JP7463887B2 - Coloring composition and near-infrared cut filter - Google Patents

Description

The present invention relates to a coloring composition and a near-infrared cut filter using the same.

In recent years, with the development of information processing technology, biometric authentication, which is personal authentication that uses biometric information that is information unique to a living body (e.g., fingerprints, irises, faces, veins, etc.), has come to be implemented. In biometric authentication, authentication is performed by irradiating a target biocomponent or biostructure with light of a wavelength corresponding to the biocomponent or biostructure, etc., and detecting the change in the light with a light receiving unit (Patent Document 1).

For example, in fingerprint authentication, a fingerprint pattern is obtained by shining blue or green light, which has low transmittance on a finger, and detecting the reflected light. During this process, red light and near-infrared light, which are natural light and have high transmittance on a finger, may enter the light-receiving section, which has a detection sensitivity in the ultraviolet to near-infrared range, and be detected as noise. To eliminate this noise, a filter that cuts out red to near-infrared light is required.

Near-infrared cut filters are manufactured using a composition containing a near-infrared absorbent, as in Patent Document 2, for example. However, their noise-cutting ability in the near-infrared region is not necessarily satisfactory. In addition, the transmittance of blue and green light used for detection is also insufficient.

Patent Publication 2017-196319 Patent Publication 2015-163956

The present invention aims to provide a coloring composition that has high transmittance for blue and green light, high noise-cutting ability in the red to near-infrared region, and good filtering properties, as well as a near-infrared cut filter that contains the coloring composition.

As a result of extensive research to solve the above problems, the inventors discovered that a coloring composition containing a squarylium dye (A) having a maximum absorption wavelength between 700 and 900 nm in the range of 400 to 1000 nm and a dye (B) having specific spectral characteristics has high transmittance for blue and green light, high noise-cutting ability in the red to near-infrared range, and good filtering properties, and have developed the present invention based on this finding.

That is, the present invention relates to a coloring composition comprising a squarylium dye (A) having a maximum absorption wavelength in the range of 400 to 1000 nm between 700 and 900 nm, and a dye (B) having spectral characteristics that satisfy the following conditions (1) and (2):
(1) When a coating film is formed so that the transmittance at 680 nm is 1%, the minimum transmittance (T1) at 400 to 450 nm is 20% or more. (2) When a coating film is formed so that the transmittance at 680 nm is 1%, the transmittance (T2) at 530 nm is 50% or more.

The present invention also relates to the coloring composition, wherein the dye (B) is a phthalocyanine pigment.

The present invention also relates to the coloring composition, wherein the dye (B) is an aluminum phthalocyanine pigment.

The present invention also relates to the colored composition, wherein the dye (B) is a compound represented by the following general formula (1):
General formula (1)

(In the formula, X ₁ to X ₄ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent.
Y ₁ to Y ₄ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
M represents Al.
Z represents -OP(=O) _R13R14 , where _R13 and _R14 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group _which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and _R13 and _R14 may bond to each other to form a ring.
m ₁ , m ₂ , m ₃ , m ₄ , n ₁ , n ₂ , n ₃ , and n ₄ each independently represent an integer of 0 to 4, and m ₁ +n ₁ , m ₂ +n ₂ , m ₃ +n ₃ , and m ₄ +n ₄ each represent an integer of 0 to 4 and may be the same or different.

The present invention also relates to the colored composition, wherein the squarylium dye (A) is at least one of compounds represented by the following general formula (2) and general formula (3):
General formula (2)
(In general formula (2), X ₁₀₁ to X ₁₁₀ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, a sulfo group, -SO ₂ NR ₁₀₁ R ₁₀₂ , -COOR ₁₀₁ , -CONR ₁₀₁ R ₁₀₂ , a nitro group, a cyano group, or a halogen atom. R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or an alkyl group which may have a substituent. X ₁₀₁ to X ₁₁₀ may be bonded to each other to form a ring.)

General formula (3)
In formula (3), Q ₁ , Q ₄ , Q ₅ and Q ₈ each independently represent a carbon atom or a nitrogen atom. When Q ₁ , Q ₄ , Q ₅ or Q ₈ is a nitrogen atom, X ₂₀₁ , X ₂₀₄ , X ₂₀₅ or X ₂₀₈ does not exist.
R ₁ to R ₅ each independently represent a hydrogen atom, a sulfo group, —SO ₃ ⁻ M ⁺ or a halogen atom, where M ⁺ represents an inorganic or organic cation.
X ₂₀₁ to X ₂₀₈ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, an amino group, -NR ₆ R ₇ , a sulfo group, -SO ₂ NR ₈ R ₉ , -COOR ₁₀ , -CONR ₁₁ R ₁₂ , a nitro group, a cyano group, or a halogen atom. X ₂₀₁ to X ₂₀₈ may be bonded to each other to form a ring.
R ₆ to R ₁₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, or a pyridinyl group which may have a substituent. R ₆ and R ₇ , R ₈ and R _{9 , and} R ₁₁ and R ₁₂ may be bonded to each other to form a ring.

The present invention also relates to the coloring composition, which further contains a basic resin-type dispersant.

The present invention also relates to the coloring composition, which further contains a photopolymerization initiator.

The present invention also relates to a near-infrared cut filter comprising the colored composition.

The present invention can provide a coloring composition that has high transmittance for blue and green light, high noise-cutting ability in the red to near-infrared region, and good filtering properties, as well as a near-infrared cut filter that contains the coloring composition.

Each of the components of the colored composition of the present invention will be described below.
In this application, unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" respectively mean "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide".
In addition, "C.I." in this specification means Color Index (C.I.).

<Squarylium dye (A)>
The coloring composition of the present invention contains a squarylium dye (A) having a maximum absorption wavelength in the range of 400 to 1000 nm between 700 and 900 nm. By having a maximum absorption wavelength of 700 to 900 nm, light in the near infrared region that is detected as noise can be widely cut, even to the longer wavelength side. The value of the maximum absorption wavelength of the squarylium dye (A) is a value measured by the method described in the examples described below.

When the absorbance of the squarylium dye (A) at the maximum absorption wavelength in the range of 400 to 1000 nm is (I1) and the absorbance at 650 nm is (I2), it is preferable that (I2)/(I1) is 0.5 or less.

The squarylium dye (A) is preferably at least one of the compounds represented by the following general formula (2) and general formula (3). Although squarylium dyes contained in cyanine dyes usually have low heat resistance, the compounds represented by general formula (2) and general formula (3) have high heat resistance.

(Compound represented by general formula (2))
General formula (2)

X ₁₀₁ to X ₁₁₀ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, a sulfo group, -SO ₂ NR ₁₀₁ R ₁₀₂ , -COOR ₁₀₁ , -CONR ₁₀₁ R ₁₀₂ , a nitro group, a cyano group, or a halogen atom. R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or an alkyl group which may have a substituent. X ₁₀₁ to X ₁₁₀ may be bonded to each other to form a ring.

Examples of the "alkyl group which may have a substituent" for X ₁₀₁ to X ₁₁₀ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a tert-amyl group, a 2-ethylhexyl group, a stearyl group, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a 2-chloroethyl group, a 2-nitroethyl group, a cyclopentyl group, a cyclohexyl group, a dimethylcyclohexyl group, etc. Among these, a methyl group, an ethyl group, and an n-propyl group are preferred from the viewpoints of imparting durability and ease of synthesis, and a methyl group is particularly preferred.

In X ₁₀₁ to X ₁₁₀ , examples of the "alkenyl group which may have a substituent" include a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, etc. Among these, a vinyl group and an allyl group are preferred from the viewpoints of imparting durability and ease of synthesis.

In X ₁₀₁ to X ₁₁₀ , examples of the "aryl group which may have a substituent" include a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, a 4-bromophenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, a 4-cyanophenyl group, etc. Among these, a phenyl group and a 4-methylphenyl group are preferred from the viewpoints of imparting durability and ease of synthesis.

In X ₁₀₁ to X ₁₁₀ , the "aralkyl group which may have a substituent" is, for example, a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, etc. Among these, a benzyl group is preferable from the viewpoint of imparting durability and ease of synthesis.

In X ₁₀₁ to X ₁₁₀ , the "alkoxy group even if it has a substituent" includes, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, a 2-ethylhexyloxy group, a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group, etc. Among these, a methoxy group, an ethoxy group, and a trifluoromethoxy group are preferable from the viewpoint of imparting durability and the ease of synthesis.

In X ₁₀₁ to X ₁₁₀ , examples of the "aryloxy group which may have a substituent" include a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group, a 4-chloro-2-methylphenyloxy group, a 4-tert-butylphenyloxy group, a 4-methoxyphenyloxy group, a 4-diethylaminophenyloxy group, a 4-nitrophenyloxy group, etc. Among these, the phenoxy group and the naphthyloxy group are preferred from the viewpoints of imparting durability and ease of synthesis.

Examples of the "substituted amino group" for X ₁₀₁ to X ₁₁₀ include a methylamino group, an ethylamino group, an isopropylamino group, an n-butylamino group, a cyclohexylamino group, a stearylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, an N,N-di(2-hydroxyethyl)amino group, a phenylamino group, a naphthylamino group, a 4-tert-butylphenylamino group, a diphenylamino group, an N-phenyl-N-ethylamino group, etc. Among these, the dimethylamino group and the diethylamino group are preferred from the viewpoints of imparting durability and ease of synthesis.

In X ₁₀₁ to X ₁₁₀ , the "halogen atom" is, for example, fluorine, bromine, chlorine, or iodine.

X ₁₀₁ to X ₁₁₀ can bond together to form a ring. When the substituents of X ₁₀₁ to X ₁₁₀ are bonded together to form a ring, examples of the structure include, but are not limited to, the following structures.

In R ₁₀₁ and R ₁₀₂ , the "alkyl group which may have a substituent" has the same meaning as, for example, X ₁ to X ₁₀ .

X ₁₀₁ to X ₁₁₀ preferably contain an unsubstituted alkyl group, at least one of X ₁₀₃ , X ₁₀₄ , X ₁₀₇ and X ₈₁₀₈ is more preferably an unsubstituted alkyl group, and X ₁₀₃ and X ₁₀₇ are further preferably an unsubstituted alkyl group. The unsubstituted alkyl group is preferably, for example, a methyl group.

