JP2022022806A - Coloring composition and near infrared cut filter - Google Patents

Abstract

To provide: a coloring composition which has high light transmittance of blue and green light, has high ability to cut noise in a red to near infrared region, and good filterability; and a near infrared cut filter comprising the coloring composition.SOLUTION: A coloring composition comprises: a squarylium pigment having a maximum absorption wavelength in a range of 400 to 1000 nm between 700 to 900 nm; and a pigment (B) having spectral characteristics which satisfy a condition (1) that, when a coating film is formed so that transmittance at 680 nm becomes 1%, a minimum value (T1) of transmittance between 400 and 450 nm becomes 20% or more, and a condition (2) that, when a coating film is formed so that transmittance at 680 nm becomes 1%, a minimum value (T2) of transmittance at 530 nm becomes 50% or more.SELECTED DRAWING: None

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 using biometric information (for example, fingerprint, iris, face, vein, etc.), which is information unique to the living body, has come to be carried out. .. In biometric authentication, authentication is performed by irradiating light having a wavelength corresponding to the biological component or biological structure of interest 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 irradiating blue or green light having low transparency to a finger and detecting the reflected light. At this time, red light or near-infrared light, which is highly transparent to the finger among natural light, may enter the light receiving portion having detection sensitivity in ultraviolet to near-infrared and be detected as noise. In order to eliminate this noise, a filter that cuts red to near infrared rays is required.

The near-infrared cut filter is manufactured by using a composition containing a near-infrared absorber as in Patent Document 2, for example. However, the noise cutting ability in the near infrared region was not always satisfactory. In addition, the transmittance of blue and green light used for detection was also insufficient.

JP-A-2017-196319 JP 2015-163956

The present invention provides a coloring composition having high transmittance of blue and green light, high noise cutting ability in the red to near infrared region, and good filterability, and a near infrared cut filter containing the coloring composition. The purpose is to provide.

As a result of diligent research to solve the above problems, the present inventors have a specific spectral characteristic with the squarylium dye (A) having a maximum absorption wavelength in the range of 400 to 1000 nm between 700 and 900 nm. We found that the coloring composition containing the dye (B) has high transmittance of blue and green light, high noise-cutting ability in the red to near-infrared region, and good filterability. The present invention is made based on this.

That is, the present invention comprises 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 satisfying the following conditions (1) and (2). The present invention relates to a coloring composition comprising.
(1) When the coating film is formed so that the transmittance at 680 nm is 1%, the minimum value (T1) of the transmittance at 400 to 450 nm is 20% or more (2) The transmittance at 680 nm becomes 1%. When the coating film is formed as described above, 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.

（式中、Ｘ_１～Ｘ_４はそれぞれ独立に、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいシクロアルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、または、置換基を有してもよいアリールチオ基を表す。
Ｙ_ｌ～Ｙ_４はそれぞれ独立に、ハロゲン原子、ニトロ基、置換基を有してもよいフタルイミドメチル基、または、置換基を有してもよいスルファモイル基を表す。
Ｍ は、Ａｌを表す。
Ｚは－ＯＰ（＝Ｏ）Ｒ_１３Ｒ_１４を表し、ここでＲ_１３およびＲ_１４はそれぞれ独立に、水素原子、水酸基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシル基、または、置換基を有してもよいアリールオキシ基を表し、Ｒ_１３、Ｒ_１４が互いに結合して環を形成しても良い。
ｍ_１，ｍ_２，ｍ_３，ｍ_４，ｎ_１，ｎ_２，ｎ_３，およびｎ_４は、それぞれ独立に、０～４の整数を表し、ｍ_１＋ｎ_１，ｍ_２＋ｎ_２，ｍ_３＋ｎ_３，ｍ_４＋ｎ_４は、各々、０～４で、同一でも異なっても良い。） The present invention also relates to the coloring 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 are independently an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent. It has 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, or a substituent. Represents a optionally arylthio group.
Y _l to Y ₄ independently represent a halogen atom, a nitro group, a phthalimide methyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
M represents Al.
Z represents −OP (= O) R ₁₃ R ₁₄ , where R ₁₃ and R ₁₄ independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, and a substituent. It represents a good aryl group, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and R ₁₃ and R ₁₄ may be bonded to each other to form a ring.
m ₁ , m ₂ , m ₃ , m ₄ , n ₁ , n ₂ , n ₃ , and n ₄ independently represent integers from 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ respectively. + N ₃ , m ₄ + n ₄ are 0 to 4, respectively, and may be the same or different. )

