are each independently CR ^x , and R ^x of CR ^x represented by X ⁶ and R ^x of CR ^x represented by X ⁷ can be formed. are combined to form a ring, or X ⁷ and X ⁸ are each independently CR ^x , and R ^x of CR ^x represented by X ⁷ and R ^x of CR ^x represented by X ⁸ are preferably bonded to form a ring, X ⁷ and X ⁸ are each independently CR ^x , and R ^x of CR ^x represented by X ⁷ and R of CR ^x represented by X ⁸ It is more preferable that ^x is bonded to form a ring.

In Requirement 3, when adjacent two of X ² to X ⁵ are CR ^x , the R ^x 's of the two adjacent CR ^x 's may combine to form a ring. Examples of the ring formed by bonding R ^x together include the rings described above, preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The ring formed by combining R ^x may further have a substituent. Examples of the substituent include the substituent T described above. The substituent is preferably a group containing a heteroatom, more preferably the specific functional group A described above.

In Requirement 3, it is also preferred that at least one of X ² to X ⁵ is CR ^x and R ^x is a heteroatom-containing group (preferably the specific functional group A described above).

Requirement 4 is that at least one of X ² and X ³ is CH, and at least one of X ² to X ⁹ is CR ^x . R ^x represents a substituent. In Requirement 4, 1 to 4 of X ² to X ⁹ are preferably CR ^x , more preferably 1 or 2 are CR ^x . Examples of the substituent represented by R ^x include the substituent T described above. The substituent is preferably a group containing a heteroatom, more preferably the specific functional group A described above.

The compound represented by formula (1-1) preferably satisfies any one of requirements 1, 3 or 4 described above, more preferably satisfies requirement 3 or requirement 4, It is more preferable that Requirement 3 is satisfied.

The compound represented by formula (1-1) is preferably a compound represented by formula (1-1-1).

In formula (1-1-1), R ¹ represents a hydrogen atom, an alkyl group or an aryl group,
R ^x2 to R ^x9 each independently represent a hydrogen atom or a substituent;
adjacent two of R ^x2 to R ^x9 may combine to form a ring;
However, formula (1-1-1) satisfies any of the following requirements 1a to 4a;
Requirement 1a Adjacent two of R ^x3 to R ^x5 are bonded to form a ring;
Requirement 2a R ^x2 and R ^x3 combine to form a heterocycle;
Requirement 3a adjacent two of R ^x6 to R ^x9 are bonded to form a ring;
Requirement 4a At least one of R ^x2 and R ^x3 is a hydrogen atom, and at least one of R ^x2 to R ^x9 is a substituent.

R ¹ in formula (1-1-1) has the same definition as R ¹ in formula (1).

Examples of substituents represented by R ^x2 to R ^x9 in formula (1-1-1) include the above-described substituent T, preferably a group containing a hetero atom, and the above-described specific functional group A. is more preferred.

In formula (1-1-1), adjacent two of R ^x2 to R ^x9 may combine to form a ring. The ring to be formed includes the rings described above. The ring thus formed may further have a substituent. Examples of the substituent include the substituent T described above. The substituent is preferably a group containing a heteroatom, more preferably the specific functional group A described above.

Formula (1-1-1) satisfies any one of the requirements 1a to 4a described above.

Requirement 1a is that adjacent two of R ^x3 to R ^x5 are bonded to form a ring. The ring to be formed includes the rings described above, preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The ring formed above may further have a substituent. Examples of the substituent include the substituent T described above. The substituent is preferably a group containing a heteroatom, more preferably the specific functional group A described above.

Specific examples of requirement 1a include an embodiment in which R ^x3 and R ^x4 are bonded to form a ring, and an embodiment in which R ^x4 and R ^x5 are bonded to form a ring.

In Requirement 1a, it is also preferred that at least one of R ^x6 to R ^x9 is a heteroatom-containing group (preferably the specific functional group A described above).

Requirement 2a is that R ^x2 and R ^x3 combine to form a heterocyclic ring. The heterocycles formed include the heterocycles described above. The hetero ring formed above may further have a substituent. Examples of the substituent include the substituent T described above. The substituent is preferably a group containing a heteroatom, more preferably the specific functional group A described above.

In Requirement 2a, it is also preferred that at least one of R ^x6 to R ^x9 is a heteroatom-containing group (preferably the specific functional group A described above).

Requirement 3a is that adjacent two of R ^x6 to R ^x9 are bonded to form a ring. The ring to be formed includes the rings described above, preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The ring formed above may further have a substituent. Examples of the substituent include the substituent T described above. The substituent is preferably a group containing a heteroatom, more preferably the specific functional group A described above.

Specific examples of requirement 3a include an aspect in which R ^x6 and R ^x7 are bonded to form a ring, an aspect in which R ^x7 and R ^x8 are bonded to form a ring, and R ^x8 and R ^x9 is bonded to form a ring, and since it is possible to form a film with more excellent light resistance, an embodiment in which R ^x6 and R ^x7 are bonded to form a ring, or R The embodiment in which ^x7 and R ^x8 are bonded to form a ring is preferable, and the embodiment in which R ^x7 and R ^x8 are bonded to form a ring is more preferable.

In requirement 3a, adjacent two of R ^x2 to R ^x5 may combine to form a ring. The ring to be formed includes the rings described above, preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The ring formed above may further have a substituent. Examples of the substituent include the substituent T described above. The substituent is preferably a group containing a heteroatom, more preferably the specific functional group A described above.

In Requirement 3a, it is also preferred that at least one of R ^x2 to R ^x5 is a heteroatom-containing group (preferably the specific functional group A described above).

Requirement 4a is that at least one of R ^x2 and R ^x3 is a hydrogen atom, and at least one of R ^x2 to R ^x9 is a substituent. In Requirement 4a, 1 to 4 of R ^x2 to R ^x9 are preferably substituents, and more preferably 1 or 2 are substituents. Examples of the substituent include the substituent T described above. The substituent is preferably a group containing a heteroatom, more preferably the specific functional group A described above.

Formula (1-1-1) preferably satisfies any of the requirements 1a, 3a or 4a described above, more preferably satisfies requirement 3a or requirement 4a, and satisfies requirement 3a More preferably.

Next, the compound represented by formula (1-2) will be described.
R ¹ in formula (1-2) has the same definition as R ¹ in formula (1).
Examples of the substituent represented by R ² to R ¹¹ in formula (1-2) include the substituent T described above. The substituent is preferably a group containing a heteroatom, more preferably the specific functional group A described above.

In formula (1-2), adjacent two of R ² to R ¹¹ may combine to form a ring. The ring to be formed includes the rings described above. The ring thus formed may further have a substituent. Examples of the substituent include the substituent T described above. The substituent is preferably a group containing a heteroatom, more preferably the specific functional group A described above.

At least one of R ² to R ¹¹ in formula (1-2) is a substituent, and is preferably a group containing a heteroatom, since a film having more excellent light resistance can be formed. More preferably, it is the specific functional group A described above.
Further, 1 to 4 (more preferably 1 or 2, still more preferably 1) of R ² to R ¹¹ in formula (1-2) are preferably substituents, and are groups containing heteroatoms. It is preferable that there is, and it is more preferable that it is the specific functional group A described above.
In addition, at least one of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ and R ¹⁰ in formula (1-2) (preferably , R ⁹ and R ¹⁰ , more preferably R ⁹ ) is preferably a substituent, preferably a group containing a heteroatom, and more preferably a specific functional group A described above. Among them, at least one of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ and R ¹⁰ in formula (1-2) (preferably It is preferred that at least one of R ⁹ and R ¹⁰ , more preferably R ⁹ ) is a heteroatom-containing group (preferably the above-described specific functional group A), and the rest are hydrogen atoms.

In compound A2, the metal atom to which compound A1 is coordinated includes a copper atom, a zinc atom, an iron atom, a titanium atom, an aluminum atom, a tin atom, a magnesium atom, a chromium atom, a calcium atom and a silicon atom. and a zinc atom, more preferably a copper atom. In addition, a ligand may be further coordinated to the metal atom. Ligands include heterocyclic compounds (e.g., pyridine, pyrimidine, imidazole, pyrazole, triazole, tetrazole, quinoline, 1,10-phenanthroline, etc.), protic compounds (e.g., water, methanol, ethanol, etc.), amine compounds ( For example, triethylamine, N,N,N',N'-tetramethylenediamine, ethylenediaminetetraacetic acid N,N,N',N'',N''-pentamethyldiethylenetriamine, etc.), amide compounds (for example, N,N- dimethylacetamide, N-methylpyrrolidone, etc.), dimethylsulfoxide, sulfolane, nitrile compounds (eg, acetonitrile, etc.), and the like. Examples of compound A2 include a compound represented by formula (A2-1), a compound represented by formula (A2-2), a compound represented by formula (A2-3), and a compound represented by formula (A2-4). and the compounds represented. In the following formulas, M ¹ to M ⁵ each independently represent a metal atom. Compound A2 is a compound in which a ligand is coordinated to a metal atom at a ratio of 1:3, a compound in which a ligand is coordinated to a metal atom at a ratio of 1:4, a metal atom A compound in which the ligand is coordinated to the metal atom in a ratio of 2:3 and a compound in which the ligand is coordinated to the metal atom in a ratio of 3:3 may be used. Also, a part of the ligand may be dissociated from the metal atom, or a compound other than the ligand may be coordinated to the metal atom.

The specific dye multimer has at least one repeating unit selected from repeating units represented by the formula (A), repeating units represented by the formula (B), and repeating units represented by the formula (C). or a dye multimer represented by the formula (D).

Hereinafter, a dye multimer having a repeating unit represented by formula (A) is also referred to as a dye multimer (A). A dye multimer having a repeating unit represented by formula (B) is also referred to as a dye multimer (B). A dye multimer having a repeating unit represented by formula (C) is also referred to as a dye multimer (C). Moreover, the dye multimer represented by Formula (D) is also called dye multimer (D).

(Pigment multimer (A))
Pigment multimer (A) contains a repeating unit represented by Formula (A). In the dye multimer (A), the proportion of repeating units represented by formula (A) is preferably 20 to 100% by mass of all repeating units constituting the specific dye multimer. The lower limit is preferably 25% by mass or more, more preferably 30% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less.

In formula (A), A ¹ represents a trivalent linking group,
L ¹ represents a single bond or a divalent linking group,
DyeI represents the dye structure.

The trivalent linking group represented by A ¹ of the formula (A) includes a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, and a polyamide linking group. A linking group, a polyether-based linking group, a polystyrene-based linking group, a bisphenol-based linking group, a novolak-based linking group and the like can be mentioned, and a poly(meth)acrylic-based linking group is preferred.

L1 in formula (A) represents a ^single bond or a divalent linking group. The divalent linking group includes an alkylene group, an arylene group, a heterocyclic group, -CH=CH-, -O-, -S-, -C(=O)-, -COO-, -NR-, -CONR -, -OCO-, -SO-, -SO ₂ -, and linking groups formed by linking two or more of these. Here, R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

The number of carbon atoms in the alkylene group is preferably 1-30. The upper limit is more preferably 25 or less, even more preferably 20 or less. The lower limit is more preferably 2 or more, and still more preferably 3 or more. The alkylene group may be linear, branched or cyclic. The alkylene group may have a substituent or may be unsubstituted.
The arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. The arylene group may have a substituent or may be unsubstituted.
The heterocyclic group is preferably a 5- or 6-membered ring. The heteroatom possessed by the heterocyclic group is preferably an oxygen atom, a nitrogen atom and a sulfur atom. The number of heteroatoms possessed by the heterocyclic group is preferably 1 to 3. The heterocyclic group may have a substituent or may be unsubstituted.

The dye structure represented by DyeI of formula (A) is preferably a residue obtained by removing one hydrogen atom from compound A1 described above, or a residue obtained by removing one hydrogen atom from compound A2 described above. More specifically, hydrogen A structure in which one atom is removed is preferable. The structure represented by formula (1) is preferably the structure represented by formula (1-1) described above or the structure represented by formula (1-2) described above. The dye structure represented by DyeI is a structure obtained by removing one hydrogen atom from the structure represented by the above formula (1), or a structure in which the structure represented by the above formula (1) is coordinated to a metal atom. The specific dye multimer having a structure obtained by removing one hydrogen atom from is also the dye multimer of the present invention.

Specific examples of the repeating unit represented by formula (A) include the following. In the structural formulas shown below, Me represents a methyl group, Et represents an ethyl group, and Ac represents an acetyl group.

The dye multimer (A) may contain other repeating units in addition to the repeating unit represented by formula (A). Other repeating units include repeating units having a crosslinkable group, repeating units having an acid group, and the like. Examples of crosslinkable groups include ethylenically unsaturated bond-containing groups such as vinyl groups, (meth)allyl groups and (meth)acryloyl groups, and cyclic ether groups such as epoxy groups and oxetanyl groups. A carboxy group, a sulfo group, a phosphoric acid group, etc. are mentioned as an acid group.

The proportion of repeating units having a crosslinkable group is preferably 35% by mass or less, more preferably 30% by mass or less, and 25% by mass or less of all repeating units constituting the dye multimer (A). It is even more preferable to have The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.

The proportion of repeating units having an acid group is preferably 25% by mass or less, more preferably 20% by mass or less, and 15% by mass or less of all repeating units constituting the dye multimer (A). is more preferred. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more.

Specific examples of the dye multimer (A) include dye multimers (S-1), (S-2), (S-5), (S-9) to (S-14) described in the examples below. ), (S-16) and the like.

(Pigment multimer (B))
Pigment multimer (B) contains a repeating unit represented by Formula (B). In the dye multimer (B), the proportion of the repeating unit represented by formula (B) is preferably 20 to 100% by mass of the total repeating units constituting the specific dye multimer. The lower limit is preferably 25% by mass or more, more preferably 30% by mass or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less.

In formula (B), A ² represents a trivalent linking group,
L2 represents a single bond or a ^divalent linking group,
^DyeII represents a dye structure having a group capable of ionic bonding or bonding with Y2,
Y2 represents a group capable of forming an ionic bond or coordinate bond with ^DyeII .

A ² in formula (B) has the same definition as A ¹ in formula (A), and the preferred range is also the same.

L2 in formula (B) represents a single bond or a ^divalent linking group. The divalent linking group includes an alkylene group, an arylene group, a heterocyclic group, -CH=CH-, -O-, -S-, -C(=O)-, -COO-, -NR-, -CONR -, -OCO-, -SO-, -SO ₂ -, and linking groups formed by linking two or more of these. Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. The details of the divalent linking group are the same as for L1 in formula ( ^A ). L ² is preferably a single bond, an alkylene group, an arylene group, -NH-, -CO-, -O-, -COO-, -OCO-, or a divalent linking group in which two or more of these are combined.

Examples of groups capable of ionic bonding or coordinative bonding with DyeII represented by Y ² of formula (B) include anionic groups and cationic groups.

Examples of the anionic group include -SO ₃ ^- , -COO ^- , -PO ₄ ^2- , -PO ₄ H ^- , a group containing a bis(sulfonyl)imide anion structure and a group containing a tris(sulfonyl)methide anion structure. be done. Specific examples include a group represented by formula (AN-1) and a group represented by formula (AN-2).