(Method for producing a compound represented by formula (2))
The compound represented by the general formula (2) can be synthesized, for example, by heating and refluxing 1,8-diaminonaphthalene and a cyclohexanone represented by the following general formula (4) in a solvent together with a catalyst to cause condensation, and then adding 3,4-dihydroxy-3-cyclobutene-1,2-dione represented by the following chemical formula (5) and further heating and refluxing to cause condensation. It goes without saying that the synthesis is not limited to the above method.

(Compound represented by general formula (3))
General formula (3)

Q ₁ , Q ₄ , Q ₅ and Q ₈ each independently represent a carbon atom or a nitrogen atom. When Q ₁ , Q ₄ , Q ₅ or Q ₈ is a nitrogen atom, X ₂₀₁ , X ₂₀₄ , X ₂₀₅ or X ₂₀₈ does not exist.
R ₁ to R ₅ each independently represent a hydrogen atom, a sulfo group, —SO ₃ ⁻ M ⁺ or a halogen atom, where M ⁺ represents an inorganic or organic cation.
X ₂₀₁ to X ₂₀₈ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, an amino group, -NR ₆ R ₇ , a sulfo group, -SO ₂ NR ₈ R ₉ , -COOR ₁₀ , -CONR ₁₁ R ₁₂ , a nitro group, a cyano group, or a halogen atom. X ₂₀₁ to X ₂₀₈ may be bonded to each other to form a ring.
R ₆ to R ₁₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, or a pyridinyl group which may have a substituent. R ₆ and R ₇ , R ₈ and R _{9, and} R ₁₁ and R ₁₂ may be bonded to each other to form a ring.

Q ₁ , Q ₄ , Q ₅ and Q ₈ are, for example, more preferably a carbon atom.

In R ₁ to R ₅ , examples of the "halogen atom" include fluorine, bromine, chlorine and iodine.

In R ₁ to R ₅ , the "inorganic or organic cation" of M ⁺ may be, for example, a known one without any restrictions, and in the case of an organic cation, it may be either a low molecular type or a high molecular type. Specific examples include metal atoms, ammonium compounds, pyridinium compounds, imidazolium compounds, phosphonium compounds, sulfonium compounds, etc. In the case of a high molecular type, examples include, but are not limited to, "resins having a quaternary ammonium base". Among these, trivalent metal atoms, ammonium compounds, and resins having a quaternary ammonium base are preferred from the viewpoint of heat resistance.

From the viewpoint of imparting resistance, it is preferred that R ₁ to R ₅ are all hydrogen atoms, or that four of R ₁ to R ₅ are hydrogen atoms and one is a sulfo group, -SO ₃ ^- M ⁺ or a halogen atom. Among these, it is particularly preferred that all are hydrogen atoms, or that four of R ₁ to R ₅ are hydrogen atoms and one is a sulfo group or a halogen atom.

In X ₂₀₁ to X ₂₀₈ , examples of the "alkyl group which may have a substituent" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an isobutyl group, a tert-amyl group, a 2-ethylhexyl group, a stearyl group, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a 2-chloroethyl group, a 2-nitroethyl group, a cyclopentyl group, a cyclohexyl group, a dimethylcyclohexyl group, etc. Among these, a methyl group and an ethyl group are preferable from the viewpoint of the difficulty of synthesis.

In X ₂₀₁ to X ₂₀₈ , examples of the "alkenyl group which may have a substituent" include a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, etc. Among these, a vinyl group and an allyl group are preferred from the viewpoint of the difficulty of synthesis.

In X ₂₀₁ to X ₂₀₈ , examples of the "aryl group which may have a substituent" include a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, a 4-bromophenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, a 4-cyanophenyl group, etc. Among these, a phenyl group and a 4-methylphenyl group are preferred from the viewpoint of the ease of synthesis.

In X ₂₀₁ to X ₂₀₈ , the "aralkyl group which may have a substituent" is, for example, a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, etc. Among these, a benzyl group is preferable from the viewpoint of the difficulty of synthesis.

In X ₂₀₁ to X ₂₀₈ , examples of the "alkoxy group even if it has a substituent" include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, a 2-ethylhexyloxy group, a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group, a 2-(diethylamino)ethoxy group, etc. Among these, a methoxy group, an ethoxy group, a trifluoromethoxy group, and a 2-(diethylamino)ethoxy group are preferable from the viewpoint of the difficulty of synthesis.

In X ₂₀₁ to X ₂₀₈ , examples of the "aryloxy group which may have a substituent" include a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group, a 4-chloro-2-methylphenyloxy group, a 4-tert-butylphenyloxy group, a 4-methoxyphenyloxy group, a 4-diethylaminophenyloxy group, a 4-nitrophenyloxy group, etc. Among these, the phenoxy group and the naphthyloxy group are preferable from the viewpoint of the ease of synthesis.

In X ₂₀₁ to X ₂₀₈ , the "halogen atom" is, for example, fluorine, bromine, chlorine, or iodine.

X ₂₀₁ to X ₂₀₈ may be bonded to each other to form a ring. Preferred structures in the case where X ₂₀₁ to X ₂₀₈ are bonded to each other to form a ring are shown below. However, the structure is not limited to these.

From the viewpoints of dispersibility, storage stability and ease of synthesis, it is particularly preferable that X ₂₀₁ to X ₂₀₈ are all hydrogen atoms.

Examples of the "alkyl group which may have a substituent" in R ₆ to R ₁₂ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an isobutyl group, a sec-butyl group, a tert-amyl group, a 2-ethylhexyl group, a stearyl group, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a 2-chloroethyl group, a 2-nitroethyl group, a cyclopentyl group, a cyclohexyl group, a dimethylcyclohexyl group, etc. Among these, a methyl group and an ethyl group are preferred from the viewpoint of the difficulty of synthesis.

Examples of the "aryl group which may have a substituent" in R ₆ to R ₁₂ include a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, a 4-bromophenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, a 4-cyanophenyl group, etc. Among these, a phenyl group and a 4-methylphenyl group are preferred from the viewpoint of the ease of synthesis.

In R ₆ to R ₁₂ , examples of the "acyl group which may have a substituent" include an acetyl group, a propioyl group, a benzoyl group, an acrylyl group, a trifluoroacetyl group, etc. Among these, the acetyl group is preferred from the viewpoint of the ease of synthesis.

In R ₆ to R ₁₂ , examples of the "pyridinyl group which may have a substituent" include a 2-pyridinyl group, a 3-pyridinyl group, a 4-pyridinyl group, a 2-methyl-4-pyridinyl group, etc. Among these, the 4-pyridinyl group is preferred from the viewpoint of ease of synthesis.

R ₆ and R ₇ , R ₈ and R _{9 , and} R ₁₁ and R ₁₂ may be bonded to each other to form a ring.

(Method for producing a compound represented by formula (3))
The compound represented by general formula (3) can be explained, for example, by the following reaction diagram. First, 1,8-diaminonaphthalenes and fluorenones are heated and refluxed in a solvent together with a catalyst to cause condensation, and then 3,4-dihydroxy-3-cyclobutene-1,2-dione is added and further heated and refluxed to cause condensation. When at least one of R ₁ to R ₅ is SO ₃ ^- M ⁺ , a dye substituted with SO ₃ ^- M ⁺ is obtained by counter ion exchange between the hydrogen ion of the sulfo group of the dye substituted with a sulfo group and a compound having the desired cation. It goes without saying that the synthesis is not limited to the above method.

The content of squarylium dye (A) in the total solid content of the coloring composition is preferably 2 to 65 mass %, and more preferably 4 to 50 mass %.

<Dye (B)>
The coloring composition of the present invention contains a dye (B) having spectral characteristics that satisfy the following conditions (1) and (2). By containing the dye (B), blue and green light can be sufficiently transmitted, and red light that is detected as noise can be cut.

(1) When a coating film is formed so that the transmittance at 680 nm is 1%, the minimum transmittance (T1) at 400 to 450 nm is 20% or more. (2) When a coating film is formed so that the transmittance at 680 nm is 1%, the transmittance (T2) at 530 nm is 50% or more.

Although the principle is unclear, the filterability is improved by combining squarylium dye (A) and dye (B).

The dye (B) is preferably a phthalocyanine pigment, more preferably an aluminum phthalocyanine pigment, and by containing an aluminum phthalocyanine pigment, blue and green light can be transmitted over a wide range of wavelengths, thereby improving detection sensitivity.Furthermore, it is preferably a compound represented by the following general formula (1):
General formula (1)

In the formula, X ₁ to X ₄ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent.
Y ₁ to Y ₄ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
M represents Al.
Z represents -OP(=O) _R13R14 , where _R13 and _R14 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group _which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and _R13 and _R14 may bond to each other to form a ring.
m ₁ , m ₂ , m ₃ , m ₄ , n ₁ , n ₂ , n ₃ , and n ₄ each independently represent an integer of 0 to 4, and m ₁ +n ₁ , m ₂ +n ₂ , m ₃ +n ₃ , and m ₄ +n ₄ each represent an integer of 0 to 4 and may be the same or different.

In the general formula (1), X ₁ to X ₄ may be the same or different, and specific examples thereof include an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, and an arylthio group which may have a substituent. When X ₁ to X ₄ have a substituent, the substituent may be the same or different, and specific examples thereof include halogen groups such as fluorine, chlorine, and bromine, characteristic groups such as amino groups, hydroxyl groups, and nitro groups, as well as alkyl groups, aryl groups, cycloalkyl groups, alkoxyl groups, aryloxy groups, alkylthio groups, and arylthio groups. Furthermore, there may be a plurality of these substituents.

The "alkyl group" of the alkyl group which may have a substituent includes a straight-chain or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a n-hexyl group, a n-octyl group, a stearyl group, or a 2-ethylhexyl group, and the "alkyl group having a substituent" includes a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, or a 2,4-dichlorobenzyl group.

The "aryl group" of the aryl group which may have a substituent includes a phenyl group, a naphthyl group, an anthryl group, etc., and the "aryl group having a substituent" includes a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-aminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-hydroxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, a 2-aminoanthraquinonyl group, etc.

Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group, etc., and examples of the "cycloalkyl group having a substituent" include a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, etc.

The "heterocyclic group" of the heterocyclic group which may have a substituent includes a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group, etc., and the "heterocyclic group having a substituent" includes a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrolyl group, etc.