（一般式（２）中、Ｘ_１０１～Ｘ_１１０は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアリール基、置換基を有してもよいアラルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、アミノ基、置換アミノ基、スルホ基、－ＳＯ_２ＮＲ_１０１Ｒ_１０２、－ＣＯＯＲ_１０１、－ＣＯＮＲ_１０１Ｒ_１０２、ニトロ基、シアノ基またはハロゲン原子を表す。Ｒ_１０１、Ｒ_１０２は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基を表す。Ｘ_１０１～Ｘ_１１０は、置換基同士が結合して環を形成してもよい。）

一般式（３）

（一般式（３）中、Ｑ_１、Ｑ_４、Ｑ_５及びＱ_８は、それぞれ独立に、炭素原子又は窒素原子を表す。Ｑ_１、Ｑ_４、Ｑ_５又はＱ_８が窒素原子の場合、Ｘ_２０１、Ｘ_２０４、Ｘ_２０５又はＸ_２０８はないものとする。
Ｒ_１～Ｒ_５は、それぞれ独立に、水素原子、スルホ基、－ＳＯ_３ ^－Ｍ^＋又はハロゲン原子を表す。Ｍ^＋は無機又は有機のカチオンを表す。
Ｘ_２０１～Ｘ_２０８は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアリール基、置換基を有してもよいアラルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、ヒドロキシル基、アミノ基、－ＮＲ_６Ｒ_７、スルホ基、－ＳＯ_２ＮＲ_８Ｒ_９、－ＣＯＯＲ_１０、－ＣＯＮＲ_１１Ｒ_１２、ニトロ基、シアノ基又はハロゲン原子を表す。Ｘ_２０１～Ｘ_２０８は、互いに結合して環を形成してもよい。
Ｒ_６～Ｒ_１２は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアシル基又は置換基を有してもよいピリジニル基を表す。Ｒ_６とＲ_７、Ｒ_８とＲ_９、Ｒ_１１とＲ_１２は、互いに結合して環を形成してもよい。） The present invention also relates to the coloring composition, wherein the squarylium dye (A) is at least one of the compounds represented by the following general formulas (2) and (3).
General formula (2)

(In the general formula (2), X ₁₀₁ to X ₁₁₀ each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. May have an aryl group, 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 , represents a nitro group, a cyano group or a halogen atom. R ₁₀₁ and R ₁₀₂ may independently have a hydrogen atom and a substituent, respectively. Represents an alkyl group. In X ₁₀₁ to X ₁₁₀ , substituents may be bonded to each other to form a ring.)

General formula (3)

(In the general formula (3), Q ₁ , Q ₄ , Q ₅ and Q ₈ independently represent a carbon atom or a nitrogen atom. When Q ₁ , Q ₄ , Q ₅ or Q ₈ are nitrogen atoms, It is assumed that there are no X ₂₀₁ , X ₂₀₄ , X ₂₀₅ or X ₂₀₈ .
R ₁ to R ₅ independently represent a hydrogen atom, a sulfo group, -SO ₃ ^- M ⁺ , or a halogen atom. M ⁺ represents an inorganic or organic cation.
Each of X ₂₀₁ to X ₂₀₈ independently contains 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, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, hydroxyl group, amino group, -NR ₆ R ₇ , sulfo group, -SO ₂ NR ₈ R ₉ , -COOR ₁₀ , -CONR ₁₁ R ₁₂ , represents a nitro group, a cyano group or a halogen atom. X ₂₀₁ to X ₂₀₈ may be coupled to each other to form a ring.
R ₆ to R ₁₂ independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an acyl group or a substituent which may have a substituent. Represents a pyridinyl group that may have. R ₆ and R ₇ , R ₈ and R _{9, and} R ₁₁ and R ₁₂ may be coupled to each other to form a ring. )