In formula (AN-1), L ^AN1 represents a single bond or a divalent linking group, and R ^AN1 represents -SO ₃ ^- , -COO ^- , -PO ₄ ^2- or -PO ₄ H ^- .
The divalent linking group represented by L ^AN1 may be —NR ^AN10 —, —O—, —SO ₂ —, an alkylene group containing a fluorine atom, an arylene group containing a fluorine atom, or a group consisting of a combination thereof. preferable. In particular, a group consisting of a combination of —NR ^AN10 — and —SO ₂ and an alkylene group containing a fluorine atom, a group consisting of a combination of —O— and an arylene group containing a fluorine atom, or —NR ^AN10 — and —SO A group consisting of a combination of ₂ and an alkylene group containing a fluorine atom is preferred.
In -NR ^AN10 -, R ^AN10 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom.
The number of carbon atoms in the alkylene group containing a fluorine atom is preferably 1-10, more preferably 1-6, and even more preferably 1-3. These alkylene groups are more preferably perfluoroalkylene groups. Specific examples of fluorine-substituted alkylene groups include a difluoromethylene group, a tetrafluoroethylene group, and a hexafluoropropylene group.
The number of carbon atoms in the arylene group containing a fluorine atom is preferably 6-20, more preferably 6-14, even more preferably 6-10. Specific examples of arylene groups containing fluorine atoms include a tetrafluorophenylene group, a hexafluoro-1-naphthylene group and a hexafluoro-2-naphthylene group.

In formula (AN-2), L ^AN2 represents a single bond or a divalent linking group, preferably a single bond. The divalent linking group represented by ^LAN2 includes an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —S—, or a group consisting of a combination thereof. L ^AN3 represents -SO ₂ - or -CO-, preferably -SO ₂ -. G represents a carbon atom or a nitrogen atom, preferably a nitrogen atom. n represents 2 when G is a carbon atom, and represents 1 when G is a nitrogen atom. ^RAN2 represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom. The fluorine atom-containing alkyl group represented by R ^AN2 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms. The fluorine atom-containing aryl group represented by R ^AN2 preferably has 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms.

Cationic groups include substituted or unsubstituted onium cations (eg, ammonium, pyridinium, imidazolium, phosphonium, etc.), with ammonium cations being particularly preferred. Ammonium cations include -N(R) ₃ ⁺ . Each R independently represents a hydrogen atom or an alkyl group, and at least one of R represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5. The alkyl group may be linear, branched, or cyclic, but is preferably linear.

^DyeII in formula (B) represents a dye structure having a group capable of ionically bonding or bonding with Y2. Groups capable of ionically bonding or bonding to ^Y2 include anionic groups and cationic groups. Specific examples of anionic groups and cationic groups include the groups described above.

The dye structure represented by DyeII of formula (B) is a structure represented by the above formula (1) or a structure in which the structure represented by the above formula (1) is coordinated to a metal atom, and At least one of X ² to X ⁹ in (1) preferably has a structure having a group capable of forming an ionic bond or coordinate bond with Y ² as a substituent. The structure represented by formula (1) is preferably the structure represented by formula (1-1) described above or the structure represented by formula (1-2) described above. However, in formula (1-1), at least one of X ² to X ⁹ has a group capable of forming an ionic bond or coordinate bond with Y ² as a substituent, and in formula (1-2), At least one of R ² to R ¹¹ has a group capable of forming an ionic bond or coordinate bond with Y ² as a substituent. The dye structure represented by DyeII is a structure represented by the above formula (1), or a structure in which the structure represented by the above formula (1) is coordinated to a metal atom, and The specific dye multimer in which at least one of X ² to X ⁹ has a group capable of forming an ionic bond or coordinate bond with Y ² as a substituent is also the dye multimer of the present invention.

Specific examples of the repeating unit represented by formula (B) include the following.

The pigment multimer (B) may contain, in addition to the repeating unit represented by formula (B), other repeating units described in the description of the embodiment of the pigment multimer (A).

Specific examples of the pigment multimer (B) include the pigment multimers (S-3), (S-4), (S-17), etc. described in the examples below.

(Pigment multimer (C))
Pigment multimer (C) contains a repeating unit represented by Formula (C). In the dye multimer (C), the proportion of repeating units represented by formula (C) is preferably 10 to 100% by mass of all repeating units constituting the specific dye multimer. The lower limit is preferably 30% by mass or more, more preferably 50% by mass or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less.

^In formula (C), L3 represents a single bond or a divalent linking group,
DyeIII represents the dye structure,
m represents 0 or 1;

L3 in formula ⁽ C) represents a single bond or a divalent linking group. The divalent linking group includes an alkylene group, an arylene group, a heterocyclic group, -CH=CH-, -O-, -S-, -C(=O)-, -COO-, -NR-, -CONR -, -OCO-, -SO-, -SO ₂ -, and linking groups formed by linking two or more of these. Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

The number of carbon atoms in the alkyl group and alkylene group is preferably 1-30. The upper limit is more preferably 25 or less, even more preferably 20 or less. The lower limit is more preferably 2 or more, and still more preferably 3 or more. Alkyl groups and alkylene groups may be linear, branched or cyclic.
The aryl group and the arylene group preferably have 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
The heterocyclic group is preferably a 5- or 6-membered ring. The heteroatom possessed by the heterocyclic group is preferably an oxygen atom, a nitrogen atom and a sulfur atom. The number of heteroatoms possessed by the heterocyclic group is preferably 1 to 3.
An alkylene group, an arylene group, a heterocyclic group, an alkyl group and an aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the groups listed above for the substituent T, the crosslinkable group, and the acid group. In addition, development promoting groups (groups containing repeating unsubstituted alkyleneoxy chains of 2 to 20, groups containing lactone structures, acid anhydride groups, cyano groups, etc.) and hydrophilicity/hydrophobicity adjusting groups (long-chain or cyclic alkyl group, long-chain or cyclic aralkyl group, aryl group, polyalkylene oxide group, hydroxy group, maleimide group, amino group, etc.) as a substituent.

L ³ of formula (C) is an alkylene group, an arylene group, -NH-, -CO-, -O-, -COO-, -OCO-, -S-, -SO ₂ -, or a combination of two or more of these Linking groups are preferred.

The dye structure represented by DyeIII of formula (C) is preferably a residue obtained by removing two hydrogen atoms from compound A1 described above, or a residue obtained by removing two hydrogen atoms from compound A2 described above. More specifically, hydrogen A structure in which two atoms are removed is preferable. The structure represented by formula (1) is preferably the structure represented by formula (1-1) described above or the structure represented by formula (1-2) described above. The dye structure represented by DyeIII is a structure obtained by removing two hydrogen atoms from the structure represented by the above formula (1), or a structure in which the structure represented by the above formula (1) is coordinated to a metal atom. The specific dye multimer having a structure obtained by removing two hydrogen atoms from is also the dye multimer of the present invention.

m in formula (C) represents 0 or 1, preferably 1.

Specific examples of the repeating unit represented by formula (C) include the following.

The pigment multimer (C) may contain, in addition to the repeating unit represented by formula (C), other repeating units described in the description of the embodiment of the pigment multimer (A).

Specific examples of the pigment multimer (C) include the pigment multimer (S-6) described in the examples below.

(Pigment multimer (D))
Dye multimer (D) is a compound represented by Formula (D).

In formula (D), L ⁴ represents an (n+k)-valent linking group,
n represents an integer from 2 to 20,
k represents an integer from 0 to 20,
DyeIV stands for dye structure,
^P4 represents a substituent,
Each of n DyeIV may be different,
When k is 2 or more, the plurality of P ⁴ may be different,
n+k represents an integer from 2 to 20;

n in formula (D) 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.

The (n+k)-valent linking group represented by L ⁴ in formula (D) includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 Groups consisting of 1 to 200 hydrogen atoms and 0 to 20 sulfur atoms are included. The (n+k)-valent linking group is preferably the following structural unit or a group (which may form a ring structure) formed by combining two or more of the following structural units. * in the following formulas represents a bond.

The (n+k) ^-valent linking group represented by L4 is preferably a linking group derived from a polyfunctional thiol, a linking group derived from a polyfunctional alcohol, or a linking group derived from an acid anhydride, A linking group derived from a polyfunctional thiol is more preferred.

The (n+k)-valent linking group represented by L ⁴ is preferably a group represented by any one of formulas (Za-1) to (Za-4).

In formula (Za-1), La ³ represents a trivalent group, Ta ³ represents a single bond or a divalent linking group, and the three Ta ³ present may be the same or different. .
In formula (Za-2), La ⁴ represents a tetravalent group, Ta ⁴ represents a single bond or a divalent linking group, and the four Ta ⁴ present may be the same or different. .
In formula (Za-3), La ⁵ represents a pentavalent group, Ta ⁵ represents a single bond or a divalent linking group, and the five Ta ⁵ present may be the same or different. .
In formula (Za-4), La ⁶ represents a hexavalent group, Ta ⁶ represents a single bond or a divalent linking group, and the six Ta ^6s present may be the same or different. .
In the above formula, * represents a bond.

The divalent linking groups represented by Ta ³ to Ta ⁶ include an alkylene group, an arylene group, a heterocyclic group, -CH=CH-, -O-, -S-, -C(=O)-, and -COO- , -NR-, -CONR-, -OCO-, -SO-, -SO ₂ - and linking groups formed by linking two or more of these. Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. The divalent linking group represented by Ta ³ to Ta ⁶ is preferably a group containing -S-, more preferably -S-.

Examples of the trivalent group represented by La ³ include groups obtained by removing one hydrogen atom from the above divalent linking group. Examples of the tetravalent group represented by La ⁴ include groups obtained by removing two hydrogen atoms from the above divalent linking group. Examples of the pentavalent group represented by La ⁵ include groups obtained by removing three hydrogen atoms from the above divalent linking group. The hexavalent group represented by La ⁶ includes a group obtained by removing 4 hydrogen atoms from the above divalent linking group. The tri- to hexavalent groups represented by La ³ to La ⁶ may have the substituents described above.

Specific examples of the (n+k)-valent linking group include linking groups having the structures shown below, linking groups described in paragraphs 0071 to 0072 of JP-A-2008-222950, and paragraphs of JP-A-2013-029760. Examples include the linking group described in No. 0176, the linking group described in paragraphs 0022 to 0024 of WO 2016/031442, and the like. A wavy line in the following formula represents a bond.

The dye structure represented by DyeIV of formula (D) is preferably a residue obtained by removing one hydrogen atom from compound A1 described above, or a residue obtained by removing one hydrogen atom from compound A2 described above. More specifically, hydrogen A structure in which one atom is removed is preferable. The structure represented by formula (1) is preferably the structure represented by formula (1-1) described above or the structure represented by formula (1-2) described above. The dye structure represented by DyeIV is a structure obtained by removing one hydrogen atom from the structure represented by the above formula (1), or a structure in which the structure represented by the above formula (1) is coordinated to a metal atom. The specific dye multimer having a structure obtained by removing one hydrogen atom from is also the dye multimer of the present invention.

Examples of substituents represented by P4 in formula ⁽ D) include an acid group and a crosslinkable group. Moreover, the substituent represented by ^P4 may be a monovalent polymer chain having a repeating unit. A monovalent polymer chain having a repeating unit derived from a vinyl compound is preferable as the monovalent polymer chain having a repeating unit. When k is ² or more, k P4's may be the same or different.

When P ⁴ is a monovalent polymer chain having repeating units and k is 1, P ⁴ has 2 to 20 (preferably 2 to 15, more preferably 2 to 10) is preferred. Further, when P ⁴ is a monovalent polymer chain having repeating units and k is 2 or more, the average number of vinyl compound-derived repeating units in k P ⁴ is 2 to 20 ( preferably 2 to 15, more preferably 2 to 10).
When ^P4 is a monovalent polymer chain having repeating units, the number of repeating units and the average number of repeating units can be determined by nuclear magnetic resonance (NMR).

When P ⁴ is a monovalent polymer chain having a repeating unit, the repeating unit constituting P ⁴ includes other repeating units described in the description of the embodiment of the dye multimer (A) described above. . Other repeating units preferably have one or more selected from repeating units having an acid group and repeating units having a crosslinkable group.
When ^P4 contains a repeating unit containing an acid group, the proportion of the repeating unit containing an acid group is preferably 10 to 80 mol%, preferably 10 to 65 mol%, relative to the ^total repeating units of P4. is more preferred.
When P ⁴ contains a repeating unit having a crosslinkable group, the ratio of the repeating unit having a crosslinkable group is preferably 10 to 80 mol%, preferably 10 to 65 mol, relative to the total repeating units of P ⁴ . % is more preferred.

The dye multimer (D) is preferably a compound represented by formula (D-1).
(DyeIV-L ⁴³ ) _n −L ⁴¹ −(L ⁴² −P ⁴ ) _k (D-1)
In formula (D-1), L ⁴¹ represents an (n+k)-valent linking group,
n represents an integer from 2 to 20,
k represents an integer from 0 to 20,
DyeIV stands for dye structure,
^P4 represents a substituent,
L ⁴² and L ⁴³ each independently represent a single bond or a divalent linking group,
each of the n DyeIV and L ⁴³ may be different,
When k is 2 or more, the plurality of P ⁴ and L ⁴² may be different,
n+k represents an integer from 2 to 20;

DyeIV, P ⁴ , n and k in formula (D-1) are synonymous with DyeIV, P ⁴ , n and k in formula (D), and preferred ranges are also the same.

The (n+k)-valent linking group represented by L ⁴¹ of formula (D-1) includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, and 0 to 50 oxygen atoms. , from 1 to 200 hydrogen atoms, and from 0 to 20 sulfur atoms. The (n+k)-valent linking group is preferably the following structural unit or a group (which may form a ring structure) formed by combining two or more of the following structural units. * in the following formulas represents a bond.

Examples of the divalent linking group represented by L ⁴² and L ⁴³ of formula (D-1) include an alkylene group, an arylene group, a heterocyclic group, -CH=CH-, -O-, -S-, and -C (= O)-, -COO-, -NR-, -CONR-, -OCO-, -SO-, -SO ₂ -, and linking groups formed by linking two or more of these. Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. L ⁴² and L ⁴³ are preferably groups containing -S-, more preferably -S-.

Specific examples of the dye multimer (D) include the dye multimers (S-7), (S-8), (S-15), etc. described in the examples below.

The weight average molecular weight of the specific dye multimer is preferably 2,000 to 50,000. If the weight-average molecular weight of the specific dye multimer is within the above range, the effects of the present invention are remarkably exhibited. The lower limit of the weight-average molecular weight is preferably 3,000 or more, more preferably 6,000 or more, from the viewpoint of storage stability. The upper limit of the weight average molecular weight is preferably 30,000 or less, more preferably 20,000 or less, from the viewpoint of suppressing residue.

The acid value of the specific dye multimer is preferably 10-400 mgKOH/g. If the acid value of the specific dye multimer is within the above range, the generation of residue can be further suppressed. The lower limit of the acid value is preferably 20 mgKOH/g or more, more preferably 50 mgKOH/g or more, from the viewpoint of pattern formability. The upper limit of the acid value is preferably 300 mgKOH/g or less, more preferably 200 mgKOH/g or less.

The ethylenically unsaturated bond-containing group value of the specific dye multimer is preferably 0.1 to 2.5 mmol/g. If the ethylenically unsaturated bond-containing group value of the specific dye multimer is within the above range, a film having excellent light resistance and solvent resistance can be easily obtained. The lower limit of the ethylenically unsaturated bond-containing group value is preferably 0.2 mmol/g or more, more preferably 0.3 mmol/g or more. The upper limit of the ethylenically unsaturated bond-containing group value is preferably 2.0 mmol/g or less, more preferably 1.5 mmol/g or less, from the viewpoint of light resistance. The ethylenically unsaturated bond-containing group value of the specific dye multimer is a numerical value representing the molar amount of the ethylenically unsaturated bond-containing group per 1 g of the solid content of the specific dye multimer. The ethylenically unsaturated bond-containing group value of the specific dye multimer can be calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of the specific dye multimer by the molecular weight of the specific dye multimer. can.