The "alkoxyl group" of the alkoxyl group which may have a substituent includes linear or branched alkoxyl groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2,3-dimethyl-3-pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, and 2-ethylhexyloxy group. The "alkoxyl group having a substituent" includes trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, and benzyloxy group.

The "aryloxy group" of the aryloxy group which may have a substituent includes a phenoxy group, a naphthoxy group, an anthryloxy group, etc., and the "aryloxy group having a substituent" includes a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, a 2-methyl-4-chlorophenoxy group, etc.

The "alkylthio group" of the alkylthio group which may have a substituent includes a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, an octadecylthio group, etc., and the "alkylthio group having a substituent" includes a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group, etc.

The "arylthio group" of the arylthio group which may have a substituent includes a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, etc., and the "arylthio group having a substituent" includes a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group, etc.

Next, specific examples of Y ₁ to Y ₄ include a halogen atom, a nitro group, a phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —) which may have a substituent, and a sulfamoyl group (H ₂ NSO ₂ —). A phthalimidomethyl group having a substituent refers to a structure in which a hydrogen atom in a phthalimidomethyl group is replaced by a substituent, and a sulfamoyl group having a substituent refers to a structure in which a hydrogen atom in a sulfamoyl group is replaced by a substituent. Preferred Y is a halogen atom or a sulfamoyl group. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. In terms of brightness, chlorine and bromine are particularly preferred. The “substituents” of the phthalimidomethyl group which may have a substituent and the sulfamoyl group which may have a substituent are the same as the substituents of X ₁ to X ₄ .

Z is represented by -OP(=O) _R13R14 , where _R13 and _R14 each represent _a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and _R13 and _R14 may be bonded to each other to form a ring.

Here, examples of the alkyl group in R ₁₃ and R ₁₄ include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, n-octyl, stearyl, and 2-ethylhexyl. In the case where the alkyl group is an alkyl group having a substituent, examples of the substituent include halogen atoms such as chlorine, fluorine, and bromine, alkoxyl groups such as methoxy, aromatic groups such as phenyl and tolyl, and nitro. The number of substituents may be multiple. Examples of the alkyl group having a substituent include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, and a 2,4-dichlorobenzyl group.

The aryl group in R ₁₃ and R ₁₄ includes a phenyl group, a naphthyl group, an anthryl group, etc., and when the aryl group has a substituent, the substituent includes a halogen atom such as chlorine, fluorine, or bromine, an alkyl group, an alkoxyl group, an amino group, a nitro group, etc. In addition, the number of the substituents may be multiple. The aryl group having a substituent includes, for example, a p-tolyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-dimethylaminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-methoxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, etc.

Examples of the alkoxyl group in R ₁₃ and R ₁₄ include linear or branched alkoxyl groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, a 2,3-dimethyl-3-pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group, and examples of the substituent of the alkoxyl group having a substituent include a halogen atom such as chlorine, fluorine, or bromine, an alkoxyl group, an aryl group such as a phenyl group or a tolyl group, a nitro group, etc. In addition, there may be a plurality of substituents. Examples of alkoxyl groups having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

The aryloxy group in R ₁₃ and R ₁₄ includes a phenoxy group, a naphthaloxy group, an anthryloxy group, etc., and when the aryloxy group has a substituent, the substituent includes a halogen atom such as chlorine, fluorine, or bromine, an alkyl group, an alkoxyl group, an amino group, a nitro group, etc. In addition, the aryloxy group may have a plurality of substituents. Examples of the aryloxy group having a substituent include a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, a 2-methyl-4-chlorophenoxy group, etc.

In the phthalocyanine compound represented by general formula (1) used in the present invention, from the viewpoint of dispersibility and color characteristics, it is preferable that at least one of R ₁₃ and R ₁₄ is an aryl group which may have a substituent or an aryloxy group which may have a substituent. More preferably, R ₁₃ and R ₁₄ are both an aryl group or an aryloxy group. Further preferably, R ₁₃ and R ₁₄ are both a phenyl group or a phenoxy group.

Typical examples of the phthalocyanine compound represented by general formula (1) in the present invention include the phthalocyanine compounds (a) to (r) shown below, but the present invention is not limited to these.

It is also preferable that the dye (B) is C.I. Pigment Blue 15:3 (PB15:3). PB15:3 with an α-type crystal content of 7% or less and a free copper content of 2000 ppm or less are more preferable. By including PB15:3, blue and green light can be transmitted over a wide range of wavelengths, increasing detection sensitivity.

The content of the dye (B) in the total solid content of the coloring composition is preferably 2 to 65% by mass, and more preferably 4 to 50% by mass.

In the coloring composition, the mass ratio of the squarylium dye (A) to the dye (B) is preferably 20/80 to 80/20, and more preferably 30/70 to 70/30.

<Other dyes>
The coloring composition of the present invention may contain other dyes as necessary within a range that does not impair the spectral characteristics of the squarylium dye (A) and the dye (B). Hereinafter, the dyes may also be referred to as pigments.

<Dye derivatives>
The coloring composition of the present invention can use a dye derivative as necessary. The dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Examples of the dye derivative include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphoric acid group, as well as amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

Specifically, diketopyrrolopyrrole dye derivatives are described in JP 2001-220520 A, WO 2009/081930 B, WO 2011/052617 B, WO 2012/102399 B, and JP 2017-156397 A; phthalocyanine dye derivatives are described in JP 2007-226161 A, WO 2016/163351 B, JP 2017-165820 B, and Japanese Patent No. 5753266 A; anthraquinone dye derivatives are described in , JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325 pamphlet; quinacridone dye derivatives are disclosed in JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383; dioxazine dye derivatives are disclosed in JP-A-2011-162662; thiazine indigo dye derivatives are disclosed in JP-A-2007-314 785, triazine-based dye derivatives are disclosed in JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, and JP-A-2007-314681, benzoisoindole-based dye derivatives are disclosed in JP-A-2009-57478, quinophthalone-based dye derivatives are disclosed in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2007-314681. Examples of the naphthol-based dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439, examples of the azo-based dye derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092, examples of the acidic substituents include those described in JP-A-2004-307854, and examples of the basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. In addition, in these documents, the dye derivative may be described as a derivative, pigment derivative, dispersant, pigment dispersant, or simply a compound, but the compound having a substituent such as an acidic group, a basic group, or a neutral group in the organic dye residue is synonymous with the dye derivative.

These dye derivatives can be used alone or in combination of two or more types.

The dye derivative is preferably added in an amount of 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass, per 100 parts by mass of the pigment.

By adding a dye derivative to the pigment and carrying out pigmentation processes such as acid pasting, acid slurry, dry milling, salt milling, and solvent salt milling, the dye derivative is adsorbed onto the pigment surface, making it possible to make the primary pigment particles finer than when the dye derivative is not added.

By adding a dye derivative to the pigment and carrying out a dispersion treatment such as wet dispersion using a two-roll roller, a three-roll roller, or beads, the dye derivative is adsorbed to the pigment surface, the pigment surface becomes polar, and the adsorption of the resin-type dispersant is promoted, and the compatibility with the pigment, the dye derivative, the resin-type dispersant, the solvent, and other additives is improved, and the dispersion stability and viscosity stability over time when the colored composition or colored curable composition is formed are improved. In addition, the improved compatibility provides excellent stability over time of the coating film when the colored curable composition is applied to a glass substrate, etc., and the stability and characteristic dependency of the pattern shape and the line width sensitivity stability on the waiting time from application of the colored curable composition to exposure (PCD: Post Coating Delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay) are good. In addition, by adsorbing and covering the pigment surface with the dye derivative and the resin-type dispersant, it is possible to suppress the aggregation of the pigment and the crystal precipitation due to sublimation when the coating film is heated and baked. In addition, the variation in development time and development residue are also suppressed.

<Resin-type dispersant>
The coloring composition of the present invention can contain a resin-type dispersant. The resin-type dispersant has a pigment affinity moiety that has the property of being adsorbed to the pigment, and a relaxation moiety that has high affinity with components other than the pigment and causes steric repulsion between dispersed particles. As the resin-type dispersant, a resin having a controlled structure, such as a graft type (comb type) or block type, is preferably used.

Resin-type dispersants include, for example, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic acid esters, and modified products thereof; amides and salts thereof formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups; (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, and phosphate esters.

In addition, examples of ionic resin-type dispersants include acidic resin-type dispersants and basic resin-type dispersants.

Examples of basic resin-type dispersants include nitrogen-atom-containing graft copolymers, and nitrogen-atom-containing acrylic block copolymers and urethane-based polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc., in the side chains.
The basic resin-type dispersant can be used by neutralizing the basic group with phosphoric acid or sulfonic acid.

The coloring composition of the present invention preferably contains a basic resin-type dispersant, and more preferably a resin-type dispersant having a tertiary amino group or a quaternary ammonium salt as a dye adsorption group.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, manufactured by BYK Japan Co., Ltd. 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324 or Lactimon, Lactimon-WS or Bykumen, etc. manufactured by Lubrizol Japan Co., Ltd. SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 2 4000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400 manufactured by BASF , 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd.

Resin-type dispersants can be used alone or in combination of two or more types.

The content of the resin-type dispersant is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, based on the total amount of pigment. If an appropriate amount is included, it is easy to form a coating.

<Binder Resin>
The coloring composition of the present invention contains a binder resin. The binder resin is a resin having a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm. The transmittance is preferably 95% or more. In terms of curability, the binder resin may be, for example, a thermoplastic resin, a thermosetting resin, or an active energy ray curable resin. The active energy ray curable resin may have an active energy ray reactive functional group in the thermoplastic resin or the thermosetting resin. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. The alkali solubility is for imparting development solubility in the alkali development step during the production of the near-infrared cut filter, and an acidic group is required.

Binder resins can be used alone or in combination of two or more types.

The content of the binder resin is preferably 20 to 400 parts by weight, more preferably 50 to 250 parts by weight, per 100 parts by weight of the colorant. If an appropriate amount is included, the coating can be easily formed and good color characteristics can be easily obtained.

<Thermoplastic resin>
Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.
Examples of the alkali-soluble thermoplastic resin include resins having an acidic group such as a carboxyl group or a sulfonic group. Examples of the alkali-soluble thermoplastic resin include acrylic resins having an acidic group, α-olefin/maleic acid (anhydride) copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, and isobutylene/maleic acid (anhydride) copolymers. Among these, acrylic resins having an acidic group and styrene/styrenesulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.