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

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

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

INDUSTRIAL APPLICABILITY According to the present invention, a coloring composition having high transmittance of blue or green light, high noise cutting ability in the red to near infrared region, and good filterability, and a near infrared cut filter containing the coloring composition can be obtained. Can be provided.

Hereinafter, each component of the coloring composition of the present invention will be described.
In the present application, the term "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" is particularly described. Unless there is an acryloyl and / or methacrylic acid, acrylic and / or methacrylic acid, acrylic acid and / or methacrylic acid, acrylate and / or methacrylate, or acrylamide and / or methacrylic acid, respectively. It shall be represented.
Further, "CI" mentioned in the present specification means a color index (CI).

<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. Since the maximum absorption wavelength is 700 to 900 nm, light in the near-infrared region detected as noise can be widely cut to the long wavelength side. The value of the maximum absorption wavelength of the squarylium dye (A) is a value measured by the method described in Examples described later.

The squalylium dye (A) has (I2) / (I1) of 0.5 or less when the absorbance at the maximum absorption wavelength in the range of 400 to 1000 nm is (I1) and the absorbance at 650 nm is (I2). Is preferable.

The squarylium dye (A) is preferably at least one of the compounds represented by the following general formulas (2) and (3). The squarylium dye normally included in the cyanine dye has low heat resistance, but the general formula (2) and the general formula (3) have high heat resistance.

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

Each of X ₁₀₁ to X ₁₁₀ independently contains 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, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, amino group, substituted amino group, sulfo group, -SO ₂ NR ₁₀₁ R ₁₀₂ ,- Represents 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 and an alkyl group which may have a substituent. In X ₁₀₁ to X ₁₁₀ , substituents may be bonded to each other to form a ring.

In X ₁₀₁ to X ₁₁₀ , the "alkyl group which may have a substituent" includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a tert-amyl group and a 2-ethylhexyl group. , Stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group and the like. Among these, a methyl group, an ethyl group and an n-propyl group are preferable from the viewpoint of imparting durability and difficulty in synthesis, and a methyl group is particularly preferable.

In X ₁₀₁ to X ₁₁₀ , the "alkenyl group which may have a substituent" includes, for example, a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, and the like. Examples thereof include 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like. Among these, a vinyl group and an allyl group are preferable from the viewpoint of imparting durability and difficulty in synthesizing.

In X ₁₀₁ to X ₁₁₀ , the "aryl group which may have a substituent" is, for example, a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, or 4-bromo. Examples thereof include a phenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, a 4-cyanophenyl group and the like. Among these, a phenyl group and a 4-methylphenyl group are preferable from the viewpoint of imparting durability and difficulty in synthesis.

Examples of the "aralkyl group which may have a substituent" in X ₁₀₁ to X ₁₁₀ include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and the like. Among these, a benzyl group is preferable from the viewpoint of imparting durability and difficulty in synthesis.

In X ₁₀₁ to X ₁₁₀ , the "alkoxy group even if it has a substituent" is, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, or 2-ethylhexyl. Examples thereof include an oxy group, a trifluoromethoxy group, a cyclohexyloxy group and a stearyloxy group. Among these, a methoxy group, an ethoxy group, and a trifluoromethoxy group are preferable from the viewpoint of imparting durability and difficulty in synthesis.