The specific dye multimer may be a dye, but is preferably a pigment from the viewpoint of heat resistance and light resistance.

The amount of the specific dye multimer dissolved in 100 g of propylene glycol monomethyl ether at 23°C is preferably 1 g or less, more preferably 0.5 g or less.

The maximum absorption wavelength of the specific dye multimer preferably exists in the wavelength range of 400 to 700 nm, more preferably in the wavelength range of 400 to 600 nm. Moreover, the specific dye multimer is preferably a yellow colorant.

The specific dye multimer may form a salt with the carboxylic acid used during synthesis.

Specific examples of the specific dye multimer include the dye multimers (S-1) to (S-17) described in the examples below.

The content of the specific dye multimer in the total solid content of the coloring composition is preferably 0.5 to 80% by mass. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 5% by mass or more, even more preferably 10% by mass or more, and 15% by mass. The above is even more preferable. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, and 35% by mass. The following are even more preferred. The coloring composition of the present invention may contain only one type of specific dye multimer, or may contain two or more types. When two or more specific dye multimers are included, the total amount thereof preferably falls within the above range.

<<Curable compound>>
The coloring composition of the present invention contains a curable compound. Examples of the curable compound include polymerizable compounds and resins. The resin may be a non-polymerizable resin (a resin having no polymerizable group) or a polymerizable resin (a resin having a polymerizable group). Polymerizable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, with the epoxy group being preferred. The epoxy group may be a cycloaliphatic epoxy group. The alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.

As the curable compound, it is preferable to use one containing at least a resin. Further, when the coloring composition of the present invention is used as a coloring composition for photolithography, a resin having an acid group and a polymerizable monomer (monomer type polymerizable compound) can be used as the curable compound. More preferably, a resin having an acid group and a polymerizable monomer having an ethylenically unsaturated bond-containing group (monomer-type polymerizable compound) are used.

(Polymerizable compound)
Examples of the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group and compounds having a cyclic ether group. A compound having an ethylenically unsaturated bond-containing group can be preferably used as a radically polymerizable compound. A compound having a cyclic ether group can also be preferably used as a cationically polymerizable compound.

Examples of resin-type polymerizable compounds include resins containing repeating units having polymerizable groups.

The molecular weight of the monomer type polymerizable compound (polymerizable monomer) is preferably less than 2000, more preferably 1500 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 200 or more. The weight average molecular weight (Mw) of the resin-type polymerizable compound is preferably 2,000 to 2,000,000. The upper limit of the weight average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit of the weight average molecular weight is preferably 3000 or more, more preferably 5000 or more.

The compound having an ethylenically unsaturated bond-containing group as a polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples include paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraph numbers 0254-0257 of JP-A-2008-292970, and JP-A-2013-253224. Paragraph numbers 0034 to 0038 of the publication, paragraph number 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, JP 6031807, JP 2017-194662 and the contents of which are incorporated herein.

Examples of compounds having an ethylenically unsaturated bond-containing group include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetra(meth)acrylate (commercially available). KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate ) 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 the (meth)acryloyl groups of these compounds are ethylene glycol and / Or a compound having a structure linked via a propylene glycol residue (for example, SR454 and SR499 commercially available from Sartomer). Examples of compounds having an ethylenically unsaturated bond-containing group include diglycerin EO (ethylene oxide)-modified (meth)acrylate (commercially available as M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (Shin-Nakamura Chemical Industry ( 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 Nippon Kayaku Co., Ltd.) Toagosei Co., Ltd.), NK Oligo UA-7200 (Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (Taisei Fine Chemical Co., Ltd.), Light acrylate POB-A0 (Kyoeisha Chemical Co., Ltd. ) made) etc. can also be used.

Examples of compounds having an ethylenically unsaturated bond-containing group include trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, and ethylene oxide isocyanurate. It is also preferable to use trifunctional (meth)acrylate compounds such as modified tri(meth)acrylate and pentaerythritol tri(meth)acrylate. Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) etc.

A compound having an ethylenically unsaturated bond-containing group may further have an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group. Commercially available products of such compounds include Aronix M-305, M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).

A compound having a caprolactone structure can also be used as the compound having an ethylenically unsaturated bond-containing group. For compounds having a caprolactone structure, the descriptions in paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, the contents of which are incorporated herein. Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as a series from Nippon Kayaku Co., Ltd.

A compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used as the compound having an ethylenically unsaturated bond-containing group. Such a compound is preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group and/or a propyleneoxy group, and is a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group. More preferably, it is a tri- to hexa-functional (meth)acrylate compound having 4 to 20 ethyleneoxy groups. Commercially available products include, for example, SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer Co., Ltd., and a trifunctional (meth)acrylate having three isobutyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. KAYARAD TPA-330, etc.

A polymerizable compound having a fluorene skeleton can also be used as the compound having an ethylenically unsaturated bond-containing group. Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).

As the compound having an ethylenically unsaturated bond-containing group, it is also preferable to use a compound such as toluene that does not substantially contain environmentally regulated substances. Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

Examples of compounds having an ethylenically unsaturated bond-containing group include 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 Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 ( Kyoeisha Chemical Co., Ltd.) and the like are also preferably used.

Compounds having a cyclic ether group include compounds having an epoxy group, compounds having an oxetanyl group, and the like, and compounds having an epoxy group are preferred. Compounds having an epoxy group include compounds having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably two or more.

A compound having a cyclic ether group may be a low-molecular compound (for example, a molecular weight of less than 1000) or a macromolecule (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight-average molecular weight of 1000 or more). The weight average molecular weight of the cyclic ether group is preferably from 200 to 100,000, more preferably from 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

As the compound having a cyclic ether group, compounds described in paragraph numbers 0034 to 0036 of JP-A-2013-011869, compounds described in paragraph numbers 0147-0156 of JP-A-2014-043556, JP 2014 The compounds described in paragraphs 0085 to 0092 of JP-A-089408 and the compounds described in JP-A-2017-179172 can also be used.

Commercially available compounds having a cyclic ether group include Denacol EX-212L, EX-212, EX-214L, EX-214, EX-216L, EX-216, EX-321L, EX-321, EX-850L, EX -850 (manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC -7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (manufactured by ADEKA Corporation) Daicel), Cychromer P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, ACA Z320 (manufactured by Daicel Co., Ltd.), jER1031S, jER157S65, jER152, jER154, jER157S70 (manufactured by Mitsubishi Chemical Co., Ltd.) ), Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.), ADEKA GLYCIROL ED-505 (manufactured by ADEKA Co., Ltd., epoxy group-containing monomer), Proof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation, epoxy group containing polymer), OXT-101, OXT-121, OXT-212, OXT-221 (manufactured by Toagosei Co., Ltd., oxetanyl group-containing monomer), OXE-10, OXE-30 (above, Osaka Organic Chemical Industry ( Co., Ltd., oxetanyl group-containing monomer), and the like.

(resin)
A resin can be used as a curable compound in the coloring composition of the present invention. It is preferable to use a curable compound containing at least a resin. The resin is blended, for example, for dispersing a pigment or the like in a coloring composition or as a binder. A resin mainly used for dispersing a pigment or the like in a coloring composition is also called a dispersant. However, such uses of the resin are only examples, and the resin can be used for purposes other than such uses. A resin having a polymerizable group also corresponds to a polymerizable compound.

The weight average molecular weight of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.

Examples of resins include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, Polyamide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, and the like. One of these resins may be used alone, or two or more may be mixed and used. As the cyclic olefin resin, norbornene resin is preferable from the viewpoint of improving heat resistance. Commercially available norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (for example, ARTON F4520). Further, as the resin, the resin described in the examples of International Publication No. 2016/088645, the resin described in JP-A-2017-057265, the resin described in JP-A-2017-032685, JP Resins described in JP-A-2017-075248, resins described in JP-A-2017-066240, resins described in JP-A-2017-167513, resins described in JP-A-2017-173787, Resins described in paragraph numbers 0041 to 0060 of JP-A-2017-206689, resins described in paragraph numbers 0022-0071 of JP-A-2018-010856, blocks described in JP-A-2016-222891 Polyisocyanate resin, resin described in JP-A-2020-122052, resin described in JP-A-2020-111656, resin described in JP-A-2020-139021, JP-A-2017-138503 A resin containing a structural unit having a ring structure in its main chain and a structural unit having a biphenyl group in its side chain as described in 1) can also be used. As the resin, a resin having a fluorene skeleton can also be preferably used. Regarding the resin having a fluorene skeleton, the description of US Patent Application Publication No. 2017/0102610 can be referred to, the content of which is incorporated herein. In addition, as the resin, the resin described in paragraphs 0199 to 0233 of JP-A-2020-186373, the alkali-soluble resin described in JP-A-2020-186325, and the Korean Patent Publication No. 10-2020-0078339. A resin represented by the formula 1 can also be used.

It is preferable to use a resin having an acid group as the resin. Examples of acid groups include carboxy groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups. Only one kind of these acid groups may be used, or two or more kinds thereof may be used. A resin having an acid group can be used, for example, as an alkali-soluble resin. The acid value of the resin having acid groups is preferably 30-500 mgKOH/g. The lower limit is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more. The upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.

As the resin, a resin containing a repeating unit derived from a compound represented by the formula (ED1) and/or a compound represented by the formula (ED2) (hereinafter, these compounds may be referred to as an "ether dimer"). It is also preferred to include

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description in JP-A-2010-168539 can be referred to.

For specific examples of ether dimers, paragraph number 0317 of JP-A-2013-029760 can be referred to, the content of which is incorporated herein.

As the resin, it is also preferable to use a resin having a polymerizable group. Polymerizable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.

Further, as the resin, at least one type of repeating unit (hereinafter also referred to as repeating unit Ep) selected from repeating units represented by formula (Ep-1) and repeating units represented by formula (Ep-2). A resin (hereinafter also referred to as resin Ep) can also be used. The resin Ep may contain only one of the repeating units represented by the formula (Ep-1) and the repeating unit represented by the formula (Ep-2). -1) and the repeating unit represented by formula (Ep-2) may be included. When both repeating units are included, the ratio of the repeating unit represented by the formula (Ep-1) to the repeating unit represented by the formula (Ep-2) is the molar ratio represented by the formula (Ep-1). Repeating unit: repeating unit represented by formula (Ep-2) = preferably 5:95 to 95:5, more preferably 10:90 to 90:10, 20:80 to 80 :20 is more preferred.

In formulas (Ep-1) and (Ep-2), L ¹ represents a single bond or a divalent linking group, and R ¹ represents a hydrogen atom or a substituent. The substituent represented by R ¹ includes an alkyl group and an aryl group, preferably an alkyl group. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, more preferably 1-3. R ¹ is preferably a hydrogen atom or a methyl group. The divalent linking group represented by L ¹ includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S- and groups formed by combining two or more of these. The alkylene group may be linear, branched or cyclic, preferably linear or branched. Moreover, the alkylene group may have a substituent or may be unsubstituted. A hydroxy group, an alkoxy group, etc. are mentioned as a substituent.

The content of the repeating unit Ep in the resin Ep is preferably 1 to 100 mol% of all repeating units in the resin Ep. The upper limit is preferably 90 mol % or less, more preferably 80 mol % or less. The lower limit is preferably 2 mol % or more, more preferably 3 mol % or more.

The resin Ep may have other repeating units in addition to the repeating unit Ep. Other repeating units include a repeating unit having an acid group, a repeating unit having an ethylenically unsaturated bond-containing group, and the like.

The acid group includes a phenolic hydroxy group, a carboxy group, a sulfo group, and a phosphoric acid group, preferably a phenolic hydroxy group or a carboxy group, more preferably a carboxy group.

Examples of ethylenically unsaturated bond-containing groups include vinyl groups, styrene groups, (meth)allyl groups, and (meth)acryloyl groups.

When the resin Ep contains a repeating unit having an acid group, the content of the repeating unit having an acid group in the resin Ep is preferably 5 to 85 mol% of all repeating units in the resin Ep. The upper limit is preferably 60 mol % or less, more preferably 40 mol % or less. The lower limit is preferably 8 mol% or more, more preferably 10 mol% or more.

When the resin Ep contains a repeating unit having an ethylenically unsaturated bond-containing group, the content of the repeating unit having an ethylenically unsaturated bond-containing group in the resin Ep is 1 to 65 mol% of the total repeating units of the resin Ep. is preferably The upper limit is preferably 45 mol % or less, more preferably 30 mol % or less. The lower limit is preferably 2 mol % or more, more preferably 3 mol % or more.

The resin Ep preferably further contains a repeating unit having an aromatic hydrocarbon ring. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The aromatic hydrocarbon ring may have a substituent. An alkyl group etc. are mentioned as a substituent. When the resin having a cyclic ether group contains a repeating unit having an aromatic hydrocarbon ring, the content of the repeating unit having an aromatic hydrocarbon ring is 1 to 65 in all repeating units of the resin having a cyclic ether group. Mole % is preferred. The upper limit is preferably 45 mol % or less, more preferably 30 mol % or less. The lower limit is preferably 2 mol % or more, more preferably 3 mol % or more. Repeating units having an aromatic hydrocarbon ring include repeating units derived from monofunctional polymerizable compounds having an aromatic hydrocarbon ring, such as vinyl toluene and benzyl (meth)acrylate.

As the resin, it is also preferable to use a resin containing a repeating unit derived from the compound represented by formula (X).

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represent an alkylene group, and n represents an integer of 0-15. The number of carbon atoms in the alkylene group represented by R ²¹ and R ²² is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, particularly 2 or 3. preferable. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.

Examples of the compound represented by formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylate of paracumylphenol. Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).

As the resin, it is also preferable to use a resin having an aromatic carboxy group (hereinafter also referred to as resin Ac). In Resin Ac, the aromatic carboxy group may be contained in the main chain of the repeating unit or may be contained in the side chain of the repeating unit. The aromatic carboxy group is preferably contained in the main chain of the repeating unit. In this specification, an aromatic carboxy group is a group having a structure in which one or more carboxy groups are bonded to an aromatic ring. In the aromatic carboxy group, the number of carboxy groups bonded to the aromatic ring is preferably 1-4, more preferably 1-2.

Resin Ac is preferably a resin containing at least one repeating unit selected from repeating units represented by formula (Ac-1) and repeating units represented by formula (Ac-2).

In formula (Ac-1), Ar ¹ represents a group containing an aromatic carboxyl group, L ¹ represents -COO- or -CONH-, and L ² represents a divalent linking group.
In formula (Ac-2), Ar ¹⁰ represents a group containing an aromatic carboxyl group, L ¹¹ represents -COO- or -CONH-, L ¹² represents a trivalent linking group, P ¹⁰ represents a polymer represents a chain.

Examples of the aromatic carboxy group-containing group represented by Ar ¹ in formula (Ac-1) include structures derived from aromatic tricarboxylic acid anhydrides, structures derived from aromatic tetracarboxylic acid anhydrides, and the like. Aromatic tricarboxylic anhydrides and aromatic tetracarboxylic anhydrides include compounds having the following structures.

In the above formula, Q ¹ is a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C(CF ₃ ) ₂ -, represented by the following formula (Q-1) or a group represented by the following formula (Q-2).

The group containing an aromatic carboxyl group represented by Ar ¹ may have a polymerizable group. The polymerizable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, more preferably an ethylenically unsaturated bond-containing group. Specific examples of the group containing an aromatic carboxy group represented by Ar ¹ include a group represented by formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13). and the like.

In formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, more preferably 2.
In formula (Ar-12), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 2.
In formula (Ar-13), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, preferably 1 More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
In formula (Ar-13), Q ¹ is a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C(CF ₃ ) ₂ -, the above formula (Q- 1) or a group represented by the above formula (Q-2).
In formulas (Ar-11) to (Ar-13), * ¹ represents the bonding position with L1.

In formula (Ac-1), L ¹ represents -COO- or -CONH-, preferably -COO-.

The divalent linking group represented by L ² in formula (Ac-1) includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and these A group obtained by combining two or more of The number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-20, even more preferably 1-15. The alkylene group may be linear, branched or cyclic. The arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. An alkylene group and an arylene group may have a substituent. A hydroxy group etc. are mentioned as a substituent. The divalent linking group represented by L ² is preferably a group represented by -L ^2a -O-. L ^2a is an alkylene group; an arylene group; a group in which an alkylene group and an arylene group are combined; at least one selected from an alkylene group and an arylene group; Examples include groups in which at least one selected from —NH— and —S— are combined, and alkylene groups are preferred. The number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-20, even more preferably 1-15. The alkylene group may be linear, branched or cyclic. An alkylene group and an arylene group may have a substituent. A hydroxy group etc. are mentioned as a substituent.

The group containing an aromatic carboxy group represented by Ar ¹⁰ in formula (Ac-2) has the same meaning as Ar ¹ in formula (Ac-1), and the preferred range is also the same.

In formula (Ac-2), L ¹¹ represents -COO- or -CONH-, preferably -COO-.

The trivalent linking group represented by L ¹² in formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and 2 of these Groups in which more than one species are combined are included. Hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-15. The aliphatic hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, even more preferably 6-10. The hydrocarbon group may have a substituent. A hydroxy group etc. are mentioned as a substituent. The trivalent linking group represented by L ¹² is preferably a group represented by formula (L12-1), more preferably a group represented by formula (L12-2).

In formula (L12-1), L ^12b represents a trivalent linking group, X ¹ represents S, *1 represents the bonding position with L ¹¹ of formula (Ac-2), *2 represents formula ( The binding position of Ac- ² ) with P10 is shown. The trivalent linking group represented by L ^12b includes a hydrocarbon group; and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- and the like, and a hydrocarbon group or a group of a combination of a hydrocarbon group and —O— is preferred.

In formula (L12-2), L ^12c represents a trivalent linking group, X ¹ represents S, *1 represents the bonding position with L ¹¹ of formula (Ac-2), *2 represents formula ( The binding position of Ac- ² ) with P10 is shown. The trivalent linking group represented by L ^12c includes a hydrocarbon group; and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- and the like, preferably a hydrocarbon group.

P ¹⁰ in formula (Ac-2) represents a polymer chain. The polymer chain represented by ^P10 preferably has at least one repeating unit selected from poly(meth)acrylic repeating units, polyether repeating units, polyester repeating units and polyol repeating units. The weight average molecular weight of the polymer chain P10 is preferably ^500-20,000 . The lower limit is preferably 1000 or more. The upper limit is preferably 10,000 or less, more preferably 5,000 or less, even more preferably 3,000 or less. If the weight average molecular weight of ^P10 is within the above range, the dispersibility of the pigment in the composition is good. When the resin having an aromatic carboxyl group is a resin having repeating units represented by formula (Ac-2), this resin is preferably used as a dispersant.

The polymer chain represented by ^P10 may contain a polymerizable group. Polymerizable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.

The coloring composition of the present invention preferably contains a resin as a dispersant. Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups. As the acidic dispersant (acidic resin), a resin having an acid group content of 70 mol % or more is preferable when the total amount of the acid group and the basic group is 100 mol %. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10-105 mgKOH/g. Further, a basic dispersant (basic resin) represents a resin in which the amount of basic groups is greater than the amount of acid groups. As the basic dispersant (basic resin), a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and basic groups is 100 mol %. The basic group possessed by the basic dispersant is preferably an amino group.

The resin used as the dispersant is also preferably a graft resin. For details of the graft resin, reference can be made to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.

The resin used as the dispersant is also preferably a polyimine-based dispersant containing nitrogen atoms in at least one of its main chain and side chains. The polyimine-based dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom. A resin having The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. Regarding the polyimine-based dispersant, the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.

The resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core. Such resins include, for example, dendrimers (including star polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.

The resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in its side chain. The content of repeating units having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70, of the total repeating units of the resin. More preferably, it is mol %.

Further, as a dispersant, resins described in JP-A-2018-087939, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, Polyethyleneimine having a polyester side chain described in International Publication No. 2016/104803, a block copolymer described in International Publication No. 2019/125940, a block polymer having an acrylamide structural unit described in JP-A-2020-066687 , a block polymer having an acrylamide structural unit described in JP-A-2020-066688, a dispersant described in WO 2016/104803, and the like can also be used.

Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine-Techno Co., Inc. Ajisper series, and the like. In addition, the product described in paragraph number 0129 of JP-A-2012-137564 and the product described in paragraph number 0235 of JP-A-2017-194662 can also be used as a dispersant.

The content of the curable compound in the total solid content of the coloring composition is preferably 1 to 70% by mass. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less. The coloring composition of the present invention may contain only one kind of curable compound, or may contain two or more kinds of curable compounds. When two or more curable compounds are included, the total amount thereof is preferably within the above range.

When the coloring composition contains a polymerizable compound as a curable compound, the content of the polymerizable compound is preferably 1 to 70% by mass based on the total solid content of the coloring composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less. The coloring composition of the present invention may contain only one polymerizable compound, or may contain two or more polymerizable compounds. When two or more polymerizable compounds are included, the total amount thereof is preferably within the above range.

When the coloring composition contains a polymerizable monomer as a curable compound, the content of the polymerizable monomer is preferably 1 to 50% by mass based on the total solid content of the coloring composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. The coloring composition of the present invention may contain only one polymerizable monomer, or may contain two or more polymerizable monomers. When two or more polymerizable monomers are included, the total amount thereof is preferably within the above range.

When the coloring composition of the present invention contains a resin as a curable compound, the content of the resin is preferably 1 to 70 wt% of the total solid content of the coloring composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.
Also, the content of the resin having an acid group is preferably 1 to 70 mass% of the total solid content of the coloring composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.
Also, the content of the alkali-soluble resin is preferably 1 to 70% by mass of the total solid content of the coloring composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.
When the coloring composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant is preferably 0.1 to 30% by mass based on the total solid content of the coloring composition. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. Also, the content of the resin as a dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the pigment. The upper limit is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less. The lower limit is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more.
The coloring composition of the present invention may contain only one resin, or may contain two or more resins. When two or more resins are included, the total amount thereof is preferably within the above range.

When the coloring composition of the present invention contains a polymerizable monomer and a resin as curable compounds, the content of the polymerizable monomer is preferably 30 to 150 parts by mass with respect to 100 parts by mass of the resin. The upper limit is preferably 130 parts by mass or less, more preferably 110 parts by mass or less. The lower limit is preferably 40 parts by mass or more, more preferably 50 parts by mass or more.

<<Other coloring agents>>
The coloring composition of the present invention can further contain a coloring agent (another coloring agent) other than the specific dye multimer described above. Other colorants include chromatic colorants such as green colorants, red colorants, yellow colorants, violet colorants, blue colorants, orange colorants, and the like. The other coloring agent is preferably at least one selected from a green coloring agent, a red coloring agent and a yellow coloring agent, more preferably a green coloring agent. Other coloring agents may be pigments or dyes, but are preferably pigments.

The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. In addition, in this specification, the primary particle diameter of the pigment can be determined from the image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle size in this specification is the arithmetic mean value of the primary particle sizes of 400 primary particles of the pigment. Further, the primary particles of the pigment refer to independent particles without agglomeration.

Examples of green colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. The green colorant is preferably a pigment, more preferably a phthalocyanine pigment, and even more preferably a halogenated phthalocyanine pigment. Specific examples of green colorants include C.I. I. Green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65 and 66 are included. Further, as a green colorant, a halogenated zinc phthalocyanine having an average number of halogen atoms of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 per molecule. Pigments can also be used. Specific examples include compounds described in International Publication No. 2015/118720. In addition, as a green colorant, the compound described in Chinese Patent Application No. 106909027, the phthalocyanine compound having a phosphoric acid ester as a ligand described in WO 2012/102395, described in JP 2019-008014. The phthalocyanine compound, the phthalocyanine compound described in JP-A-2018-180023, the compound described in JP-A-2019-038958, the aluminum phthalocyanine compound described in JP-A-2020-070426, JP-A-2020-076995 Core-shell type dyes described in, diarylmethane compounds described in JP-A-2020-504758, and the like can also be used.

The green coloring agent is C.I. I. Pigment Green 7, 36, 58, 59, 62 and 63 are preferred, C.I. I. Pigment Green 7, 36, 58 and 59 are more preferred.

Examples of red colorants include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, and thioindigo compounds. The red colorant is preferably a pigment, more preferably a diketopyrrolopyrrole pigment, anthraquinone pigment, azo pigment, naphthol pigment, azomethine pigment, xanthene pigment, quinacridone pigment, perylene pigment or thioindigo pigment. Pyrrole pigments, anthraquinone pigments and azo pigments are more preferred, and diketopyrrolopyrrole pigments are particularly preferred. Specific examples of red colorants include C.I. I. (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, 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 and other red pigments. Further, as a red colorant, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, a diketopyrrolopyrrole described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838 Pyrrole compounds, diketopyrrolopyrrole compounds described in WO 2012/102399, diketopyrrolopyrrole compounds described in WO 2012/117965, brominated diketopyrrolo described in JP 2020-085947 Pyrrole compound, naphthol azo compound described in JP-A-2012-229344, red coloring agent described in JP-A-6516119, red coloring agent described in JP-A-6525101, paragraph of JP-A-2020-090632 Brominated diketopyrrolopyrrole compounds described in No. 0229, anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140741, anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140744, JP 2020 -Perylene compounds described in JP-A-079396, perylene compounds described in JP-A-2020-083982, xanthene compounds described in JP-A-2018-035345, paragraph numbers 0025 to 0041 of JP-A-2020-066702 The described diketopyrrolopyrrole compounds and the like can also be used. Also, as a red colorant, a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton is used. can also Lumogen F Orange 240 (manufactured by BASF, red pigment, perylene pigment) can also be used as a red colorant.

The red coloring agent is C.I. I. Pigment Red 122, 177, 179, 254, 255, 264, 269, 272 and 291 are preferred, and C.I. I. Pigment Red 254, 264, 272 are more preferred.

Examples of yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds and perylene compounds. The yellow colorant is preferably a pigment, more preferably an azo pigment, an azomethine pigment, an isoindoline pigment, a pteridine pigment, a quinophthalone pigment or a perylene pigment, and even more preferably an isoindoline pigment or an azo pigment. Specific examples of yellow colorants include C.I. I. 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, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236 and other yellow pigments.

In addition, as a yellow colorant, an azobarbiturate nickel complex having the following structure can also be used.

Further, as a yellow colorant, compounds described in JP-A-2017-201003, compounds described in JP-A-2017-197719, paragraphs 0011-0062, 0137-0276 of JP-A-2017-171912 Compounds described in paragraph numbers 0010 to 0062 and 0138 to 0295 of JP-A-2017-171913, compounds described in paragraph numbers 0011-0062 and 0139-0190 of JP-A-2017-171914, JP 2017 Compounds described in paragraph numbers 0010 to 0065 and 0142 to 0222 of JP-A-171915, quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP-A-2013-054339, paragraph numbers 0013- of JP-A-2014-026228 0058, the isoindoline compound described in JP-A-2018-062644, the quinophthalone compound described in JP-A-2018-203798, the quinophthalone compound described in JP-A-2018-062578, and the patent No. 6432076. Quinophthalone compounds described in JP-A-2018-155881, quinophthalone compounds described in JP-A-2018-111757, quinophthalone compounds described in JP-A-2018-040835, JP-A-2017 -Quinophthalone compounds described in JP-A-197640, quinophthalone compounds described in JP-A-2016-145282, quinophthalone compounds described in JP-A-2014-085565, quinophthalone compounds described in JP-A-2014-021139, in particular Quinophthalone compounds described in JP-A-2013-209614, quinophthalone compounds described in JP-A-2013-209435, quinophthalone compounds described in JP-A-2013-181015, quinophthalone compounds described in JP-A-2013-061622 , the quinophthalone compound described in JP-A-2013-032486, the quinophthalone compound described in JP-A-2012-226110, the quinophthalone compound described in JP-A-2008-074987, the JP-A-2008-081565. Quinophthalone compounds, quinophthalone compounds described in JP-A-2008-074986, quinophthalone compounds described in JP-A-2008-074985, quinophthalone compounds described in JP-A-2008-050420, JP-A Quinophthalone compounds described in 2008-031281, quinophthalone compounds described in JP-B-48-032765, quinophthalone compounds described in JP-A-2019-008014, quinophthalone compounds described in Japanese Patent No. 6607427, published in Korea Compounds described in Patent No. 10-2014-0034963, compounds described in JP 2017-095706, compounds described in Taiwan Patent Application Publication No. 201920495, compounds described in Patent No. 6607427, Compounds described in JP-A-2020-033525, compounds described in JP-A-2020-033524, compounds described in JP-A-2020-033523, compounds described in JP-A-2020-033522, JP-A-2020 - compound described in WO 2020/045200, compound described in WO 2020/045199, compound described in WO 2020/045197, JP 2020-093994 Azo compound described in the publication, a perylene compound described in International Publication No. 2020/105346, a quinophthalone compound described in JP 2020-517791, a compound represented by the following formula (QP1), the following formula (QP2) A compound represented by can also be used. Moreover, those obtained by polymerizing these compounds are also preferably used from the viewpoint of improving the color value.

In formula (QP1), X ¹ to X ¹⁶ each independently represent a hydrogen atom or a halogen atom, and Z ¹ represents an alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by formula (QP1) include compounds described in paragraph 0016 of Japanese Patent No. 6443711.

In formula (QP2), Y ¹ to Y ³ each independently represent a halogen atom. n and m are integers from 0 to 6; p is an integer from 0 to 5; (n+m) is 1 or more. Specific examples of the compound represented by formula (QP2) include compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.

The yellow coloring agent is C.I. I. Pigment Yellow 117, 129, 138, 139, 150 and 185 are preferred.

As an orange coloring agent, C.I. I. 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. of orange pigments.

As a purple colorant, C.I. I. Purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61 are included.

As a blue colorant, C.I. I. 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. be done. An aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue colorant. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A-2012-247591 and paragraph number 0047 of JP-A-2011-157478.

Dyes can also be used as other coloring agents. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, Phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes can be used.

Other colorants include diarylmethane compounds described in JP-A-2020-504758, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, and JP-A-2020-117638. Xanthene compounds described, phthalocyanine compounds described in International Publication No. 2020/174991, isoindoline compounds described in JP-A-2020-160279 or salts thereof, Korean Patent Publication No. 10-2020-0069442 described Compound represented by Formula 1, compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069730, represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069070 Compounds, compounds represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069067, compounds represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069062, Patent No. 6809649 and the isoindoline compound described in JP-A-2020-180176. The chromatic colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, may be used in the rod-like structure, or may be used in both structures.