<Active energy ray-curable alkali-soluble resin>
The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated double bond. The ethylenically unsaturated double bond can be introduced, for example, by the following methods (i) and (ii). The resin is three-dimensionally crosslinked by the effect of active energy rays, increasing the crosslink density and improving chemical resistance.

[Method (i)]
In the method (i), for example, an ethylenically unsaturated monomer having an epoxy group is copolymerized with another monomer to obtain a copolymer, and a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is subjected to an addition reaction with the side chain epoxy group of the copolymer.Then, a polybasic acid anhydride is reacted with the generated hydroxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

Examples of ethylenically unsaturated monomers having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acids.

Examples of unsaturated monobasic acids include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. If necessary, for example, to increase the number of carboxyl groups, it is also possible to use a tricarboxylic acid anhydride such as trimellitic anhydride, or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride to hydrolyze the remaining anhydride groups.

Examples of the other monomers include the following: (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate;
Alternatively, examples of the vinyl monomer include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide Examples of such compounds include N-substituted maleimides such as imidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

A method similar to method (i) is, for example, a method in which an ethylenically unsaturated monomer having an epoxy group is added to some of the side chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another monomer, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
The method (ii) is a method in which an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group is reacted with a side chain hydroxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer.

Examples of ethylenically unsaturated monomers having a hydroxyl group include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to a hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylates obtained by addition of poly(γ-valerolactone), poly(ε-caprolactone, and/or poly(12-hydroxystearic acid), etc. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred, and from the viewpoint of sensitivity, it is preferred to use one having 2 to 6 hydroxyl groups, with glycerol mono(meth)acrylate being even more preferred.

Examples of ethylenically unsaturated monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

Examples of other monomers that can constitute the alkali-soluble resin include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimides, alkyleneoxy group-containing monomers, phosphate group-containing ethylenically unsaturated monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like.
Examples of N-substituted maleimides include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-( 2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimide acridine and the like. Examples of the alkyleneoxy group-containing monomer include EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

The carboxyl group-containing ethylenically unsaturated monomer can be any of the monomers already described.

The phosphate ester group-containing ethylenically unsaturated monomer is, for example, a compound obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

<Alkali-soluble resin having no ethylenically unsaturated double bond>
The coloring composition of the present invention can contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of hardening of the coating.

In the present invention, the weight average molecular weight (Mw) of the alkali-soluble resin is 2,000 to 40,000, preferably 3,000 to 30,000, more preferably 4,000 to 20,000, in order to provide alkali development solubility. The value of Mw/Mn is preferably 10 or less. If the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate decreases, and the exposed pattern is less likely to remain. If it exceeds 40,000, the alkali development solubility decreases, residues are generated, and the linearity of the pattern deteriorates.
The acid value of the alkali-soluble resin in the present invention is from 50 to 200 (KOH mg/g) in order to impart solubility in alkaline development, preferably from 70 to 180, and more preferably from 90 to 170. If the acid value is less than 50, the solubility in alkaline development decreases, residues are generated, and linearity of the pattern deteriorates. If the acid value exceeds 200, adhesion to the substrate decreases, making it difficult to leave an exposed pattern.

Each raw material used in the synthesis of the binder resin can be used alone or in combination of two or more types.

<Thermosetting Compound>
In the present invention, a thermosetting compound can be further included in addition to the thermoplastic resin as a binder resin. When a color filter is produced using the coloring composition for color filters of the present invention, the thermosetting compound reacts during baking of the filter segment to increase the crosslink density of the coating film, thereby improving the heat resistance of the filter segment, suppressing pigment aggregation during baking of the filter segment, and improving the contrast ratio.

The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds, but the present invention is not limited thereto. In the coloring composition for color filters of the present invention, epoxy compounds and oxetane compounds are preferably used.

<Polymerizable Compound>
The coloring composition of the present invention can be a photosensitive coloring composition by including a polymerizable compound and a photopolymerization initiator. The polymerizable compound includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to produce a transparent resin. The photosensitive coloring composition may also be simply called a coloring composition.

Examples of the polymerizable compound include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, Examples of the acrylic acid esters and methacrylic acid esters include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methylolated melamine (meth)acrylic acid ester, epoxy (meth)acrylate, and urethane acrylate, as well as (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile.

(Polymerizable compound having an acid group)
The polymerizable compound may contain a photopolymerizable monomer having an acid group, such as a sulfonic acid group, a carboxyl group, or a phosphoric acid group.

Examples of photopolymerizable monomers having an acid group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates, etc. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and free carboxyl group-containing oligoesters of tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid with monohydroxy monoacrylates or monohydroxy monomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

(Polymerizable compound having a urethane bond)
The polymerizable compound may contain a monomer having an ethylenically unsaturated bond and a urethane bond. Examples of the monomer include a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylate.

Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, etc.

The polymerizable compounds can be used alone or in combination of two or more types.

The amount of the polymerizable compound is preferably 1 to 50 mass % and more preferably 2 to 40 mass parts based on 100 mass % of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is added, the curing property and developability are further improved.

<Photopolymerization initiator>
Examples of the photopolymerization initiator include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; benzophenone compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine. triazine-based compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, or 1-(O-acetyloxime) or other oxime ester-based compounds; phosphine-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, or ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanocene-based compounds. Among these, oxime ester-based compounds are preferred.

Photopolymerization initiators can be used alone or in combination of two or more types.

(Oxime ester compounds)
In the oxime ester compound, the N-O bond of the oxime is cleaved by absorbing ultraviolet light, generating an iminyl radical and an alkyloxy radical. These radicals further decompose to generate highly active radicals, so that a pattern can be formed with a small amount of exposure. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may decrease, and the degree of curing of the coating film may decrease, but the oxime ester compound has a high quantum efficiency and is therefore preferably used.

Examples of oxime ester compounds include oxime ester photopolymerization initiators described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc.

The content of the photopolymerization initiator is preferably 2 to 50 parts by weight, and more preferably 2 to 30 parts by weight, per 100 parts by weight of the colorant. When an appropriate amount is added, the photocuring property and developability are further improved.

<Sensitizer>
Furthermore, the photosensitive coloring composition of the present invention may contain a sensitizer.
Examples of sensitizers include chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. , phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

Among the above sensitizers, particularly suitable sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole are used.

More specifically, examples of sensitizers include those described in "Dye Handbook" edited by Okawara Makoto et al. (Kodansha, 1986), "Chemistry of Functional Dyes" edited by Okawara Makoto et al. (CMC, 1981), "Tokushu No Futon Zairyo" edited by Ikemori Chuzaburo et al., and "Tokushu No Futon Zairyo" (CMC, 1986), but are not limited to these. In addition, sensitizers that absorb light from the ultraviolet to near infrared regions can also be included.

Sensitizers can be used alone or in combination of two or more types.

The content of the sensitizer is preferably 3 to 60 parts by weight, more preferably 5 to 50 parts by weight, per 100 parts by weight of the photopolymerization initiator. When an appropriate amount is included, the curing property and developability are further improved.

<Thiol-based chain transfer agent>
The photosensitive coloring composition of the present invention preferably contains a thiol-based chain transfer agent as a chain transfer agent. By using thiol together with a photopolymerization initiator, the thiol acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates a thiyl radical that is not easily inhibited by oxygen, so that the obtained coloring composition has high sensitivity.

In addition, polyfunctional aliphatic thiols having two or more thiol groups bonded to aliphatic groups such as methylene or ethylene groups are preferred. Polyfunctional aliphatic thiols having four or more thiol groups are more preferred. By increasing the number of functional groups, the polymerization initiation function is improved, and curing can be achieved from the surface of the pattern to near the substrate.

Examples of polyfunctional thiols include hexanedithiol and decanedithiol. , 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. are included, and preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate.

Thiol-based chain transfer agents can be used alone or in combination of two or more types.

The content of the thiol chain transfer agent is preferably 0.1 to 10% by mass, and more preferably 0.1 to 3% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is included, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the coating surface.

<Polymerization inhibitor>
The photosensitive coloring composition may contain a polymerization inhibitor, which can suppress photosensitivity due to diffracted light from a mask during exposure in a photolithography method, making it easier to obtain a pattern of a desired shape.

Examples of polymerization inhibitors include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, and 3,5-di-tert-butylcatechol; 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, and 2-n-butylcatechol. Examples of such compounds include alkyl resorcinol compounds such as ethylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucinol.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. Within this range, the effect of the polymerization inhibitor becomes greater, and the linearity of the taper, wrinkles in the coating film, pattern resolution, etc. become better.

<Ultraviolet absorbing agent>
The photosensitive coloring composition of the present invention may contain an ultraviolet absorbing agent. The ultraviolet absorbing agent in the present invention is an organic compound having an ultraviolet absorbing function, and examples of the ultraviolet absorbing agent include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds.

The content of the UV absorber is preferably 5 to 70% by mass, with the total of the photopolymerization initiator and the UV absorber being 100% by mass. If an appropriate amount is included, the resolution after development will be further improved.

The total content of the photopolymerization initiator and the UV absorber is preferably 1 to 20% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the adhesion between the substrate and the coating is further improved, and good resolution can be obtained.

Benzotriazole compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α, α-Dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 branched and linear alkyl ester mixture, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction products, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t- Butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate. Other oligomer and polymer type compounds having a benzotriazole structure can also be used.

Triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of such compounds include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Other oligomer and polymer type compounds having a triazine structure can also be used.

Benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Other oligomer and polymer compounds having a benzophenone structure can also be used.

Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Other oligomer and polymer type compounds having a salicylic acid ester structure can also be used.

<Antioxidants>
The photosensitive coloring composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator or thermosetting compound contained in the photosensitive coloring composition from being oxidized and yellowed by the thermal process during thermal curing or ITO annealing, and can improve the transmittance of the coating film. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film crosslinking component is reduced, so that a highly sensitive crosslinking component is used or the amount of the photopolymerization initiator is increased, resulting in a phenomenon in which yellowing during the thermal process becomes stronger. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

Examples of antioxidants include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present invention, the antioxidant is preferably a compound that does not contain a halogen atom.

Among these, from the viewpoint of achieving both transmittance and sensitivity of the coating film, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

Antioxidants can be used alone or in combination of two or more types.