In X ₁₀₁ to X ₁₁₀ , the "aryloxy group which may have a substituent" is, for example, a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group, a 4-chloro-2. -Methylphenyloxy group, 4-tert-butylphenyloxy group, 4-methoxyphenyloxy group, 4-diethylaminophenyloxy group, 4-nitrophenyloxy group and the like can be mentioned. Among these, a phenoxy group and a naphthyloxy group are preferable from the viewpoint of imparting durability and difficulty in synthesis.

In X ₁₀₁ to X ₁₁₀ , the "substituted amino group" is, for example, 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, or a dibutylamino. Groups, N, N-di (2-hydroxyethyl) amino groups, phenylamino groups, naphthylamino groups, 4-tert-butylphenylamino groups, diphenylamino groups, N-phenyl-N-ethylamino groups and the like can be mentioned. .. Among these, a dimethylamino group and a diethylamino group are preferable from the viewpoint of imparting durability and difficulty in synthesis.

Examples of the "halogen atom" in X ₁₀₁ to X ₁₁₀ include fluorine, bromine, chlorine and iodine.

In X ₁₀₁ to X ₁₁₀ , substituents can be bonded to each other to form a ring. Examples of the structure when the substituents of X ₁₀₁ to X ₁₁₀ are bonded to each other to form a ring 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, and 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 Unsubstituted alkyl groups are more preferred. The unsubstituted alkyl group is preferably, for example, a methyl group.

(Method for producing a compound represented by the general formula (2))
The compound represented by the general formula (2) is prepared by, for example, condensing 1,8-diaminonaphthalene and cyclohexanones represented by the following general formula (4) by heating and refluxing in a solvent together with a catalyst, and then condensing the following. It can be synthesized by adding 3,4-dihydroxy-3-cyclobutene-1,2-dione represented by the chemical formula (5), further heating and refluxing, and condensing. Needless to say, the synthesis is not limited to the above method.

(Compound represented by the 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. If Q ₁ , Q ₄ , Q ₅ or Q ₈ are nitrogen atoms, then X ₂₀₁ , X ₂₀₄ , X ₂₀₅ or X ₂₀₈ shall not be present.
R ₁ to R ₅ independently represent a hydrogen atom, a sulfo group, -SO ₃ ^- M ⁺ , or a halogen atom. M ⁺ represents an inorganic or organic cation.
Each of X ₂₀₁ to X ₂₀₈ independently contains 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, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, hydroxyl group, amino group, -NR ₆ R ₇ , sulfo group, -SO ₂ NR ₈ R ₉ , -COOR ₁₀ , -CONR ₁₁ R ₁₂ , represents a nitro group, a cyano group or a halogen atom. X ₂₀₁ to X ₂₀₈ may be coupled to each other to form a ring.
R ₆ to R ₁₂ independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an acyl group or a substituent which may have a substituent. Represents a pyridinyl group that may have. R ₆ and R ₇ , R ₈ and R _{9, and} R ₁₁ and R ₁₂ may be coupled to each other to form a ring.

For Q ₁ , Q ₄ , Q ₅ and Q ₈ , for example, a carbon atom is more preferable.

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

As the "inorganic or organic cation" of M ⁺ in R ₁ to R ₅ , for example, known ones can be adopted without limitation, and in the case of organic cations, either a small molecule type or a polymer type may be used. Specific examples thereof include metal atoms, ammonium compounds, pyridinium compounds, imidazolium compounds, phosphonium compounds, and sulfonium compounds. In the case of the polymer type, for example, "resin having a quaternary ammonium base" and the like can be mentioned, but the present invention is not limited thereto. Among these, a resin having a trivalent metal atom, an ammonium compound, and a quaternary ammonium base is preferable from the viewpoint of heat resistance.

From the viewpoint of imparting resistance, R ₁ to R ₅ are all hydrogen atoms, or four of R ₁ to R ₅ are hydrogen atoms and one is a sulfo group, -SO ₃ ^- M ⁺ or a halogen atom. It is preferable to have. Among these, it is particularly preferable that all of them are hydrogen atoms, or 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 , the "alkyl group which may have a substituent" includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an isobutyl group, a tert-amyl group, and 2 -Examples include ethylhexyl group, stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group and the like. Of these, a methyl group and an ethyl group are preferable from the viewpoint of difficulty in synthesis.