Other colorants may be used in combination of two or more. Further, when two or more other colorants are used in combination, black color may be formed by the combination of the specific dye multimer and two or more other colorants. Such a colored composition is preferably used as a colored composition for forming an infrared transmission filter. In the case of forming a black color by combining the specific dye multimer described above and two or more other colorants, the combination of two or more other colorants includes, for example, the following (1) to (5) A combination of
(1) A mode containing a red colorant and a blue colorant.
(2) A mode containing a red colorant, a blue colorant, and a purple colorant.
(3) A mode containing a red colorant, a blue colorant, a purple colorant, and a green colorant.
(4) A mode containing a red colorant, a blue colorant, and a green colorant.
(5) In (1) to (4), an embodiment further containing a yellow colorant.

Other colorants include at least one selected from phthalocyanine pigments, dioxazine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, azo pigments, azomethine pigments, diketopyrrolopyrrole pigments, pyrrolopyrrole pigments, isoindoline pigments and quinophthalone pigments. It preferably contains a phthalocyanine pigment, more preferably at least one selected from diketopyrrolopyrrole pigments and pyrrolopyrrole pigments, and more preferably contains a phthalocyanine pigment from the viewpoint of light resistance and solvent resistance. .
Further, the phthalocyanine pigment is preferably a halogenated phthalocyanine pigment. That is, the other coloring agent preferably contains a halogenated phthalocyanine pigment. Further, the halogenated phthalocyanine pigment used as another coloring agent is preferably a green pigment. A halogenated phthalocyanine pigment is a phthalocyanine pigment having a halogen atom as a substituent.
Further, the phthalocyanine pigment is preferably a phthalocyanine pigment having a central metal, more preferably a phthalocyanine pigment having a copper atom, a zinc atom or an aluminum atom as the central metal, and having a copper atom or a zinc atom as the central metal. Phthalocyanine pigments are more preferred. A ligand may be further coordinated to the central metal.

Other colorants include halogenated copper phthalocyanine pigments (halogenated phthalocyanine pigments having a copper atom as the central metal), halogenated zinc phthalocyanine pigments (halogenated phthalocyanine pigments having a zinc atom as the central metal), and halogenated aluminum phthalocyanines. It preferably contains at least one selected from pigments (halogenated phthalocyanine pigments having an aluminum atom as a central metal), and more preferably contains at least one selected from halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments. preferable. Halogenated copper phthalocyanine pigments include C.I. I. Pigment Green 7, 36 and the like. Halogenated zinc phthalocyanine pigments include C.I. I. Pigment Green 58, 59 and the like. Examples of halogenated aluminum phthalocyanine pigments include C.I. I. Pigment Green 63 and the like.

The content of other colorants in the total solid content of the coloring composition is preferably 10 to 80% by mass. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, and even more preferably 40% by mass or more.
Also, the content of the other colorant is preferably 50 to 1000 parts by mass with respect to 100 parts by mass of the specific dye multimer. The upper limit is preferably 900 parts by mass or less, more preferably 800 parts by mass or less. The lower limit is preferably 70 parts by mass or more, more preferably 100 parts by mass or more.
Further, the total content of the specific dye multimer and the other colorant in the total solid content of the coloring composition is preferably 20 to 90% by mass. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and even more preferably 50% by mass or more.

When the coloring composition of the present invention is used as a coloring composition for forming green pixels of a color filter, the other coloring agent preferably contains a green coloring agent. It is also preferable to use a green coloring agent and a yellow coloring agent together. Also, the green colorant is preferably a phthalocyanine pigment, more preferably a halogenated phthalocyanine pigment.
In this aspect, the content of the green coloring agent in the other coloring agent is preferably 50% by mass or more, more preferably 70% by mass or more. Also, the content of the green colorant is preferably 150 to 600 parts by mass with respect to 100 parts by mass of the specific pigment multimer. The upper limit is preferably 550 parts by mass or less, more preferably 500 parts by mass or less. The lower limit is preferably 200 parts by mass or more, more preferably 250 parts by mass or more.
Moreover, when a green coloring agent and a yellow coloring agent are used together as other coloring agents, the yellow coloring agent is preferably an isoindoline pigment or an azo pigment.

When the coloring composition of the present invention is used as a coloring composition for forming red pixels of a color filter, the other coloring agent preferably contains a red coloring agent. It is also preferable to use a red coloring agent and a yellow coloring agent together. Also, the red colorant is preferably a diketopyrrolopyrrole pigment.
In this aspect, the content of the red colorant in the other colorant is preferably 40% by mass or more, more preferably 50% by mass or more. Also, the content of the red coloring agent is preferably 50 to 900 parts by mass with respect to 100 parts by mass of the specific pigment multimer. The upper limit is preferably 850 parts by mass or less, more preferably 800 parts by mass or less. The lower limit is preferably 70 parts by mass or more, more preferably 100 parts by mass or more.

<Photoinitiator>>
The coloring composition of the present invention can contain a photopolymerization initiator. When a polymerizable monomer is used as the curable compound, the colored composition of the invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet range to the visible range are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds and the like. From the viewpoint of exposure sensitivity, photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbi imidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl-substituted coumarin compounds, oxime compounds, α-hydroxyketones compounds, α-aminoketone compounds, and acylphosphine compounds, more preferably oxime compounds. Further, as the photopolymerization initiator, compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37-60p, vol. 19, No. 3, the peroxide photopolymerization initiator described in 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 The photopolymerization initiator described in JP-A-2019-044030, the photopolymerization initiator described in JP-A-2019-167313, the peroxide-based initiator described in JP-A-2020-055992. An aminoacetophenone-based initiator having an oxazolidine group described, an oxime-based photopolymerization initiator described in JP-A-2013-190459, a polymer described in JP-A-2020-172619, and International Publication No. 2020/152120. and the compounds of Formula 1 described, the contents of which are incorporated herein.

Specific examples of hexaarylbiimidazole compounds include 2,2′,4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1′-biimidazole, etc. is mentioned.

Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above company) and the like. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (manufactured by Irgacure 369E, Irgacure 379EG). made), etc. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (manufactured by BASF).

Examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication No. 2015 / 152153, compounds described in WO 2017/051680, compounds described in JP 2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017/164127, Compounds described in International Publication No. 2013/167515, compounds described in Japanese Patent No. 5430746, compounds described in Japanese Patent No. 5647738, and the like. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropane-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime) and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (manufactured by BASF), TR-PBG-304, TR-PBG-327 (manufactured by Tronly), and Adeka Optomer N-1919 (manufactured by Tronly). ) manufactured by ADEKA, photopolymerization initiator 2) described in JP-A-2012-014052. As the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Corporation).

An oxime compound having a fluorene ring can also be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466, compounds described in Japanese Patent No. 6636081, and compounds described in Korean Patent Publication No. 10-2016-0109444. mentioned.

As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in WO2013/083505.

An oxime compound having a fluorine atom can also be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of.

An oxime compound having a nitro group can be used as the photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.

An oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator. Specific examples include OE-01 to OE-75 described in WO 2015/036910.

As the photopolymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to the carbazole skeleton can also be used. Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.

As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar 2 ^OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used. Examples of the electron-withdrawing group of the aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An acyl group and a nitro group are preferred, an acyl group is more preferred, and a benzoyl group is even more preferred because a film having excellent light resistance can be easily formed. A benzoyl group may have a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group. A sulfanyl group or an amino group is more preferred.

The oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.

In the formula, R ^X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group,
R ^X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, aryl represents a sulfonyl group, an acyloxy group or an amino group,
R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent;
However, at least one of R ^X10 to R ^X14 is an electron-withdrawing group.

Examples of electron-withdrawing groups include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups, with acyl groups and nitro groups being preferred. An acyl group is more preferred, and a benzoyl group is even more preferred, because a film having excellent properties can be easily formed.

In the above formula, R ^X12 is an electron-withdrawing group, and R ^X10 , R ^X11 , R ^X13 and R ^X14 are preferably hydrogen atoms.

Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.

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

The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. Further, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high from the viewpoint of sensitivity, more preferably 1000 to 300000, further preferably 2000 to 300000, even more preferably 5000 to 200000. It is particularly preferred to have The molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As a photopolymerization initiator, it is also preferable to use a combination of Irgacure OXE01 (manufactured by BASF) and/or Irgacure OXE02 (manufactured by BASF) and Omnirad 2959 (manufactured by IGM Resins B.V.).

As the photopolymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is reduced, the solubility in a solvent or the like is improved, the precipitation becomes difficult over time, and the stability over time of the colored composition can be improved. . Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Paragraph numbers 0407 to 0412, dimers of oxime compounds described in paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compounds described in JP-A-2013-522445 ( G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of JP 2017-523465, JP 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, described in Japanese Patent No. 6469669 and oxime ester photoinitiators.

The content of the photopolymerization initiator in the total solid content of the coloring composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less.
In the coloring composition of the present invention, only one type of photopolymerization initiator may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.

<<Solvent>>
The coloring composition of the present invention preferably contains a solvent. An organic solvent is mentioned as a solvent. The type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition. Organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For these details, reference can be made to paragraph 0223 of WO2015/166779, the content of which is incorporated herein. Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxy butanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropyl alcohol and the like. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be better reduced for environmental reasons (e.g., 50 mass ppm (parts per million), 10 mass ppm or less, or 1 mass ppm or less).

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 a ppt (parts per trillion) level by mass may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015). .

Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore size of the filter used for filtration 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.

The organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one isomer may be contained, or a plurality of isomers may be contained.

The content of peroxide in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.

The content of the solvent in the coloring composition is preferably 10-95% by mass, more preferably 20-90% by mass, and even more preferably 30-90% by mass.

In addition, from the viewpoint of environmental regulations, it is preferable that the colored composition of the present invention does not substantially contain environmentally regulated substances. In the present invention, "substantially free of environmentally regulated substances" means that the content of environmentally regulated substances in the colored composition is 50 ppm by mass or less, preferably 30 ppm by mass or less. , is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Environmental control substances include, for example, benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These substances are registered as environmental controlled substances under the REACH (Registration Evaluation Authorization and Restriction of Chemicals) Regulations, the Pollutant Release and Transfer Register (PRTR) Law, and the VOC (Volatile Organic Compounds) Regulations. methods are strictly regulated. These compounds may be used as a solvent when producing each component used in the coloring composition, and may be mixed into the coloring composition as a residual solvent. From the viewpoint of safety to humans and consideration for the environment, it is preferable to reduce these substances as much as possible. As a method for reducing the amount of environmentally regulated substances, there is a method in which the system is heated or decompressed to raise the temperature to the boiling point of the environmentally regulated substances or higher, and the environmentally regulated substances are distilled off from the system. In the case of distilling off a small amount of environmentally regulated substances, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to increase the efficiency. In addition, when a compound having radical polymerizability is contained, a polymerization inhibitor or the like is added and distilled off under reduced pressure in order to suppress the radical polymerization reaction from progressing during the vacuum distillation and the intermolecular cross-linking. may These distillation methods are the raw material stage, the reaction product of the raw materials (for example, the resin solution or polyfunctional monomer solution after polymerization), or the colored composition stage produced by mixing these compounds. It is possible at any stage such as

<<Pigment derivative>>
The coloring composition of the present invention can contain pigment derivatives. Pigment derivatives are used, for example, as dispersing aids. Pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.

Dye skeletons constituting pigment derivatives include quinoline dye skeletons, benzimidazolone dye skeletons, benzoisoindole dye skeletons, benzothiazole dye skeletons, iminium dye skeletons, squarylium dye skeletons, croconium dye skeletons, oxonol dye skeletons, and pyrrolopyrrole dye skeletons. skeleton, diketopyrrolopyrrole dye skeleton, azo dye skeleton, azomethine dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, anthraquinone dye skeleton, quinacridone dye skeleton, dioxazine dye skeleton, perinone dye skeleton, perylene dye skeleton, thioindigo dye skeleton, Isoindoline dye skeletons, isoindolinone dye skeletons, quinophthalone dye skeletons, iminium dye skeletons, dithiol dye skeletons, triarylmethane dye skeletons, pyrromethene dye skeletons, and the like can be mentioned.

The acid group includes a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imidic acid group and salts thereof. Atoms or atomic groups constituting the salt include alkali metal ions (Li ⁺ , Na ⁺ , K ⁺ etc.), alkaline earth metal ions (Ca ²⁺ , Mg ²⁺ etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ion and the like. As the carboxylic acid amide group, a group represented by —NHCOR ^X1 is preferable. As the sulfonic acid amide group, a group represented by —NHSO ₂ R ^X2 is preferable. The imidic acid group is preferably a group represented by —SO ₂ NHSO ₂ R ^X3 , —CONHSO ₂ R ^X4 , —CONHCOR ^X5 or —SO ₂ NHCOR ^X6 , more preferably —SO ₂ NHSO ₂ R ^X3 . R ^X1 to R ^X6 each independently represent an alkyl group or an aryl group. The alkyl groups and aryl groups represented by R ^X1 to R ^X6 may have substituents. The substituent is preferably a halogen atom, more preferably a fluorine atom.

Basic groups include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups. Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

A pigment derivative having excellent visible transparency (hereinafter also referred to as a transparent pigment derivative) can also be used as the pigment derivative. The maximum value (εmax) of the molar extinction coefficient of the transparent pigment derivative in the wavelength region of 400 to 700 nm is preferably 3000 L·mol ⁻¹ ·cm ⁻¹ or less, and 1000 L·mol ⁻¹ ·cm ⁻¹ or less. is more preferable, and 100 L·mol ⁻¹ ·cm ⁻¹ or less is even more preferable. The lower limit of εmax is, for example, 1 L·mol ⁻¹ ·cm ⁻¹ or more, and may be 10 L·mol ⁻¹ ·cm ⁻¹ or more.

Specific examples of pigment derivatives include compounds described in JP-A-56-118462, compounds described in JP-A-63-264674, compounds described in JP-A-01-217077, JP-A-03- 009961, compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, compounds described in JP-A-03-045662, JP-A-04-285669 Compounds described in publications, compounds described in JP-A-06-145546, compounds described in JP-A-06-212088, compounds described in JP-A-06-240158, JP-A-10-030063 Compounds described, compounds described in JP-A-10-195326, compounds described in paragraphs 0086 to 0098 of WO 2011/024896, WO 2012/102399 described in paragraphs 0063 to 0094 Compounds, compounds described in paragraph number 0082 of WO 2017/038252, compounds described in paragraph number 0171 of JP 2015-151530, JP 2011-252065 described in paragraphs 0162 to 0183 Compounds, compounds described in JP-A-2003-081972, compounds described in Patent No. 5299151, compounds described in JP-A-2015-172732, compounds described in JP-A-2014-199308, JP Compounds described in 2014-085562, compounds described in JP-A-2014-035351, compounds described in JP-A-2008-081565, compounds described in JP-A-2019-109512, JP-A-2019- Compounds described in 133154, diketopyrrolopyrrole compounds having a thiol linking group described in WO 2020/002106, benzimidazolone compounds described in JP 2018-168244 or salts thereof. .

The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the specific coloring agent. In addition, the total content of the pigment derivative and the colorant is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and 50% by mass of the total solid content of the coloring composition. More than % by mass is particularly preferred. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

<<Polyalkyleneimine>>
The coloring composition of the present invention can also contain a polyalkyleneimine. Polyalkyleneimines are used, for example, as dispersing aids for pigments. A dispersing aid is a material for enhancing dispersibility of a pigment in a coloring composition. Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine. Polyalkyleneimine is preferably a polymer having at least a secondary amino group. The polyalkyleneimine may contain a primary amino group or a tertiary amino group in addition to the secondary amino group. The polyalkyleneimine is preferably a polymer having a branched structure each containing a primary amino group, a secondary amino group and a tertiary amino group. The alkyleneimine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, still more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.

The molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less. Regarding the value of the molecular weight of the polyalkyleneimine, when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, when the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used. When the boiling point elevation method cannot be used or the measurement is difficult, the value of the number average molecular weight measured by the viscosity method is used. In addition, when measurement by the viscosity method is not possible or measurement by the viscosity method is difficult, the value of the number average molecular weight in terms of polystyrene measured by the GPC (gel permeation chromatography) method is used.

The amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.

Specific examples of alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine and the like, preferably ethyleneimine or propyleneimine, more preferably ethyleneimine. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. In addition, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more, of the primary amino group with respect to the total of the primary amino group, the secondary amino group and the tertiary amino group. , more preferably 30 mol % or more. Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, P-1000 (manufactured by Nippon Shokubai Co., Ltd.).

The content of polyalkyleneimine in the total solid content of the coloring composition is preferably 0.1 to 5% by mass. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. Also, the content of the polyalkyleneimine is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. Only one kind of polyalkyleneimine may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.

<<Curing accelerator>>
The coloring composition of the present invention can contain a curing accelerator. 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 and the like. Specific examples of the curing accelerator include compounds described in paragraph numbers 0094 to 0097 of WO 2018/056189, compounds described in paragraph numbers 0246 to 0253 of JP 2015-034963, JP 2013-041165 Compounds described in paragraph numbers 0186 to 0251 of the publication, ionic compounds described in JP 2014-055114, compounds described in paragraph numbers 0071 to 0080 of JP 2012-150180, JP 2011-253054 Alkoxysilane compounds having an epoxy group described in JP-A-2005-200557, compounds described in paragraphs 0085 to 0092 of Japanese Patent No. 5765059, and carboxy group-containing epoxy curing agents described in JP-A-2017-036379. The content of the curing accelerator in the total solid content of the coloring composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.

<<Infrared Absorber>>
The coloring composition of the present invention can further contain an infrared absorbing agent. For example, in the case of forming an infrared transmission filter using the coloring composition of the present invention, the wavelength of the light transmitted through the film obtained by containing an infrared absorbing agent in the coloring composition is shifted to the longer wavelength side. can be made The infrared absorbing agent is preferably a compound having a maximum absorption wavelength on the longer wavelength side than the wavelength of 700 nm. The infrared absorbing agent is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 nm or more and 1800 nm or less. In addition, the ratio A ¹ /A ² between the absorbance A ¹ at a wavelength of 500 nm and the absorbance A ² at the maximum absorption wavelength of the infrared absorbent is preferably 0.08 or less, more preferably 0.04 or less. .

Examples of infrared absorbers include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, and azomethine. compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, and the like. As the pyrrolopyrrole compound, compounds described in paragraph numbers 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph numbers 0037-0052 of JP-A-2011-068731, WO 2015/166873 Compounds described in Paragraph Nos. 0010 to 0033 and the like. Examples of the squarylium compound include compounds described in paragraph numbers 0044 to 0049 of JP-A-2011-208101, compounds described in paragraph numbers 0060 to 0061 of Japanese Patent No. 6065169, and paragraph number 0040 of WO 2016/181987. Compounds described in, compounds described in JP-A-2015-176046, compounds described in paragraph No. 0072 of WO 2016/190162, compounds described in paragraph Nos. 0196 to 0228 of JP-A-2016-074649 , the compound described in paragraph number 0124 of JP 2017-067963, the compound described in WO 2017/135359, the compound described in JP 2017-114956, the compound described in Patent 6197940, Examples include compounds described in International Publication No. 2016/120166. As the cyanine compound, compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267, compounds described in paragraphs 0026-0030 of JP-A-2002-194040, and JP-A-2015-172004. The compound, the compound described in JP-A-2015-172102, the compound described in JP-A-2008-088426, the compound described in paragraph number 0090 of WO 2016/190162, JP-A-2017-031394 and the like compounds described in. Examples of croconium compounds include compounds described in JP-A-2017-082029. As the iminium compound, for example, compounds described in JP-A-2008-528706, compounds described in JP-A-2012-012399, compounds described in JP-A-2007-092060, International Publication No. 2018/043564 and the compounds described in paragraphs 0048 to 0063 of. Examples of the phthalocyanine compound include compounds described in paragraph number 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraph numbers 0013 to 0029 of JP-A-2013-195480. compounds, vanadium phthalocyanine compounds described in Japanese Patent No. 6081771, vanadium phthalocyanine compounds described in International Publication No. 2020/071486, and phthalocyanine compounds described in International Publication No. 2020/071470. Examples of naphthalocyanine compounds include compounds described in paragraph number 0093 of JP-A-2012-077153. Dithiolene metal complexes include compounds described in Japanese Patent No. 5733804. Examples of metal oxides include indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, and tungsten oxide. For details of tungsten oxide, paragraph 0080 of JP-A-2016-006476 can be referred to, the content of which is incorporated herein. Examples of metal borides include lanthanum boride. Commercially available lanthanum boride products include LaB ₆ -F (manufactured by Nippon New Metal Co., Ltd.). Moreover, as a metal boride, the compound as described in international publication 2017/119394 can also be used. Commercially available products of indium tin oxide include F-ITO (manufactured by DOWA Hitech Co., Ltd.).

Further, as the infrared absorbing agent, the squarylium compound described in JP-A-2017-197437, the squarylium compound described in JP-A-2017-025311, the squarylium compound described in WO 2016/154782, and the patent No. 5884953. No. 6036689, squarylium compounds described in Japanese Patent No. 5810604, squarylium compounds described in paragraphs 0090 to 0107 of International Publication No. 2017/213047, Pyrrole ring-containing compounds described in paragraph numbers 0019 to 0075 of JP-A-2018-054760, pyrrole ring-containing compounds described in paragraph numbers 0078 to 0082 of JP-A-2018-040955, paragraphs of JP-A-2018-002773 Pyrrole ring-containing compounds described in numbers 0043 to 0069, squarylium compounds having an aromatic ring at the amide α-position described in paragraph numbers 0024 to 0086 of JP-A-2018-041047, amides described in JP-A-2017-179131 Linked squarylium compounds, compounds having a pyrrole bis-type squarylium skeleton or croconium skeleton described in JP-A-2017-141215, dihydrocarbazole-bis-type squarylium compounds described in JP-A-2017-082029, JP-A-2017-068120 Asymmetric compounds described in paragraphs 0027 to 0114 of the publication, pyrrole ring-containing compounds (carbazole type) described in JP 2017-067963, phthalocyanine compounds described in JP 6251530, JP A squarylium compound described in 2020-075959, a copper complex described in Korean Patent Publication No. 10-2019-0135217, and the like can also be used.

The content of the infrared absorbing agent in the total solid content of the coloring composition is preferably 1 to 40% by mass. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less. The coloring composition of the present invention may contain only one type of infrared absorbing agent, or may contain two or more types thereof. When two or more kinds of infrared absorbing agents are included, the total amount thereof is preferably within the above range.

<<Ultraviolet absorber>>
The coloring composition of the present invention can 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, and triazine compounds. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP-A-2009-217221, paragraph numbers 0052-0072 of JP-A-2012-208374, and paragraph numbers 0317-0317 of JP-A-2013-068814. 0334, and compounds described in paragraphs 0061 to 0080 of JP-A-2016-162946, the contents of which are incorporated herein. Examples of commercially available UV absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.), Tinuvin series and Uvinul series manufactured by BASF, and Sumisorb series manufactured by Sumika Chemtex Co., Ltd. . Benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil (Kagaku Kogyo Nippo, February 1, 2016). In addition, the ultraviolet absorber is a compound described in paragraph numbers 0049 to 0059 of Japanese Patent No. 6268967, a compound described in paragraph numbers 0059 to 0076 of WO 2016/181987, and WO 2020/137819. A thioaryl group-substituted benzotriazole-type ultraviolet absorber described in can also be used. The content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. Only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.

<<polymerization inhibitor>>
The coloring composition of the present invention can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, 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% by mass. Only one kind of polymerization inhibitor may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.

<<Silane coupling agent>>
The coloring composition of the present invention can contain a silane coupling agent. As used herein, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction. Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group and isocyanate group. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferred. Specific examples of the silane coupling agent include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-amino propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxy Propylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503), and the like. Further, specific examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. , the contents of which are incorporated herein. The content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass. Only one kind of silane coupling agent may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.

<<Surfactant>>
The coloring composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant. For surfactants, reference can be made to surfactants described in paragraphs 0238-0245 of WO2015/166779, the contents of which are incorporated herein.

The fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the coloring composition.

As the fluorine-based surfactant, JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-132503 and surfactants described in JP-A-2020-008634, the contents of which are incorporated herein. Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 and F-144. , F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560 , F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-01, R-40, R-40-LM, R-41, R -41-LM, RS-43, R-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH- 40 (manufactured by AGC), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), Futergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS , FTX-218 (manufactured by NEOS Corporation) and the like.

The fluorosurfactant has a molecular structure with a functional group containing a fluorine atom, and an acrylic compound in which the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied is also suitable. Available. Examples of such fluorine-based surfactants include MegaFac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Mega Fac DS-21.

It is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant. Such fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.

A block polymer can also be used as the fluorosurfactant. The fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. In addition, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.

The weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol%.

A fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain can also be used as the fluorosurfactant. Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, MEGAFACE RS-101, RS-102 and RS-718K manufactured by DIC Corporation, and RS-72-K. Further, as the fluorosurfactant, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.

It is also preferable from the viewpoint of environmental regulations to use the surfactant described in International Publication No. 2020/084854 as a substitute for the surfactant having a perfluoroalkyl group with 6 or more carbon atoms.

It is also preferable to use a fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant.

In the formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, a represents 1 or 2, X ^{a +} is a valent metal ion, primary ammonium ion, Represents secondary ammonium ion, tertiary ammonium ion, _quaternary ammonium ion or NH4 ⁺ .

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fujifilm Wa Kojunyaku Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto Oil Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.) ) and the like.

Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) , BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by BYK-Chemie) and the like.

A compound having the following structure can also be used as the silicone-based surfactant.

The content of the surfactant in the total solid content of the coloring composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.

<<Antioxidant>>
The coloring composition of the present invention can contain an antioxidant. Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like. In addition, antioxidants are compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967, compounds described in WO 2017/006600, compounds described in WO 2017/164024, Compounds described in Korean Patent Publication No. 10-2019-0059371 can also be used. The content of the antioxidant in the total solid content of the coloring composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.

<<Other Ingredients>>
The coloring composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. In addition, the coloring composition of the present invention may contain a latent antioxidant, if desired. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).

The coloring composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film. Examples of metal oxides include TiO ₂ , ZrO ₂ , Al ₂ O ₃ and SiO ₂ . The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, even more preferably 5 to 50 nm. Metal oxides may have a core-shell structure. Moreover, in this case, the core portion may be hollow.

The coloring composition of the present invention may contain a light resistance improver. As the light resistance improver, compounds described in paragraph numbers 0036 to 0037 of JP-A-2017-198787, compounds described in paragraph numbers 0029-0034 of JP-A-2017-146350, JP-A-2017-129774 Compounds described in paragraph numbers 0036 to 0037, 0049 to 0052 of JP 2017-129674 JP 2017-129674 paragraph numbers 0031 to 0034, 0058 to 0059 compounds described in JP 2017-122803 paragraph numbers 0036 to 0037 , compounds described in 0051 to 0054, compounds described in paragraph numbers 0025 to 0039 of WO 2017/164127, compounds described in paragraph numbers 0034 to 0047 of JP 2017-186546, JP 2015-025116 Compounds described in paragraph numbers 0019 to 0041 of JP-A-2012-145604, compounds described in paragraph numbers 0101-0125 of JP-A-2012-103475, compounds described in paragraph numbers 0018-0021 of JP-A-2012-103475, in particular Compounds described in paragraphs 0015 to 0018 of JP 2011-257591, compounds described in paragraphs 0017 to 0021 of JP 2011-191483, described in paragraphs 0108 to 0116 of JP 2011-145668 and compounds described in paragraph numbers 0103 to 0153 of JP-A-2011-253174.

The coloring composition of the present invention preferably does not substantially contain terephthalic acid ester. Here, "substantially free" means that the content of terephthalic acid ester is 1000 mass ppb or less in the total amount of the coloring composition, and more preferably 100 mass ppb or less, Zero is particularly preferred.

From the perspective of environmental regulations, the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts may be regulated. In the coloring composition of the present invention, when the content of the above compounds is reduced, perfluoroalkylsulfonic acid (especially perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and salts thereof, and per The content of fluoroalkylcarboxylic acid (especially perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is 0.01ppb to 1,000ppb with respect to the total solid content of the coloring composition. is preferably in the range of , more preferably in the range of 0.05 ppb to 500 ppb, even more preferably in the range of 0.1 ppb to 300 ppb. The coloring composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts. For example, by using a compound that can substitute for perfluoroalkylsulfonic acid and its salt, and a compound that can substitute for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and salts thereof may be selected. Examples of compounds that can substitute for regulated compounds include compounds that are excluded from the scope of regulation due to differences in the number of carbon atoms in perfluoroalkyl groups. However, the above content 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 within the maximum permissible range.

The water content of the coloring composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

The coloring composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface state (such as flatness) and adjusting the film thickness. The viscosity value can be appropriately selected as necessary, and is preferably, for example, 0.3 mPa·s to 50 mPa·s, more preferably 0.5 mPa·s to 20 mPa·s at 25°C. As a method for measuring the viscosity, for example, a cone-plate type viscometer can be used, and the viscosity can be measured in a state where the temperature is adjusted to 25°C.
The colored composition of the present invention preferably has a chloride ion content of 10000 ppm or less, more preferably 1000 ppm or less, from the viewpoint of environmental friendliness, suppression of foreign matter generation, suppression of equipment contamination, etc. preferable. In order to make the chloride ion in the coloring composition within the above range, the use of raw materials with a low chloride ion content, washing with water, ion exchange resin, a method of removing chloride ions by filter filtration, etc. be done. A known method can be used as a method for measuring chloride ions, and examples thereof include ion chromatography and combustion ion chromatography.

<<Container>>
The container for the coloring composition is not particularly limited, and known containers can be used. In addition, as a storage container, a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resins and a bottle with a 7-layer structure of 6 types of resins for the purpose of suppressing contamination of raw materials and coloring compositions. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351. In addition, the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the coloring composition, and suppressing deterioration of components.

<Method for preparing coloring composition>
The coloring composition of the present invention can be prepared by mixing the aforementioned ingredients. In preparing the colored composition, all components may be simultaneously dissolved and / or dispersed in a solvent to prepare a colored composition, and if necessary, each component may be appropriately mixed into two or more solutions or dispersions. , these may be mixed at the time of use (at the time of coating) to prepare a colored composition.

In addition, it is preferable to include a process of dispersing the pigment when preparing the coloring composition. In the process of dispersing pigments, mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like. In pulverizing the pigment in a sand mill (bead mill), it is preferable to use beads with a small diameter or to increase the filling rate of the beads so as to increase the pulverization efficiency. Moreover, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. In addition, the process and dispersing machine for dispersing pigments are described in "Dispersion Technology Complete Works, Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial Practical Application General Documents, Published by Management Development Center Publishing Department, October 10, 1978", the process and dispersing machine described in paragraph number 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used. In the process of dispersing the pigment, the particles may be made finer in the salt milling process. Materials, equipment, processing conditions, etc. used in the salt milling step can be referred to, for example, Japanese Patent Application Laid-Open Nos. 2015-194521 and 2012-046629.

In preparing the colored composition, it is preferable to filter the colored composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high-molecular-weight polyolefin resin) and other materials. Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore size of the filter is preferably 0.01-7.0 μm, more preferably 0.01-3.0 μm, and even more preferably 0.05-0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For the pore size value of the filter, reference can be made to the filter manufacturer's nominal value. Various filters provided by Nippon Pall Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used as filters. .