In addition, when the content of the antioxidant is 0.5 to 5.0% by mass based on 100% by mass of the solid content of the coloring composition, the transmittance, spectral characteristics, and sensitivity are good, which is more preferable.

<Leveling Agent>
In order to improve the coating property of the composition on a transparent substrate and the drying property of the colored coating film, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used.

When the coloring composition of the present invention contains a surfactant, the amount of the surfactant added is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition of the present invention. When the amount is within this range, the balance between the coatability of the coloring composition, the pattern adhesion, and the transmittance is good.
The photosensitive coloring composition of the present invention may contain only one type of surfactant, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

<Storage stabilizer>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, organic phosphines such as tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer may be used in an amount of 0.1 to 10% by mass based on the total amount of the colorant (100% by mass).

<Adhesion improver>
The coloring composition of the present invention may contain an adhesion improver such as a silane coupling agent in order to improve adhesion to a substrate. By improving adhesion with the adhesion improver, the reproducibility of fine lines is improved and the resolution is improved.

Adhesion improvers include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3- Examples of the silane coupling agent include aminosilanes such as aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanates such as 3-isocyanatepropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the colorant in the coloring composition. This range is more effective and provides a good balance of adhesion, resolution, and sensitivity, making it more preferable.

<Method of producing colored composition>
The coloring composition included in the present invention can be produced by finely dispersing a colorant in a colorant carrier such as a dispersant or binder resin and/or a solvent, preferably together with a dispersion aid (dye derivative or surfactant), using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more types of colorants may be dispersed simultaneously in a colorant carrier, or may be mixed with those dispersed separately in a colorant carrier. When the solubility of a colorant such as a dye is high, specifically, when the solubility is high in the solvent used and the colorant is dissolved by stirring and no foreign matter is confirmed, it is not necessary to produce the colorant by fine dispersion as described above.

When used as a photosensitive coloring composition (resist material) for color filters, it can be prepared as a solvent-developable or alkali-developable coloring composition. The solvent-developable or alkali-developable coloring composition can be prepared by mixing the colorant dispersion, the photopolymerizable monomer and/or the photopolymerization initiator, and, if necessary, a solvent, other dispersing aids, and additives. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Solvent>
The colored composition of the present invention contains a solvent in order to easily form a colored film by coating the composition on a substrate such as glass so that the dry film thickness is 0.2 to 5 μm. The solvent is selected in consideration of the good coatability of the colored composition, the solubility of each component of the colored composition, and safety.

Solvents that are commonly used in the field can be used, and they can be used alone or in combination as appropriate to suit the application conditions (speed, drying conditions, etc.) taking into account performance such as boiling point, SP value, evaporation rate, and viscosity.

Solvents that can be used include, for example, ester solvents (solvents that contain -COO- in the molecule but do not contain -O-), ether solvents (solvents that contain -O- in the molecule but do not contain -COO-), ether ester solvents (solvents that contain -COO- and -O- in the molecule), ketone solvents (solvents that contain -CO- in the molecule but do not contain -COO-), alcohol solvents (solvents that contain OH in the molecule but do not contain -O-, -CO- or -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

Among the above solvents, from the viewpoint of coatability and drying property, it is preferable to use an organic solvent having a boiling point of 120°C or more and 180°C or less at 1 atm. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred.

<Removal of coarse particles>
The coloring composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation at a gravitational acceleration of 3,000 to 25,000 G, filtration with a sintered filter or membrane filter, etc. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

<Method of manufacturing near-infrared cut filter>
The near-infrared cut filter of the present invention can be manufactured by a printing method or a photolithography method. The formation of filter segments by a printing method can be patterned by printing and drying a coloring composition, so that the method for manufacturing the filter is low cost and has excellent mass productivity. Furthermore, the development of printing technology allows printing of fine patterns with high dimensional accuracy and smoothness. In order to perform printing, it is preferable to use a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, control of the fluidity of the ink on the printing machine is also important, and the ink viscosity can be adjusted by a dispersant or an extender pigment.

When forming filter segments by photolithography, a coloring composition prepared as a solvent-developable or alkali-developable resist material is applied to a substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern that is in contact with or not in contact with the film. Thereafter, the uncured parts are removed by immersing the film in a solvent or alkali developer or spraying the developer with a spray or the like to form a desired pattern, and the same operation can be repeated for other colors to produce filters. Furthermore, heating can be performed as necessary to promote polymerization of the resist material. According to the photolithography method, a filter with higher precision can be produced than by the above printing method.

The substrate is not particularly limited, but a transparent substrate in the form of a sheet, film, or plate can be used. The color can be colorless or colored, and is not particularly limited. The material of the transparent substrate is a highly transparent material, for example, polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), triacetyl cellulose (TAC), acrylic resin such as methyl methacrylate copolymer, styrene resin, polysulfone resin, polyethersulfone resin, polycarbonate resin, vinyl chloride resin, polymethacrylimide resin, glass plate, etc.

For development, an aqueous solution of sodium carbonate, sodium hydroxide, etc. is used as an alkaline developer, and organic alkalis such as dimethylbenzylamine, triethanolamine, etc. can also be used. An antifoaming agent or surfactant can also be added to the developer. In order to increase the sensitivity to ultraviolet light exposure, after the colored resist material is applied and dried, a water-soluble or alkaline water-soluble resin, such as polyvinyl alcohol or water-soluble acrylic resin, can be applied and dried to form a film that prevents polymerization inhibition by oxygen, and then ultraviolet light exposure can be performed.

In addition to the above method, the near-infrared cut filter of the present invention can also be manufactured by electrodeposition, transfer printing, inkjet printing, etc.

<Applications>
The colored composition of the present invention can be used, for example, in sensors for biometric authentication (fingerprint authentication or vein authentication), or in touch sensors or touch panels incorporating such sensors.
For example, biometric authentication functions such as fingerprint authentication and finger vein authentication are installed for security purposes in smartphones, tablet PCs, bank ATMs, multimedia terminals, etc. Fingerprint authentication technology used in smartphones and tablet PCs in particular has been developing rapidly, and as the authentication range has expanded to the screen size (full screen), fingerprint authentication sensors built into displays such as organic electroluminescence displays and liquid crystal displays have been developed.
However, most of the fingerprint sensors with built-in displays use an optical system in which various light sources installed in the display are irradiated onto the fingerprint and the reflected light is sensed, so when external unauthorized light (strong light having a wide range of wavelengths such as sunlight or LED lighting) is incident on the sensor, it causes noise during imaging, and there are some concerns about the accuracy when used outdoors. The colored composition of the present invention is effective in solving these problems by absorbing and preventing unauthorized external light from being incident on the sensor.
In addition, since the colored composition of the present invention has excellent heat resistance, it can be preferably used in the process of producing a sensor, or a touch sensor or touch panel incorporating the sensor.
Furthermore, the external light that becomes noise in biometric authentication applications is light of 650 nm to 1000 nm that passes through the living body, and since light of 650 nm to 800 nm in particular is abundant in living spaces, cutting out light in this wavelength range further improves the accuracy of biometric authentication.

The present invention will be described below based on examples, but the present invention is not limited thereto. In the examples and comparative examples, "parts" means "parts by weight." Also, "PGMAC" means propylene glycol monomethyl ether acetate.

(Method of Identifying Squarylium Dye (A))
The near infrared absorbing pigment used in the present invention was identified by MALDI TOF-MS spectrometry. The MALDI TOF-MS spectrometry was performed using a MALDI mass spectrometer AutoflexIII manufactured by Bruker Daltonics, and the compound obtained was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

(Acid Value of Resin-Type Dispersant and Binder Resin)
The acid values of the resin-type dispersant and the binder resin were determined by potentiometric titration using a 0.1 N potassium hydroxide-ethanol solution. The acid values of the resin and the resin-type dispersant indicate the acid value of the non-volatile content.

(Weight average molecular weight (Mw) of resin type dispersant and binder resin)
The weight average molecular weight (Mw) of the resin-type dispersant and the binder resin is a polystyrene-equivalent weight average molecular weight (Mw) measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, using THF as a developing solvent.

(Amine value of resin type dispersant)
The amine value of the resin-type dispersant was determined by potentiometric titration using a 0.1 N aqueous hydrochloric acid solution, and then converted into the equivalent amount of potassium hydroxide. The amine value of the resin-type dispersant indicates the amine value of the non-volatile content.

(Quaternary Ammonium Salt Value of Resin-Type Dispersant)
The quaternary ammonium salt value of the resin-type dispersant was determined by titration with 0.1 N silver nitrate aqueous solution using 5% potassium chromate aqueous solution as an indicator, and then converted into the potassium hydroxide equivalent. The quaternary ammonium salt value of the resin-type dispersant below indicates the quaternary ammonium salt value of the non-volatile content.

<Production of fine squarylium dye (P)>
(Synthesis of squarylium dye (A2-1))
400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 25.1 parts of cyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 3 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 8 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation.
After the reaction was completed, the solvent was distilled, and 200 parts of hexane was added to the resulting reaction mixture while stirring. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain 61.9 parts of squarylium dye (A2-1) (yield: 92%). As a result of mass analysis by TOF-MS, the squarylium dye (A2-1) was identified.

(Synthesis of squarylium dye (A2-2))
The same procedure as in the synthesis of the squarylium dye (A2-1) was carried out, except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the synthesis of the squarylium dye (A2-1), to obtain 72.6 parts of a squarylium dye (A2-2) (yield: 98%). As a result of mass analysis by TOF-MS, the squarylium dye was identified as the squarylium dye (A2-2).

(Synthesis of squarylium dye (A2-3))
The same procedure as in the synthesis of squarylium dye (A2-1) was carried out, except that 28.6 parts of 4-methylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the synthesis of squarylium dye (A2-1), to obtain 67.2 parts of squarylium dye (A2-3) (yield: 95%). As a result of mass analysis by TOF-MS, the squarylium dye was identified as squarylium dye (A2-3).

(Synthesis of squarylium dye (A3-1))
400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 46.0 parts of 9-fluorenone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 3 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After the reaction was completed, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 8 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After the reaction was completed, the solvent was distilled, and 200 parts of hexane was added while stirring the resulting reaction mixture. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol and acetone, and dried under reduced pressure to obtain 84.6 parts (yield: 97%) of a squarylium dye (A3-1). As a result of mass spectrometry and elemental analysis by TOF-MS, the squarylium dye (A3-1) was identified.