In X ₂₀₁ to X ₂₀₈ , the "alkenyl group which may have a substituent" includes, for example, a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, and the like. Examples thereof include 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like. Of these, vinyl groups and allyl groups are preferable from the viewpoint of difficulty in synthesis.

In X ₂₀₁ to X ₂₀₈ , the "aryl group which may have a substituent" is, for example, a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, or 4-bromo. Examples thereof include a phenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, a 4-cyanophenyl group and the like. Of these, a phenyl group and a 4-methylphenyl group are preferable from the viewpoint of difficulty in synthesis.

Examples of the "aralkyl group which may have a substituent" in X ₂₀₁ to X ₂₀₈ include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and the like. Among these, the benzyl group is preferable from the viewpoint of the difficulty of synthesis.

In X ₂₀₁ to X ₂₀₈ , the "alkoxy group even if it has a substituent" is, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, or 2-ethylhexyl. Examples thereof include an oxy group, a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group, a 2- (diethylamino) ethoxy group and the like. Among these, a methoxy group, an ethoxy group, a trifluoromethoxy group, and a 2- (diethylamino) ethoxy group are preferable from the viewpoint of difficulty in synthesis.

In X ₂₀₁ to X ₂₀₈ , the "aryloxy group which may have a substituent" is, for example, a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group, a 4-chloro-2. -Methylphenyloxy group, 4-tert-butylphenyloxy group, 4-methoxyphenyloxy group, 4-diethylaminophenyloxy group, 4-nitrophenyloxy group and the like can be mentioned. Among these, a phenoxy group and a naphthyloxy group are preferable from the viewpoint of difficulty in synthesis.

Examples of the "halogen atom" in X ₂₀₁ to X ₂₀₈ include fluorine, bromine, chlorine and iodine.

In X ₂₀₁ to X ₂₀₈ , substituents may be bonded to each other to form a ring. The following is an example of a preferable structure when the substituents of X ₂₀₁ to X ₂₀₈ are bonded to each other to form a ring. The structure is not limited to these.

It is particularly preferable that X ₂₀₁ to X ₂₀₈ are all hydrogen atoms from the viewpoint of dispersibility, storage stability and synthesis difficulty.

In R ₆ to R ₁₂ , the "alkyl group which may have a substituent" includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an isobutyl group, a sec-butyl group and a tert. -Amil group, 2-ethylhexyl group, stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group And so on. Of these, a methyl group and an ethyl group are preferable from the viewpoint of difficulty in synthesis.

In R ₆ to R ₁₂ , the "aryl group which may have a substituent" includes, for example, a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group and a 4-bromo. Examples thereof include a phenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, a 4-cyanophenyl group and the like. Of these, a phenyl group and a 4-methylphenyl group are preferable from the viewpoint of difficulty in synthesis.

Examples of the "acyl group which may have a substituent" in R ₆ to R ₁₂ include an acetyl group, a propioil group, a benzoyl group, an acrylyl group, a trifluoroacetyl group and the like. Of these, an acetyl group is preferable from the viewpoint of difficulty in synthesis.

Examples of the "pyridinyl group which may have a substituent" in R ₆ to R ₁₂ include 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 2-methyl-4-pyridinyl group and the like. Of these, the 4-pyridinyl group is preferable from the viewpoint of difficulty in 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 the general formula (3))
The compound represented by the general formula (3) can be described, for example, by the following reaction diagram. First, 1,8-diaminonaphthalene and fluorenone are heated under reflux together with a catalyst and condensed, and then 3,4-dihydroxy-3-cyclobutene-1,2-dione is added and further heated. It can be synthesized by refluxing and condensing. When at least one of R ₁ to R ₅ is SO ₃ ^- M ⁺ , SO is obtained by counter ion exchange between the hydrogen ion of the sulfo group of the dye substituted with the sulfo group and the compound having the desired cation. A dye substituted with ₃ ^- M ⁺ is obtained. Needless to say, the synthesis is not limited to the above method.