It is also preferable to use a fiber-like filter medium as the filter. Examples of fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.

When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed. In addition, the filter can be appropriately selected according to the hydrophilicity/hydrophobicity of the composition.

<Membrane>
The film of the present invention is a film obtained from the colored composition of the present invention described above. The film of the present invention can be used for optical filters such as color filters and infrared transmission filters. In particular, it can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. Green pixels, yellow pixels, or red pixels are preferred, and green pixels are more preferred. preferable.

The film thickness of the film of the present invention can be appropriately adjusted according to the purpose, but is preferably 0.1 to 20 μm. The upper limit of the film thickness is preferably 10 µm or less, more preferably 5 µm or less, still more preferably 3 µm or less, and particularly preferably 1.5 µm or less. The lower limit of the film thickness is preferably 0.2 μm or more, more preferably 0.3 μm or more.

<Method for producing membrane>
The film of the invention can be produced through a step of applying the coloring composition of the invention onto a support. Preferably, the film manufacturing method further includes a step of forming a pattern (pixels). A method for forming the pattern (pixels) includes a photolithography method and a dry etching method, and the photolithography method is preferable.

Pattern formation by photolithography includes the steps of forming a colored composition layer on a support using the colored composition of the present invention, a step of patternwise exposing the colored composition layer, and a step of exposing the colored composition layer. forming a pattern (pixels) by developing and removing the exposed portion. If necessary, a step of baking the coloring composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.

In the step of forming the colored composition layer, the colored composition layer of the present invention is used to form the colored composition layer on the support. The support is not particularly limited and can be appropriately selected depending on the application. Examples thereof include glass substrates and silicon substrates, and silicon substrates are preferred. Also, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. In some cases, the silicon substrate is formed with a black matrix that isolates each pixel. In addition, the silicon substrate may be provided with an underlying layer for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface. The underlayer may be formed using a composition obtained by removing the coloring agent from the colored composition described herein, or a composition containing the resin, polymerizable compound, surfactant, etc. described herein. good. The surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferably 30 to 80° when measured with water.

A known method can be used as a method for applying the coloring composition. For example, dropping method (drop cast); slit coating method; spray method; roll coating method; spin coating method (spin coating); methods described in publications); inkjet (e.g., on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Examples include various printing methods; transfer methods using molds and the like; nanoimprinting methods and the like. The application method for inkjet is not particularly limited. 133 page), and methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. mentioned. In addition, regarding the method of applying the coloring composition, the descriptions of WO2017/030174 and WO2017/018419 can be referred to, and the contents thereof are incorporated herein.

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

Next, the colored composition layer is exposed in a pattern (exposure step). For example, the colored composition layer can be exposed in a pattern by exposing through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.

Radiation (light) that can be used for exposure includes g-line, i-line, and the like. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferable. A long-wave light source of 300 nm or more can also be used.

In addition, when exposing, the light may be continuously irradiated and exposed, or may be irradiated and exposed in pulses (pulse exposure). Note that pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and rest in short-time (for example, millisecond level or less) cycles.

The dose (exposure dose) is, for example, preferably 0.03 to 2.5 J/cm ² , more preferably 0.05 to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be selected as appropriate. The exposure may be in an oxygen-free atmosphere, or in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). In addition, the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W/m ² to 100000 W/m ² (eg, 5000 W/m ² , 15000 W/m ² or 35000 W/m ² ). can be done. The oxygen concentration and exposure illuminance may be appropriately combined. For example, the illuminance may be 10000 W/m ² at an oxygen concentration of 10% by volume and 20000 W/m ² at an oxygen concentration of 35% by volume.

Next, the unexposed areas of the colored composition layer are removed by development to form a pattern (pixels). The development and removal of the unexposed portion of the colored composition layer can be performed using a developer. As a result, the unexposed portion of the colored composition layer in the exposure step is eluted into the developer, leaving only the photocured portion. The temperature of the developer is preferably 20 to 30° C., for example. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the step of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.

The developer includes an organic solvent, an alkaline developer, etc., and an alkaline developer is preferably used. As the alkaline developer, an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water is preferable. Examples of alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene, etc. Examples include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate and sodium metasilicate. A compound having a large molecular weight is preferable for the alkaline agent from the standpoint of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Moreover, the developer may further contain a surfactant. From the viewpoint of transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinse solution to the developed colored composition layer while rotating the support on which the developed colored composition layer is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support. At this time, when moving the nozzle from the center of the support to the periphery, the moving speed of the nozzle may be gradually decreased. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. A similar effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the periphery.

After development, it is preferable to perform additional exposure processing and heat processing (post-baking) after drying. Additional exposure processing and post-baking are post-development curing treatments for complete curing. The heating temperature in post-baking is, for example, preferably 100 to 240.degree. C., more preferably 200 to 240.degree. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. . When the additional exposure process is performed, the light used for exposure preferably has a wavelength of 400 nm or less. Also, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

Pattern formation by a dry etching method is a step of forming a colored composition layer on a support using the colored composition of the present invention, and curing the entire colored composition layer to form a cured product layer; a step of forming a photoresist layer on the cured layer; a step of patternwise exposing the photoresist layer and then developing it to form a resist pattern; and etching the cured layer using the resist pattern as a mask. and dry etching using a gas. In forming the photoresist layer, it is preferable to further perform a pre-baking process. In particular, as the formation process of the photoresist layer, a mode in which heat treatment after exposure and heat treatment (post-baking treatment) after development are performed is desirable. Regarding pattern formation by a dry etching method, descriptions in paragraphs 0010 to 0067 of JP-A-2013-064993 can be referred to, and the contents thereof are incorporated herein.

<Optical filter>
The optical filter of the present invention has the film of the present invention as described above. Types of optical filters include color filters and infrared transmission filters, and color filters are preferred. A color filter preferably has the film of the present invention as its colored pixels.

In the optical filter, 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, even 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 even more preferably 0.3 μm or more.

The width of pixels included in the optical filter is preferably 0.4 to 10.0 μm. The lower limit is preferably 0.4 μm or more, more preferably 0.5 μm or more, and even more preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, even more preferably 1.0 μm or less, and even more preferably 0.8 μm or less. Also, the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.

Each pixel included in the optical filter preferably has high flatness. Specifically, the pixel surface roughness Ra is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example. The surface roughness of a pixel can be measured using, for example, AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco. Also, the contact angle of water on the pixel can be appropriately set to a preferable value, but is typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT-A type (manufactured by Kyowa Interface Science Co., Ltd.). Moreover, it is preferable that the volume resistance value of the pixel is high. Specifically, the volume resistance value of the pixel is preferably 10 ⁹ Ω·cm or more, more preferably 10 ¹¹ Ω·cm or more. Although the upper limit is not specified, it is preferably 10 ¹⁴ Ω·cm or less, for example. The volume resistance value of the pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest).

In the optical filter, a protective layer may be provided on the surface of the film of the present invention. By providing the protective layer, it is possible to impart various functions such as blocking oxygen, reducing reflection, making the film hydrophilic and hydrophobic, and blocking light of a specific wavelength (ultraviolet rays, near-infrared rays, etc.). The thickness of the protective layer is preferably 0.01-10 μm, more preferably 0.1-5 μm. Examples of the method of forming the protective layer include a method of applying a protective layer-forming composition, a chemical vapor deposition method, and a method of adhering a molded resin with an adhesive. Components constituting the protective layer include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, and polyimides. Resin, polyamideimide 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, fluorine Resins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , Si ₂ N ₄ and the like, and two or more of these components may be contained. For example, in the case of a protective layer intended to block oxygen, the protective layer preferably contains a polyol resin, SiO ₂ and Si ₂ N ₄ . In the case of a protective layer intended to reduce reflection, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.

If necessary, the protective layer contains organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index modifiers, antioxidants, adhesion agents, additives such as surfactants. may contain. Examples of organic/inorganic fine particles include polymeric fine particles (eg, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like. A known absorber can be used as the absorber for light of a specific wavelength. The content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass of the protective layer.

Further, as the protective layer, the protective layers described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.

The optical filter may have a structure in which each pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.

<Solid-state image sensor>
The solid-state imaging device of the present invention includes the film of the present invention described above. The configuration of the solid-state imaging device is not particularly limited as long as it functions as a solid-state imaging device.

A plurality of photodiodes and transfer electrodes made of polysilicon or the like are provided on the substrate, forming the light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal-oxide semiconductor) image sensor, etc.). and a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion. and a color filter on the device protective film. Furthermore, a configuration having a condensing means (for example, a microlens or the like; the same shall apply hereinafter) on the device protective film and below the color filter (on the side close to the substrate), or a configuration having a condensing means on the color filter, etc. There may be. Moreover, the color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition wall preferably has a lower refractive index than each color pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478, JP-A-2014-179577, and International Publication No. 2018/043654. Further, as disclosed in Japanese Patent Application Laid-Open No. 2019-211559, an ultraviolet absorption layer may be provided in the structure of the solid-state imaging device to improve light resistance. An imaging device equipped with the solid-state imaging device of the present invention can be used not only for digital cameras and electronic devices having an imaging function (mobile phones, etc.), but also for vehicle-mounted cameras and monitoring cameras.

<Image display device>
The image display device of the present invention includes the film of the present invention described above. Examples of image display devices include liquid crystal display devices and organic electroluminescence display devices. For a definition of an image display device and details of each image display device, see, for example, "Electronic Display Device (by Akio Sasaki, Industrial Research Institute, 1990)", "Display Device (by Junsho Ibuki, Sangyo Tosho ( Co., Ltd.) issued in 1989). Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied.

The present invention will be described more specifically below with reference to examples. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In the structural formulas shown below, Me represents a methyl group, Et represents an ethyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

<Synthesis of dye monomer>
Dye monomers (X-1) to (X-6) were synthesized according to the following scheme. In the schemes below, DMF is N,N-dimethylformamide and THF is tetrahydrofuran.

Synthetic scheme of dye monomer (X-1)

Synthetic scheme of dye monomer (X-2)

Synthetic scheme of dye monomer (X-3)

Synthetic scheme of dye monomer (X-4)

Synthetic scheme of dye monomer (X-5)

Synthetic scheme of dye monomer (X-6)

<Synthesis of dye multimer>
Dye multimers (S-1) to (S-17) were synthesized according to the scheme below.

Synthetic scheme of dye multimer (S-1)

Synthetic scheme of dye multimer (S-2)

Synthetic scheme of dye multimer (S-3)

Synthetic scheme of dye multimer (S-4)

Synthetic scheme of dye multimer (S-5)

Synthetic scheme of dye multimer (S-6)

Synthetic scheme of dye multimer (S-7)

In formula (S-7), one of R ¹ and R ² is a hydrogen atom, the other is a group represented by formula A shown below, one of R ³ and R ⁴ is a hydrogen atom, and the other is It is a group represented by the formula A shown in.

Synthetic scheme of dye multimer (S-8)

Synthetic scheme of dye multimer (S-9)

Synthetic scheme of dye multimer (S-10)

Synthetic scheme of dye multimer (S-11)

Synthetic scheme of dye multimer (S-12)

Synthetic scheme of dye multimer (S-13)

Synthetic scheme of dye multimer (S-14)

Synthetic scheme of dye multimer (S-15)

Synthetic scheme of dye multimer (S-16)

Synthetic scheme of dye multimer (S-17)

The weight average molecular weight, acid value, and ethylenically unsaturated bond-containing group value (C=C value) of the pigment multimers (S-1) to (S-17) are as follows. In addition, the dye multimers (S-1) to (S-17) dissolved in 100 g of propylene glycol monomethyl ether at 23° C. in an amount of 1.0 g or less.

<Production of dispersion liquid>
A mixed liquid obtained by mixing raw materials shown in the table below was mixed and dispersed for 3 hours using a bead mill (zirconia beads with a diameter of 0.1 mm). Then, dispersion treatment was carried out using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) equipped with a decompression mechanism under conditions of a pressure of 2000 kg/cm ² and a flow rate of 500 g/min. This dispersing treatment was repeated 10 times to obtain a dispersion. Numerical values indicating compounding amounts in the following table are parts by mass. In addition, the numerical value of the compounding quantity of a dispersing agent is a numerical value in solid content conversion.

The details of the materials indicated by the abbreviations in the table showing the formulation of the dispersion are as follows.

(coloring agent)
PG36: C.I. I. Pigment Green 36 (halogenated phthalocyanine pigment, green pigment)
PG58: C.I. I. Pigment Green 58 (halogenated phthalocyanine pigment, green pigment)
PG59: C.I. I. Pigment Green 59 (halogenated phthalocyanine pigment, green pigment)
PG63: C.I. I. Pigment Green 63 (halogenated phthalocyanine pigment, green pigment)
PR254: C.I. I. Pigment Red 254 (diketopyrrolopyrrole pigment, red pigment)
PY129: C.I. I. Pigment Yellow 129 (azomethine pigment, yellow pigment)
PY139: C.I. I. Pigment Yellow 139 (isoindoline pigment, yellow pigment)
PY150: C.I. I. Pigment Yellow 150 (azo pigment, yellow pigment)
PY155: C.I. I. Pigment Yellow 155 (azo pigment, yellow pigment)
PY215: C.I. I. Pigment Yellow 215 (pteridine pigment, yellow pigment)
PY185: C.I. I. Pigment Yellow 185 (isoindoline pigment, yellow pigment)
PB15:6: C.I. I. Pigment Blue 15:6 (phthalocyanine pigment, blue pigment)

(pigment multimer)
S-1 to S-17: the dye multimers S-1 to S-17 described above

(Infrared absorber)
IR-1: a compound having the following structure (infrared absorber)

(pigment derivative)
A-1 to A-6: compounds having the following structures

(dispersant)
B-1: Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 24,000)

B-2: Resin having the following structure (The numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 10,000)

(solvent)
Z-1: Propylene glycol monomethyl ether acetate (PGMEA)

<Production of coloring composition>
A coloring composition was produced by mixing the materials shown in the table below.

The details of the materials indicated by the abbreviations in the table showing the formulation of the coloring composition are as follows.

(dispersion liquid)
Dispersions 1 to 53, c1: Dispersions 1 to 53, c1 described above

(Photoinitiator)
E-1 to E-4: compounds having the following structures E-5: 2,2′,4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1 '-Biimidazole

(alkali-soluble resin)
J-1: Resin having the following structure (numerical values attached to the main chain are molar ratios; weight average molecular weight: 15,000)

J-2: Resin having the following structure (numerical values attached to the main chain are molar ratios; weight average molecular weight: 15,000)

J-3: Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 24,000)

J-4: Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight 16000)

J-5: Resin having the following structure (numerical values attached to the main chain are molar ratios, weight average molecular weight 16000)

J-6: Resin having the following structure (numerical values attached to the main chain are molar ratios. Weight average molecular weight: 30,000)

J-7: Resin having the following structure (the numerical value attached to the main chain is the mass ratio, weight average molecular weight 14600)

J-8: Resin having the following structure (the numerical value attached to the main chain is the mass ratio. Weight average molecular weight 10600)

J-9: Resin synthesized by the following method A flask equipped with a reflux condenser, a dropping funnel and a stirrer is filled with an appropriate amount of nitrogen to replace the atmosphere with nitrogen, and 371 parts by mass of 1-methoxy-2-propyl acetate is added. was heated to 85° C. with stirring. Next, 54 parts by mass of acrylic acid, 225 parts by mass of a mixture of 3,4-epoxytricyclo[5.2.1.02,6]decane-8 and 9-yl acrylate, and 81 parts by mass of vinyl toluene (isomer mixture) , and 80 parts by mass of 1-methoxy-2-propyl acetate was added dropwise over 4 hours. On the other hand, a solution prepared by dissolving 30 parts by mass of 2,2-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator in 160 parts by mass of 1-methoxy-2-propyl acetate was added dropwise over 5 hours. After the completion of the dropwise addition of the initiator solution, the temperature was maintained at 85° C. for 4 hours, and then cooled to room temperature to obtain a resin. The obtained resin had a weight average molecular weight of 10,600, a dispersity of 2.01, and an acid value of 43 mgKOH/g.