(Synthesis of squarylium dye (A3-2))
The same procedure as in the synthesis of squarylium dye (A3-1) was carried out, except that 80.7 parts of 2,7-bis(trifluoromethyl)-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the synthesis of squarylium dye (A3-1), to obtain 109.8 parts of squarylium dye (A3-2) (yield: 91%). As a result of mass spectrometry and elemental analysis by TOF-MS, the squarylium dye was identified as squarylium dye (A3-2).

(Synthesis of squarylium dye (A3-3))
The same procedure as in the synthesis of squarylium dye (A3-1) was carried out, except that 50.1 parts of 2-hydroxy-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the synthesis of squarylium dye (A3-1), to obtain 83.9 parts of squarylium dye (A3-3) (yield: 92%). As a result of mass spectrometry and elemental analysis by TOF-MS, the squarylium dye was identified as squarylium dye (A3-3).

(Solvent treatment and pulverization of squarylium dye (A))
[Solvent treatment process]
50 parts of the squarylium dye (A2-1) was mixed with 250 parts of N-methylpyrrolidone and stirred for 24 hours at 23° C. Then, the mixture was filtered, washed with 150 parts of methanol, and then taken out and dried at 80° C. for one day to obtain 25 parts of powder.
[Miniaturization process]
10 parts of the obtained powder, 100 parts of sodium chloride, and 12.5 parts of ethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 12 hours at 60° C. Next, the kneaded mixture was poured into warm water and stirred for 1 hour while heating to about 80° C. to form a slurry, which was then filtered and washed with water to remove the salt and diethylene glycol, and then dried overnight at 80° C. and pulverized to obtain 9.4 parts of a finely divided squarylium dye (P2-1).
[Average particle size]
The average primary particle size of the pigment was measured by a method of directly measuring the size of the primary particles from an electron microscope photograph. Specifically, the minor axis diameter and major axis diameter of each primary particle of the pigment were measured, and the average was taken as the particle size of the pigment particle. Next, for 100 or more pigment particles, the volume (weight) of each particle was calculated by approximating it to a cube of the calculated particle size, and the volume average particle size was taken as the average primary particle size. Note that a transmission electron microscope (TEM) was used.
As a result of measurement by this method, the average primary particle diameter was found to be 50 nm.
[Component ratio]
5.0 mg of squarylium dye (P2-1) was placed in a 100 ml measuring flask, HPLC grade THF was added, and the dye was dissolved by irradiating with ultrasound for 30 minutes to prepare a 100 ml THF solution. Using this solution, HPLC measurement of dye compound B was carried out using the above-mentioned device and conditions.
The HPLC measurement was performed by reversed-phase liquid chromatography using a mixed solution of acetonitrile and water in a volume ratio of 8:2 as a mobile phase.
The results showed multiple peaks.
Specifically, it is composed of a peak (Peak 1) that appears at a retention time of 12±1 minutes, a peak (Peak 2) that appears at a retention time of 42±1 minutes, a peak (Peak 3) that appears at a retention time of 46±2 minutes, a peak (Peak 4) that appears at a retention time of 50±2 minutes, and a peak (Peak 5) that appears at a retention time of 57±2 minutes.
The area of peak 5 was 70% of the total area of peaks 1 to 5.

Squaryllium dyes (A2-2) and (A2-3) were treated with a solvent and micronized in the same manner as squarylium dye (A2-1), to give micronized squarylium dyes (P2-2) and (P2-3). Squaryllium dyes (A3-1) to (A3-3) were not treated with a solvent and were only micronized to give micronized squarylium dyes (P3-1) to (P3-3). The micronized squarylium dyes (P) are shown in Table 1.

<Other squarylium dyes (X)>
G pigment SQ-R1 used in the examples of patent document WO2020/013089 was used as another squarylium dye (X) and was subjected to micronization in the same manner as for the squarylium dye (A2-1). The micronized squarylium dye (X) is referred to as micronized squarylium dye (PX).

The structures of the squarylium dye (A) produced as described above and other squarylium dyes (X) are as follows:

<Production of dye (B)>
(Production of Dye (B-1))
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were added to 1250 parts of n-amyl alcohol and stirred. 266 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) were added to the mixture, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water under stirring to obtain a blue slurry. The slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Furthermore, 100 parts of chloroaluminum phthalocyanine were slowly added to 1200 parts of concentrated sulfuric acid in a reaction vessel at room temperature. The mixture was stirred at 40°C for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3°C. The blue precipitate was filtered, washed with water, and dried to obtain 102 parts of an aluminum phthalocyanine pigment represented by the following formula (6).

Equation (6)

In a reaction vessel, 100 parts of the aluminum phthalocyanine pigment represented by the above formula (6) and 43.2 parts of diphenylphosphinic acid were added to 1,000 parts of methanol, heated to 40° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 112 parts of dye (B-1).
Next, 100 parts of the obtained dye (B-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 70° C. This kneaded product was added to 3000 parts of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. for one day to obtain a finely divided dye (B-1). The average primary particle size was 29.5 nm.

(Production of Dye (B-2))
In a reaction vessel, 100 parts of the aluminum phthalocyanine pigment represented by the above formula (6) and 49.5 parts of diphenyl phosphate were added to 1,000 parts of methanol, heated to 40° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of dye (B-2).
The obtained dye (B-2) was subjected to the same salt milling treatment as for the dye (B-1) to obtain a finely divided dye (B-2). The average primary particle size was 31.2 nm.

(Production of Dye (B-3))
Into a three-neck flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (7), and 104.4 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred, and reacted at 20°C for 4 hours. Thereafter, the above reaction mixture was poured into 5,000 parts of ice water at 3°C, and the precipitated solid was collected by filtration and washed with water. Into a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the collected residue were added, and stirred at 80°C for 1 hour. Thereafter, this mixture was filtered, washed with water, and dried, to obtain a pigment in which an average of 8.0 bromine atoms were substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of the pigment having an average of 8.0 bromine atoms substituted on the phthalocyanine ring, and 18.2 parts of diphenyl phosphate were added to a three-neck flask, heated to 90° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain dye (B-3). The average primary particle size was 27 nm.

Equation (7)

(Production of Dye (B-4))
A pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring was obtained by carrying out the same operation as in the production of dye (B-3), except that 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) used in the production of dye (B-3) was changed from 104.4 parts to 129.3 parts, and the reaction time was changed from 4 hours to 6 hours.
Next, 500 parts of N-methylpyrrolidone, 50 parts of the pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added to a three-neck flask, heated to 90° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain dye (B-4). The average primary particle size was 27 nm.

(Production of Dye (B-5))
In a three-neck flask, 250 parts of aluminum chloride, 60 parts of sodium chloride, and 2.25 parts of iodine were added and stirred at 150 ° C for 30 minutes. 50 parts of aluminum phthalocyanine pigment represented by the above formula (6) was added thereto, and stirred at 155 ° C for 30 minutes to dissolve. 58.5 parts of trichloroisocyanuric acid was further added and stirred at 190 ° C for 5 hours. Then, the reaction mixture was poured into 5,000 parts of ice water at 3 ° C, and the precipitated solid was filtered and washed with water. 500 parts of 2.5% sodium hydroxide aqueous solution and the filtered residue were added to a beaker, and stirred at 80 ° C for 1 hour. Then, the mixture was filtered, washed with water, and dried to obtain a pigment in which an average of 8.1 chlorine atoms were substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of the pigment having an average of 8.1 chlorine atoms substituted on the phthalocyanine ring, and 22.6 parts of diphenyl phosphate were added to a three-neck flask, heated to 90° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain dye (B-5). The average primary particle size was 29 nm.

(Production of Dye (B-6))
100 parts of C.I. Pigment Blue 15:3 (PB15:3) ("Lionol Blue FG-7351" manufactured by Toyo Color Co., Ltd.), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80° C. This mixture was poured into 2000 parts of hot water, heated to 80° C. and stirred for 1 hour to form a slurry, which was filtered and washed repeatedly to remove salt and the solvent, and then dried at 80° C. for 24 hours to obtain 95 parts of dye (B-6).

The structure of the dye (B) produced as described above is as follows:

<Other dyes>
As other dyes, the following dyes were obtained by subjecting them to the same salt milling treatment method as for dye (B-1) to fine milling.
PG58: C.I. Pigment Green 58 (DIC Corporation "FASTGEN GREEN A110")
PG36: C.I. Pigment Green 36 ("Leonol Green 6YK" manufactured by Toyo Color Co., Ltd.)
PB15:6: C.I. Pigment Blue 15:6 ("Leonor Blue ES" manufactured by Toyo Color Co., Ltd.)

<Dye derivative 1>
A compound represented by the following formula (8) was used as dye derivative 1.

Equation (8)
(In formula (8), CuPc is a copper phthalocyanine structure residue.)

<Preparation of Dispersant Solution>
(Preparation of Basic Resin-Type Dispersant 1 Solution)

In a reaction vessel equipped with a stirrer and a thermometer, 41 parts of N,N-dimethylpropanediamine and 120 parts of chloroform were charged and stirred at room temperature, and 50 parts of methacrylic acid chloride were added dropwise over 1 hour. After stirring at room temperature for 3 hours, the completion of the reaction was confirmed by ¹ H-NMR, and then the reaction solution was washed with 300 parts of ion-exchanged water and 200 parts of saturated saline solution in that order, and then 20 g of magnesium sulfate was added to the organic layer, stirred, and then filtered. The solvent in the obtained solution was distilled off with a rotary evaporator, and 58 parts of compound [b] represented by the following formula (9) was obtained as a pale yellow transparent liquid (yield 85%). The obtained compound was identified by ¹ H-NMR.

Equation (9)

A reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer was charged with 15.7 parts of methyl methacrylate, 47.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the non-volatile content.
Next, 25 parts of PGMAc and 30.3 parts of the compound [b] as the second block monomer were added to the reaction tank, and the reaction was continued by stirring while maintaining a nitrogen atmosphere at 110° C. Two hours after the addition of the compound [b] represented by the formula (9) above, a sample of the polymerization solution was taken and the solid content was measured, and it was confirmed that the polymerization conversion rate of the second block was 98% or more, calculated from the non-volatile content.
Further, 6.8 parts of benzyl chloride was added to the reaction vessel, and the mixture was stirred for 3 hours while maintaining the temperature at 110° C. under a nitrogen atmosphere, and then cooled.
PGMAc was added to the block copolymer solution synthesized above so that the nonvolatile content was 40% by weight. In this way, a basic resin-type dispersant 1 solution was obtained, which had an amine value per solid content of 70 mg KOH/g, a quaternary ammonium salt value of 30 mg KOH/g, a weight average molecular weight (Mw) of 9,800, and a nonvolatile content of 40% by weight.