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

<Dye (B)>
The coloring composition of the present invention contains a dye (B) having spectral characteristics satisfying the following conditions (1) and (2). By containing the dye (B), it is possible to sufficiently transmit blue or green light and cut red light detected as noise.

(1) When the coating film is formed so that the transmittance at 680 nm is 1%, the minimum value (T1) of the transmittance at 400 to 450 nm is 20% or more (2) The transmittance at 680 nm becomes 1%. When the coating film is formed as described above, the transmittance (T2) at 530 nm is 50% or more.

Further, although the principle is not clear, the filterability is improved by combining the squarylium dye (A) and the dye (B).

The dye (B) is preferably a phthalocyanine pigment, more preferably an aluminum phthalocyanine pigment, and by containing the aluminum phthalocyanine pigment, blue or green light is transmitted in a wide range of wavelengths to improve the detection sensitivity. be able to. Further, it is preferably a compound represented by the following general formula (1).
General formula (1)

In the formula, X ₁ to X ₄ independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent. It has a heterocyclic group which may have, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or a substituent. Represents a optionally arylthio group.
Y _l to Y ₄ independently represent a halogen atom, a nitro group, a phthalimide methyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
M represents Al.
Z represents −OP (= O) R ₁₃ R ₁₄ , where R ₁₃ and R ₁₄ independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, and a substituent. It represents a good aryl group, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and R ₁₃ and R ₁₄ may be bonded to each other to form a ring.
m ₁ , m ₂ , m ₃ , m ₄ , n ₁ , n ₂ , n ₃ , and n ₄ independently represent integers from 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ respectively. + N ₃ , m ₄ + n ₄ are 0 to 4, respectively, 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, and a substituent. It has a cycloalkyl group which may have a group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, and a substituent. Examples thereof include an alkylthio group which may have a substituent and an arylthio group which may have a substituent. When the above X ₁ to X ₄ have a substituent, the substituent may be the same or different, and specific examples thereof include characteristics of a halogen group such as fluorine, chlorine and bromine, an amino group, a hydroxyl group and a nitro group. In addition to the group, an alkyl group, an aryl group, a cycloalkyl group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group and the like can be mentioned. Further, there may be a plurality of these substituents.

Examples of the "alkyl group" of the alkyl group which may have a substituent include 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 and an n-hexyl group. Examples thereof include a linear or branched alkyl group such as an n-octyl group, a stearyl group and a 2-ethylhexyl group, and examples of the "alkyl group having a substituent" include a trichloromethyl group, a trifluoromethyl group and 2,2. 2-Trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4 -Methylbenzyl group, 4-tert-putylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like can be mentioned.

Examples of the "aryl group" of the aryl group which may have a substituent include a phenyl group, a naphthyl group, an anthryl group and the like, and examples of the "aryl group having a substituent" include p-methylphenyl group and p-. Bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl Examples thereof include a group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, a 2-aminoanthraquinonyl group and the like.

Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like, and examples of the "cycloalkyl group having a substituent" include 2,5. -Dimethylcyclopentyl group, 4-tert-pentylcyclohexyl group and the like can be mentioned.

Examples of the "heterocyclic group" of the heterocyclic group which may have a substituent include a pyridyl group, a pyrazil group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group and the like, and "a heterocyclic group having a substituent". Examples thereof include a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrolyl group and the like.

Examples of the "alkoxyl group" of the alkoxyl group which may have a substituent include 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 and 2 , 3-Dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group and other linear or branched alkoxyl groups can be mentioned. "Groups" include trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoromethylpropoxy group, 2- Examples thereof include an ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, a benzyloxy group and the like.

Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group and the like, and examples of the "aryloxy group having a substituent" include p-methyl. Examples thereof include a phenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, a 2-methyl-4-chlorophenoxy group and the like.