(Polymerizable monomer)
D-1: A compound having the following structure

D-2: A mixture of compounds having the following structure (a mixture in which the molar ratio of the left compound (hexafunctional (meth)acrylate compound) and the right compound (pentafunctional (meth)acrylate compound) is 7:3)

D-3: A compound having the following structure

D-4: Trimethylolpropane ethyleneoxy-modified triacrylate (manufactured by Toagosei Co., Ltd., Aronix M-350)
D-5: EBECRYL80 (manufactured by Daicel Allnex, amine-containing tetrafunctional acrylate)
D-6: ethoxylated dipentaerythritol hexamethacrylate

(Surfactant)
F-1: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone surfactant, carbinol-modified polydimethylsiloxane at both ends, hydroxy value 62 mgKOH/g)
F-2: A compound having the following structure (weight average molecular weight: 14,000). In the following formulas, % indicating the ratio of repeating units is mol %. (Fluorine surfactant)

F-3: Futergent 208G (manufactured by NEOS, fluorosurfactant)
F-4: BYK-330 (manufactured by BYK-Chemie, silicone surfactant)
F-5: DOWSIL SH8400 FLUID (manufactured by Dow Toray Industries, Inc., silicone surfactant)

(Additive)
G-1: compound having the following structure (ultraviolet absorber)

G-2: compound having the following structure (compound having an epoxy group, weight average molecular weight: 3500)

G-3: EHPE3150 (manufactured by Daicel Corporation, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2′-bis(hydroxymethyl)-1-butanol)
G-4: A compound having the following structure (silane coupling agent)

(Polymerization inhibitor)
H-1: p-methoxyphenol

(solvent)
Z-1: Propylene glycol monomethyl ether acetate (PGMEA)
Z-2: propylene glycol monomethyl ether (PGME)
Z-3: cyclopentanone Z-4: cyclohexanone Z-5: anisole Z-6: diacetone alcohol

<Evaluation>
(light resistance)
The coloring composition described in the table above was applied to a glass substrate by spin coating, then heated (pre-baked) at 100°C for 120 seconds using a hot plate, and then irradiated with i-line at 1000 mJ/cm ² . It was exposed to light and then heated at 200° C. for 5 minutes to form a film with a thickness of 0.6 μm. The obtained film was measured for light transmittance (transmittance) in a wavelength range of 400 to 700 nm using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. Next, the film prepared above was irradiated with light of 100,000 Lux for 2,000 hours using a light resistance tester (super xenon weather meter SX75, manufactured by Suga Test Instruments Co., Ltd.) (total irradiation amount: 200 million Lux hr. ). The transmittance of the film after light irradiation was measured, and the light resistance was evaluated according to the following criteria.
A: The integrated value of the transmittance of the film at a wavelength of 400 to 700 nm after light irradiation is 98% or more of the integrated value of the transmittance of the film before light irradiation at a wavelength of 400 to 700 nm.
B: The integrated transmittance of the film at a wavelength of 400 to 700 nm after light irradiation is 95% or more and less than 98% of the integrated transmittance of the film at a wavelength of 400 to 700 nm before light irradiation.
C: The integrated transmittance of the film at a wavelength of 400 to 700 nm after light irradiation is 93% or more and less than 95% of the integrated transmittance of the film at a wavelength of 400 to 700 nm before light irradiation.
D: The integrated value of the transmittance of the film at a wavelength of 400 to 700 nm after light irradiation is 90% or more and less than 93% of the integrated value of the transmittance of the film at a wavelength of 400 to 700 nm before light irradiation.
E: The integrated value of the transmittance of the film at a wavelength of 400 to 700 nm after light irradiation is less than 90% of the integrated value of the transmittance of the film at a wavelength of 400 to 700 nm before light irradiation.

(Development residue)
The coloring composition described in the above table is applied to a silicon wafer by spin coating, and then heated (pre-baked) at 100° C. for 120 seconds using a hot plate to form a composition layer having a thickness of 1 μm. bottom. Next, the obtained composition layer was irradiated with light having a wavelength of 365 nm at 1000 mJ/cm ² through a 2.0 μm square Bayer pattern mask using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.). was exposed at an exposure dose of Then, the exposed composition layer was puddle-developed at 23° C. for 60 seconds using an alkaline developer (3% aqueous solution of tetramethylammonium hydroxide). Next, the silicon wafer after the paddle development is fixed on a horizontal rotary table by a vacuum chuck method, and while the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, pure water is sprayed from above the center of rotation in the form of a shower. Supply and rinse treatment (23 seconds × 2 times), then spin drying, then heat treatment (post-baking) using a hot plate at 200 ° C. for 300 seconds to form a pattern (pixel) bottom.
Using a scanning electron microscope (measurement magnification: 40,000 times), the presence or absence of residues between patterns on the silicon wafer was observed, and development residues were evaluated according to the following criteria.
A: No residue between the patterns B: A residue was present between the patterns, but the pattern could be formed C: The space between the patterns was filled with residues (pattern could not be formed)

(Storage stability)
The viscosities of the coloring compositions described in the table above were measured immediately after production. The viscosity was measured after storing the coloring composition which measured the viscosity for 72 hours in a 45 degreeC constant temperature bath. The viscosity was measured by adjusting the temperature of the coloring composition to 23°C. The viscosity increase rate was calculated from the following formula, and the storage stability was evaluated.
Thickening rate (%) = ((viscosity of the coloring composition after storage for 72 hours in a constant temperature bath at 45 ° C. / viscosity of the coloring composition immediately after production) -1) × 100
A: The viscosity increase rate of the coloring composition is 5% or less.
B: The viscosity increase rate of the coloring composition exceeds 5% and is 7.5% or less.
C: The viscosity increase rate of the coloring composition exceeds 7.5% and is 10% or less.
D: The viscosity increase rate of the coloring composition exceeds 10%.

As shown in the table above, the colored compositions of Examples were able to form films with excellent light resistance. Furthermore, the colored compositions of Examples were also excellent in storage stability. Furthermore, the use of the coloring composition of the example could suppress the generation of development residue.

The same colored compositions as in Examples 1 to 53 were prepared without adding a surfactant, and the light resistance and development residue were evaluated. The results were the same as in Examples 1 to 53.

By using the films obtained from the colored compositions of Examples 1 to 53, optical filters, solid-state imaging devices, and image display devices with excellent light resistance can be obtained.

Claims

A coloring composition comprising a dye multimer and a curable compound,
The dye multimer includes a dye structure having a structure a1 in which aromatic rings having a hydroxy group as a substituent are bonded via an azomethine group, or a structure a2 in which the structure a1 is coordinated to a metal atom.
coloring composition.
The dye multimer has at least one repeating unit selected from repeating units represented by formula (A), repeating units represented by formula (B), and repeating units represented by formula (C). is a dye multimer comprising
A dye multimer represented by formula (D),
The coloring composition of claim 1;

In formula (A), A 1 represents a trivalent linking group,
L 1 represents a single bond or a divalent linking group,
DyeI represents the dye structure;

In formula (B), A 2 represents a trivalent linking group,
L2 represents a single bond or a divalent linking group,
DyeII represents the dye structure having a group capable of forming an ionic bond or a coordinate bond with Y2,
Y 2 represents a group capable of forming an ionic bond or coordinate bond with DyeII;

In formula (C), L3 represents a single bond or a divalent linking group,
DyeIII represents the dye structure,
m represents 0 or 1;

In formula (D), L 4 represents an (n+k)-valent linking group,
n represents an integer from 2 to 20,
k represents an integer from 0 to 20,
DyeIV represents the dye structure,
P4 represents a substituent,
Each of n DyeIV may be different,
When k is 2 or more, the plurality of P 4 may be different,
n+k represents an integer from 2 to 20;
The dye structure represented by DyeI of formula (A) is a structure obtained by removing one hydrogen atom from the structure represented by formula (1), or a structure represented by formula (1) coordinated to a metal atom. A structure in which one hydrogen atom is removed from the structure,
The dye structure represented by DyeII of the formula (B) is a structure represented by the formula (1) or a structure in which the structure represented by the formula (1) is coordinated to a metal atom,
The dye structure represented by DyeIII of formula (C) is a structure obtained by removing two hydrogen atoms from the structure represented by formula (1), or a structure represented by formula (1) coordinated to a metal atom. A structure obtained by removing two hydrogen atoms from the structure,
The dye structure represented by DyeIV of formula (D) is a structure obtained by removing one hydrogen atom from the structure represented by formula (1), or a structure represented by formula (1) coordinated to a metal atom. A structure in which one hydrogen atom is removed from the structure,
The coloring composition of claim 2;

In formula (1), R 1 represents a hydrogen atom, an alkyl group or an aryl group,
X 2 to X 9 each independently represents a nitrogen atom, CH or CR x ,
R x represents a substituent,
When adjacent two of X 2 to X 9 are CR x , R x of two adjacent CR x may combine to form a ring,
In the case of DyeII of formula (B), at least one of X 2 to X 9 has a group capable of forming an ionic bond or coordinate bond with Y 2 as a substituent.
The structure represented by the formula (1) is a structure represented by the formula (1-1) or a structure represented by the formula (1-2), the coloring composition according to claim 3;

In formula (1-1), R 1 represents a hydrogen atom, an alkyl group or an aryl group,
X 2 to X 9 each independently represents a nitrogen atom, CH or CR x ,
R x represents a substituent,
When adjacent two of X 2 to X 9 are CR x , R x of two adjacent CR x may combine to form a ring,
In the case of DyeII of formula (B), at least one of X 2 to X 9 has a group capable of forming an ionic bond or coordinate bond with said Y 2 as a substituent;
However, formula (1-1) satisfies any of the following requirements 1 to 4;
Requirement 1 Adjacent two of X 3 to X 5 are CR x , and the R x 's of the two adjacent CR x 's are bonded to form a ring;
Requirement 2 X 2 and X 3 are CR x , and R x of CR x represented by X 2 and R x of CR x represented by X 3 combine to form a heterocyclic ring;
Requirement 3 Adjacent two of X 6 to X 9 are CR x , and the R x 's of the two adjacent CR x 's are bonded to form a ring;
Requirement 4 at least one of X 2 and X 3 is CH and at least one of X 2 to X 9 is CR x ;

In formula (1-2), R 1 represents a hydrogen atom, an alkyl group or an aryl group,
R 2 to R 11 each independently represent a hydrogen atom or a substituent;
Adjacent two of R 2 to R 11 may combine to form a ring, and at least one of R 2 to R 11 is a substituent;
However, in the case of DyeII of formula (B), at least one of R 2 to R 11 has a group capable of ionic or coordinate bonding with Y 2 as a substituent.
Furthermore, containing a coloring agent other than the dye multimer,
3. The coloring composition according to claim 1 or 2, wherein the coloring agent comprises a halogenated phthalocyanine pigment.
A film obtained from the colored composition according to claim 1 or 2.
An optical filter having the film according to claim 6.
A solid-state imaging device having the film according to claim 6.
An image display device having the film according to claim 6.
A dye polymer comprising a dye structure having a structure a1 in which aromatic rings having a hydroxy group as a substituent are bonded via an azomethine group, or a structure a2 in which the structure a1 is coordinated to a metal atom,
A dye multimer containing at least one repeating unit selected from repeating units represented by formula (A), repeating units represented by formula (B), and repeating units represented by formula (C), or , a dye multimer which is a dye multimer represented by the formula (D);

In formula (A), A 1 represents a trivalent linking group,
L 1 represents a single bond or a divalent linking group,
DyeI is a structure obtained by removing one hydrogen atom from the structure represented by formula (1), or a structure obtained by removing one hydrogen atom from a structure in which the structure represented by formula (1) is coordinated to a metal atom represents the dye structure of;

In formula (B), A 2 represents a trivalent linking group,
L2 represents a single bond or a divalent linking group,
DyeII is the dye structure having a group capable of forming an ionic bond or a coordinate bond with Y 2 , the structure represented by formula (1), or the structure represented by formula (1) on a metal atom represents the dye structure of the coordinated structure,
Y 2 represents a group capable of forming an ionic bond or coordinate bond with DyeII;

In formula (C), L3 represents a single bond or a divalent linking group,
DyeIII is a structure obtained by removing two hydrogen atoms from the structure represented by formula (1), or a structure obtained by removing two hydrogen atoms from a structure in which the structure represented by formula (1) is coordinated to a metal atom represents the pigment structure of
m represents 0 or 1;

In formula (D), L 4 represents an (n+k)-valent linking group,
n represents an integer from 2 to 20,
k represents an integer from 0 to 20,
DyeIV is a structure obtained by removing one hydrogen atom from the structure represented by formula (1), or a structure obtained by removing one hydrogen atom from a structure in which the structure represented by formula (1) is coordinated to a metal atom represents the pigment structure of
P4 represents a substituent,
Each of n DyeIV may be different,
When k is 2 or more, the plurality of P 4 may be different,
n+k represents an integer from 2 to 20;

In formula (1), R 1 represents a hydrogen atom, an alkyl group or an aryl group,
X 2 to X 9 each independently represents a nitrogen atom, CH or CR x ,
R x represents a substituent,
When adjacent two of X 2 to X 9 are CR x , R x of two adjacent CR x may combine to form a ring,
In the case of DyeII of formula (B), at least one of X 2 to X 9 has a group capable of forming an ionic bond or coordinate bond with Y 2 as a substituent.
The structure represented by the formula (1) is a structure represented by the formula (1-1) or a structure represented by the formula (1-2), the dye multimer according to claim 10;

In formula (1-1), R 1 represents a hydrogen atom, an alkyl group or an aryl group,
X 2 to X 9 each independently represents a nitrogen atom, CH or CR x ,
R x represents a substituent,
When adjacent two of X 2 to X 9 are CR x , R x of two adjacent CR x may combine to form a ring,
In the case of DyeII of formula (B), at least one of X 2 to X 9 has a group capable of forming an ionic bond or coordinate bond with said Y 2 as a substituent;
However, formula (1-1) satisfies any of the following requirements 1 to 4;
Requirement 1 Adjacent two of X 3 to X 5 are CR x , and the R x 's of the two adjacent CR x 's are bonded to form a ring;
Requirement 2 X 2 and X 3 are CR x , and R x of CR x represented by X 2 and R x of CR x represented by X 3 combine to form a heterocyclic ring;
Requirement 3 Adjacent two of X 6 to X 9 are CR x , and the R x 's of the two adjacent CR x 's are bonded to form a ring;
Requirement 4 at least one of X 2 and X 3 is CH and at least one of X 2 to X 9 is CR x ;

In formula (1-2), R 1 represents a hydrogen atom, an alkyl group or an aryl group,
R 2 to R 11 each independently represent a hydrogen atom or a substituent;
Adjacent two of R 2 to R 11 may combine to form a ring, and at least one of R 2 to R 11 is a substituent;
However, in the case of DyeII of formula (B), at least one of R 2 to R 11 has a group capable of ionic or coordinate bonding with Y 2 as a substituent.