(Preparation of other dispersant 2 solutions)
A reaction vessel equipped with a gas inlet tube, a temperature controller, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 90 parts of methyl methacrylate, 50 parts of ethyl acrylate, 50 parts of tert-butyl acrylate, and 50 parts of propylene glycol monomethyl ether acetate, and the atmosphere was replaced with nitrogen gas. The inside of the reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile added to 90 parts of propylene glycol monomethyl ether acetate was added and reacted for 7 hours. It was confirmed that 95% had reacted by solid content measurement.
19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted for 7 hours at 100° C. The reaction was terminated when it was confirmed by measuring the acid value that 98% or more of the acid anhydride had been half-esterified, and the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content was 40% by measuring the solid content, thereby obtaining a solution of other dispersant 2 having an acid value of 70 mgKOH/g and a mass average molecular weight of 8,500.

<Preparation of binder resin solution>
(Preparation of binder resin 1 solution)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer. 70.0 parts of cyclohexanone was charged in the reaction vessel, which was then heated to 80 ° C. and substituted with nitrogen in the reaction vessel. A mixture of 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl ether acetate was added to the previously synthesized resin solution so that the non-volatile content was 20 mass % to prepare binder resin 1 solution.

(Preparation of binder resin 2 solution)
A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 370 parts of cyclohexanone, heated to 80°C, and the atmosphere in the flask was replaced with nitrogen. A mixture of 18 parts of dicyclopentanyl methacrylate, 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours from the dropping tube. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was continued at 100°C for 1 hour. Next, the inside of the vessel was replaced with air, and 9.3 parts of acrylic acid (100% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the vessel, and the reaction was continued for 6 hours at 120° C., and the reaction was terminated when the solid acid value reached 0.5, to obtain an acrylic resin solution. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added, and the reaction was continued for 3.5 hours at 120° C., to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried at 180° C. for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass to prepare a binder resin 2 solution. The weight average molecular weight (Mw) was 19,000.

<Production of coloring composition (S)>

(Production of Colored Composition (S-1))
The mixture having the following composition was stirred and mixed uniformly, dispersed in an Eiger mill using zirconia beads having a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a colored composition (S-1).
Finely divided squarylium dye (P2-1): 10.0 parts Basic resin type dispersant 1 solution: 7.5 parts Basic resin type dispersant 1 solution: 35.0 parts PGMAC: 47.5 parts

(Production of Colored Compositions (S-2) to (S-7))
Hereinafter, colored compositions (S-2) to (S-7) were prepared in the same manner as in the colored composition (S-1), except that the fine squarylium dye (P2-1) was changed to the fine squarylium dye shown in Table 1.

<Measurement of maximum absorption wavelength of colored composition (S)>
The obtained colored composition (S): 60.0 parts, binder resin 1 solution: 15.0 parts, PGMAC: 25.0 parts were uniformly mixed and stirred, then spin-coated on a 1.1 mm thick glass substrate using a spin coater to a film thickness of 1.0 μm, dried at 60 ° C. for 5 minutes, and heated at 230 ° C. for 20 minutes to prepare a substrate. The spectrum of the obtained substrate was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) to measure the absorption spectrum in the wavelength range of 400 to 1000 nm. The results of the maximum absorption wavelength are shown in Table 1.

<Production of coloring composition (C)>

(Production of Colored Composition (C-1))
The mixture having the following composition was stirred and mixed uniformly, dispersed in an Eiger mill using zirconia beads having a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a colored composition (C-1).
Dye (B-1): 12.0 parts Basic resin type dispersant 1 solution: 9.0 parts Binder resin 1 solution: 22.0 parts PGMAC: 57.0 parts

(Production of Colored Compositions (C-2) to (C-9))
Thereafter, colored compositions (C-2) to (C-9) were prepared in the same manner as for the colored composition (C-1), except that the colorant (B-1) was changed to the colorant shown in Table 2.

<Evaluation of Spectral Characteristics of Colored Composition (C)>
The obtained colored composition (C): 50.0 parts, binder resin 1 solution: 25.0 parts, and PGMAC: 25.0 parts were uniformly mixed and stirred, and then spin-coated on a 1.1 mm thick glass substrate using a spin coater so that the minimum transmittance in the range of 400 to 1000 nm was 1%, dried at 60° C. for 5 minutes, and then heated at 230° C. for 20 minutes to prepare a substrate. The spectrum of the obtained substrate was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) to measure the absorption spectrum in the wavelength range of 400 to 1000 nm.
The transmittance at each wavelength was calculated from the measured absorption spectrum, and it was confirmed whether the spectral characteristics satisfied the following conditions (1) and (2). The results are shown in Table 3.

(1) When a coating film is formed so that the transmittance at 680 nm is 1%, the minimum transmittance (T1) at 400 to 450 nm is 20% or more. (2) When a coating film is formed so that the transmittance at 680 nm is 1%, the transmittance (T2) at 530 nm is 50% or more.

The dyes (B-1) to (B-6) used in the coloring compositions (C-1) to (C-6) have spectral characteristics that satisfy both of the above conditions (1) and (2). On the other hand, the PG58 and PG36 used in the coloring compositions (C-7) and (C-8) do not satisfy the above condition (1), and the PB15:6 used in the coloring composition (C-9) has spectral characteristics that do not satisfy the above condition (2).

<Production of Colored Composition (D)>
(Examples 1 to 38: Colored compositions (D-1) to (D-38),
Comparative Examples 1 to 5: Production of Colored Compositions (D-39) to (D-43)
Colored compositions (D-1) to (D-43) were prepared in the same manner as for colored composition (C-1), except that the pigment and dispersant were changed to the compositions and amounts shown in Tables 4-1 to 4-3.

Coloring composition (C-2) was used as Comparative Example 6.

<Evaluation of Spectral Characteristics of Colored Composition>
The obtained colored composition (D) or colored composition (C-2): 31.0 parts, binder resin 1 solution: 44.0 parts, PGMAC: 25.0 parts were uniformly stirred and mixed, and then spin-coated on a 1.1 mm thick glass substrate using a spin coater so that the coating film thickness was 1.5 μm, dried at 60 ° C. for 5 minutes, and then heated at 230 ° C. for 20 minutes to prepare a substrate. The spectrum of the obtained substrate was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) to measure the absorption spectrum in the wavelength range of 400 to 1000 nm.
The average transmittance (T) of each region was calculated from the measured absorption spectrum and evaluated according to the following criteria. The evaluation results are shown in Tables 4-1 to 4-3.

Spectral characteristic 1: 450 nm to 550 nm
○: 75%≦(T)
△: 65%≦(T)＜75%
×: (T) < 65%

Spectral characteristic 2: 600 nm to 750 nm
〇: (T) ≦ 10%
△: 10% < (T) ≦ 15%
×: 15% < (T)

Spectral characteristic 3: 750 nm to 850 nm
〇: (T) ≦ 10%
△: 10% < (T) ≦ 15%
×: 15% < (T)

Spectral characteristic 4: 550 nm to 600 nm
○: (T)≦20%
△: 20% < (T) ≦ 65%
×: 65% < (T)

<Evaluation of Filterability of Colored Composition>
10 g of the obtained colored composition (D) or colored composition (C-2) was passed through a filter (φ0.2 μm, manufactured by ADVANTEC Co., Ltd., model number: 39115221) under nitrogen pressure (0.3 MPa), and the amount obtained through the filter was measured and evaluated according to the following criteria.
The evaluation results are shown in Tables 4-1 to 4-3.
◯: 5.0g ≦ filtration amount △: 3.0g ≦ filtration amount < 5.0g
×: Filtration amount ≦ 3.0 g

By including squarylium dye (A) having a maximum absorption wavelength between 700 and 900 nm in the range of 400 to 1000 nm, and dye (B) having spectral characteristics that satisfy the above conditions (1) and (2), it was possible to obtain a coloring composition that has high transmittance of blue and green light used in detection such as fingerprint authentication (spectral characteristic 1), and cuts out red light and near-infrared light that become noise (spectral characteristics 2 and 3). It was also confirmed that by including dye (B-6), it is possible to cut out red light that becomes noise from the shorter wavelength side (spectral characteristic 4). Furthermore, it was confirmed that by including squarylium dye (A) and dye (B), filterability is improved.

<Production of photosensitive coloring composition (R)>
(Example 39: Production of photosensitive coloring composition (R-1))
The mixture having the following composition was stirred and mixed uniformly, and then filtered through a 0.5 μm filter to prepare a photosensitive coloring composition (R-1).
Colored composition (D-1): 31.3 parts Binder resin 2 solution: 8.5 parts Thermosetting compound (E): 0.8 parts Polymerizable compound (F): 4.5 parts Photopolymerization initiator (G): 0.7 parts Sensitizer (H): 0.1 parts Thiol chain transfer agent (I): 0.2 parts Polymerization inhibitor (J): 0.2 parts Ultraviolet absorber (K): 0.2 parts Antioxidant (L): 0.2 parts Leveling agent (M): 5.0 parts Storage stabilizer (N): 0.2 parts Adhesion improver (O): 0.2 parts Solvent (P): 48.4 parts

(Examples 40 to 42: Photosensitive coloring compositions (R-2) to (R-4),
Comparative Examples 7 to 10: Production of Photosensitive Coloring Compositions (R-5) to (R-8)
Hereinafter, photosensitive coloring compositions (R-2) to (R-8) were prepared in the same manner as the photosensitive coloring composition (R-1), except that the coloring composition (D-1) was changed to the coloring composition shown in Table 5.

Details of the materials used in producing the photosensitive coloring composition (R) are as follows:

[Thermosetting compound (E)]
Epoxy compound (E-1)
(E-1-1) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol
[EHPE-3150 (manufactured by Daicel)],
(E-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase ChemteX Corporation)],
(E-1-3) Triglycidyl isocyanurate (E-1-1) to (E-1-3) were mixed in equal amounts to obtain an epoxy compound (E-1).
Oxetane compound (E-2):
3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane
[Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

[Polymerizable compound (F)]
(F-1) Trimethylolpropane triacrylate
[Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(F-2) Dipentaerythritol penta- and hexaacrylate (E-2)
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
(F-3) Polybasic acidic acrylic oligomer
[Aronix M520 (manufactured by Toagosei Co., Ltd.)]
(F-4) Caprolactone-modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (manufactured by Nippon Kayaku)]

(F-5) Multifunctional urethane acrylate as described below: Pentaerythritol triacrylate (432 g) and 84 g of hexamethylene diisocyanate were charged into a 1-liter five-necked reaction vessel and reacted at 60°C for 8 hours to obtain a product containing a multifunctional urethane acrylate (F-5) having a (meth)acryloyl group. The proportion of the multifunctional urethane acrylate (F-5) in the product was 70 mass%, with the remainder being other photopolymerizable monomers. It was confirmed by IR analysis that no isocyanate groups were present in the reaction product.

(F-6) Difunctional bisphenol A type (meth)acrylate
[ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(F-7) Ethoxylated isocyanuric acid triacrylate
[A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
The above (F-1) to (F-7) were mixed in equal amounts to prepare a photopolymerizable monomer (E).

[Photopolymerization initiator (G)]
(G-1) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
[Omnirad 907 (IGM Resins)]
(G-2) 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone
[Omnirad 379EG (manufactured by IGM Resins)]
(G-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
[Omnirad TPO (manufactured by IGM Resins)]
(G-4) 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole
[Biimidazole (Kurokane Chemicals)]
(G-5) p-Dimethylaminoacetophenone
[DMA (manufactured by Daikifine)]
(G-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan)]
(G-7) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one
[Omnirad 2959 (manufactured by IGM Resins)]
(G-8) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide
[Omnirad 819 (manufactured by IGM Resins)]
The above (G-1) to (G-8) were mixed in equal amounts to prepare a photopolymerization initiator (G).

[Sensitizer (H)]
(H-1) 2,4-Diethylthioxanthone
[Kayacure DETX-S (manufactured by Nippon Kayaku)]
(H-2) 4,4'-bis(diethylamino)benzophenone
[CHEMARK DEABP (manufactured by Chemark Chemical Co.)]
The above (H-1) and (H-2) were mixed in equal amounts to prepare a sensitizer (H).

[Thiol-based chain transfer agent (I)]
(I-1) Trimethylolethane tris(3-mercaptobutyrate)
[TEMB (Showa Denko)]
(I-2) Trimethylolpropane tris(3-mercaptobutyrate)
[TPMB (Showa Denko)]
(I-3) Pentaerythritol tetrakis(3-mercaptopropionate)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-4) Trimethylolpropane tris(3-mercaptopropionate)
[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate
[TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
The above (I-1) to (I-5) were mixed in equal amounts to prepare a thiol-based chain transfer agent (I).

[Polymerization inhibitor (J)]
(J-1) 3-methylcatechol (J-2) methylhydroquinone (J-3) tert-butylhydroquinone The above (J-1) to (J-3) were mixed in equal amounts to prepare a polymerization inhibitor (J).

[Ultraviolet absorber (K)]
(K-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[TINUVIN 400 (manufactured by BASF Japan)]
(K-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
[TINUVIN900 (manufactured by BASF Japan)]
The above (K-1) and (K-2) were mixed in equal amounts to prepare an ultraviolet absorber (K).

[Antioxidant (L)]
(L-1) pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (L-2) dioctadecyl 3,3'-thiodipropanoate (L-3) tris[2,4-di-(tert)-butylphenyl]phosphite (L-4) bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (L-5) p-octylphenyl salicylate. The above (L-1) to (L-5) were mixed in equal amounts to give antioxidant (L).

[Leveling Agent (M)]
1 part of "MEGAFAC F-551: Fluorine-containing lipophilic group-containing oligomer" manufactured by DIC Corporation,
1 part of BYK-330: polyether-modified polydimethylsiloxane manufactured by BYK,
A mixed solution of 1 part of Kao Corporation's "Emulgen 103: polyoxyethylene lauryl ether" dissolved in 97 parts of propylene glycol monomethyl ether acetate.

[Storage stabilizer (N)]
(N-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol ("BHT" manufactured by Honshu Chemical Industry Co., Ltd.)
(N-2) Triphenylphosphine ("TPP" manufactured by Hokko Chemical Industry Co., Ltd.)
The above (N-1) and (N-2) were mixed in equal amounts to prepare a storage stabilizer (N).

[Adhesion improver (O)]
(O-1) 3-Glycidoxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-2) 3-Methacryloxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-3) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-4) 3-Mercaptopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
The above (O-1) to (O-4) were mixed in equal amounts to prepare a silane coupling agent (O).

[Solvent (P)]
(P-1) Propylene glycol monomethyl ether acetate 30 parts (P-2) Cyclohexanone 30 parts (P-3) Ethyl 3-ethoxypropionate 10 parts (P-4) Propylene glycol monomethyl ether 10 parts (P-5) Cyclohexanol acetate 10 parts (P-6) Dipropylene glycol methyl ether acetate 10 parts The above (P-1) to (P-6) were mixed in the above parts by mass to obtain solvent (P).

<Evaluation of Spectral Characteristics of Photosensitive Coloring Composition>
The obtained photosensitive coloring composition (R) was spin-coated on a 1.1 mm thick glass substrate using a spin coater so that the coating thickness was 1.5 μm, and after drying at 60 ° C. for 5 minutes, it was irradiated with 100 mJ / cm ² ultraviolet light using an ultra-high pressure mercury lamp, spray-developed with an alkaline developer consisting of a 0.2 mass % aqueous sodium carbonate solution, and then heated at 230 ° C. for 20 minutes to prepare a substrate. The spectrum of the obtained substrate was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) to measure the absorption spectrum in the wavelength range of 400 to 1000 nm.
The average transmittance (T) of each range was calculated from the measured absorption spectrum, and evaluated according to the same criteria as in the evaluation of the spectral characteristics of the colored composition (D). The evaluation results are shown in Table 5.

<Evaluation of Filterability of Photosensitive Coloring Composition>
The photosensitive coloring composition (R) thus obtained was evaluated in the same manner as in the evaluation of the filterability of the coloring composition. The evaluation results are shown in Table 5.

In the case of the photosensitive coloring composition, the results were similar to those of the coloring composition. By including a squarylium dye (A) having a maximum absorption wavelength between 700 and 900 nm in the range of 400 to 1000 nm, and a dye (B) having spectral characteristics that satisfy the above conditions (1) and (2), a coloring composition was obtained that has high transmittance of blue and green light used in detection such as fingerprint authentication (spectral characteristic 1) and cuts out red light and near-infrared light that become noise (spectral characteristics 2 and 3). It was also confirmed that by including dye (B-6), it is possible to cut out red light that becomes noise from the shorter wavelength side (spectral characteristic 4). Furthermore, it was confirmed that by including squarylium dye (A) and dye (B), filterability is improved.

Claims (6)

A coloring composition comprising a squarylium dye (A) having a maximum absorption wavelength in the range of 400 to 1000 nm between 700 and 900 nm, and a dye (B) having spectral characteristics that satisfy the following conditions (1) and (2) :
The squarylium dye (A) is at least one of a compound represented by the following general formula (2) and general formula (3):
A coloring composition, characterized in that the colorant (B) is a phthalocyanine pigment .
(1) When a coating film is formed so that the transmittance at 680 nm is 1%, the minimum transmittance (T1) at 400 to 450 nm is 20% or more. (2) When a coating film is formed so that the transmittance at 680 nm is 1%, the transmittance (T2) at 530 nm is 50% or more.

General formula (2)
(In general formula (2), X ₁₀₁ to X ₁₁₀ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, a sulfo group, -SO ₂ NR ₁₀₁ R ₁₀₂ , -COOR ₁₀₁ , -CONR ₁₀₁ R ₁₀₂ , a nitro group, a cyano group, or a halogen atom. R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or an alkyl group which may have a substituent. X ₁₀₁ to X ₁₁₀ may be bonded to each other to form a ring.)

General formula (3)
In formula (3), Q ₁ , Q ₄ , Q ₅ and Q ₈ each independently represent a carbon atom or a nitrogen atom. When Q ₁ , Q ₄ , Q ₅ or Q ₈ is a nitrogen atom, X ₂₀₁ , X ₂₀₄ , X ₂₀₅ or X ₂₀₈ does not exist.
R ₁ to R ₅ each independently represent a hydrogen atom, a sulfo group, —SO ₃ ⁻ M ⁺ or a halogen atom, where M ⁺ represents an inorganic or organic cation.
X ₂₀₁ to X ₂₀₈ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, an amino group, -NR ₆ R ₇ , a sulfo group, -SO ₂ NR ₈ R ₉ , -COOR ₁₀ , -CONR ₁₁ R ₁₂ , a nitro group, a cyano group, or a halogen atom. X ₂₀₁ to X ₂₀₈ may be bonded to each other to form a ring.
R ₆ to R ₁₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, or a pyridinyl group which may have a substituent. R ₆ and R ₇ , R ₈ and R _{9 , and} R ₁₁ and R ₁₂ may be bonded to each other to form a ring. 2. The colored composition according to claim 1 , wherein the colorant (B) is an aluminum phthalocyanine pigment. 3. The colored composition according to claim 2 , wherein the dye (B) is a compound represented by the following general formula (1):

General formula (1)
(In the formula, X ₁ to X ₄ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent.
Y ₁ to Y ₄ each independently represent a halogen atom, a nitro group, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
M represents Al.
Z represents -OP(=O) _R13R14 , where _R13 and _R14 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group _which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and _R13 and _R14 may bond to each other to form a ring.
m ₁ , m ₂ , m ₃ , m ₄ , n ₁ , n ₂ , n ₃ , and n ₄ each independently represent an integer of 0 to 4, and m ₁ +n ₁ , m ₂ +n ₂ , m ₃ +n ₃ , and m ₄ +n ₄ each represent an integer of 0 to 4 and may be the same or different. The colored composition according to any one of claims 1 to 3 , further comprising a basic resin-type dispersant. 5. The colored composition according to claim 4 , further comprising a photopolymerization initiator. A near infrared cut filter comprising the colored composition according to any one of claims 1 to 5 .