Examples of the "alkylthio group" of the alkylthio group which may have a substituent include 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 and the like. Examples of the "alkylthio group having a substituent" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group and the like.

Examples of the "arylthio group" of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group and the like, and examples of the "arylthio group having a substituent" include. , Chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group, 2-aminophenylthio group, 2-hydroxyphenylthio group and the like.

Next, specific examples of Y _l to Y ₄ include a halogen atom, a nitro group, a phthalimide methyl group which may have a substituent (C ₆ H ₄ (CO) ₂ N-CH _2- ), and a sulfamoyl group (C 6 H 4 (CO) 2 N-CH 2-). H ₂ NSO _2- ) can be mentioned. Further, the phthalimidemethyl group having a substituent represents a structure in which a hydrogen atom in the phthalimidemethyl group is substituted with a substituent, and the sulfamoyl group having a substituent represents a structure in which a hydrogen atom in the sulfamoyl group is substituted with a substituent. Represents the structure that was created. Preferred Y is a halogen atom and a sulfamoyl group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Chlorine and bromine are particularly preferable from the viewpoint of brightness. The "substituent" of the phthalimidemethyl group which may have a substituent and the sulfamoyll group which may have _a substituent is synonymous with the substituents of X1 to _X4 .

Z is represented by −OP (= O) R ₁₃ R ₁₄ , where R ₁₃ and R ₁₄ each have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, and a substituent. It represents an aryl group which may have an aryl group, an alkoxyl group which may have a substituent, and an aryloxy group which may have a substituent, and R ₁₃ and R ₁₄ may be bonded to each other to form a ring.

Here, the alkyl groups in R ₁₃ and R ₁₄ include 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, an n-hexyl group and an n-octyl group. , Stearyl group, 2-ethylhexyl group and other linear or branched alkyl groups, and examples of the substituent when the alkyl group is an alkyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine. There are an alkoxyl group such as a methoxy group, an aromatic group such as a phenyl group and a trill group, and a nitro group. Further, there may be a plurality of substituents. 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 and a 2-butoxyethyl group. , 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group, etc. Can be mentioned.

Examples of the aryl group in R ₁₃ and R ₁₄ include a phenyl group, a naphthyl group, an anthryl group and the like, and when the aryl group has a substituent, the substituent includes a halogen atom such as chlorine, fluorine and bromine, an alkyl group and the like. There are an alkoxyl group, an amino group, a nitro group and the like. Further, there may be a plurality of substituents. Examples of the aryl group having a substituent include a p-tolyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group and a 2-dimethylamino group. There are a phenyl 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 and the like.

The alkoxyl groups in R ₁₃ and R ₁₄ include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group and 2,3-dimethyl-3-. Examples thereof include a linear or branched alkoxyl group such as a 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 substituent. There are halogen atoms such as chlorine, fluorine and bromine, aryl groups such as an alkoxyl group, phenyl group and trill group, and nitro groups. Further, there may be a plurality of substituents. Examples of the alkoxyl group having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group and a 2,2-ditrifluoro group. There are a methylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, a benzyloxy group and the like.

Examples of the aryloxy group in R _{13 "} and R ₁₄ include a phenoxy group, a naphthaloxy group, an anthryloxy group and the like, and when the aryloxy group has a substituent, the substituent includes a halogen such as chlorine, fluorine and bromine. There are an atom, an alkyl group, an alkoxyl group, an amino group, a nitro group and the like. Further, there may be a plurality of substituents. Examples of the aryloxy group having a substituent include a p-methylphenoxy group and a p-nitro group. There are a phenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, a 2-methyl-4-chlorophenoxy group and the like.

As the phthalocyanine compound represented by the general formula (1) used _in the present invention, at least one of R13 and _R14 may have a substituent from the viewpoint of dispersibility and color characteristics. It is preferably an aryloxy group that may have a group or a substituent. More preferably, R ₁₃ and R ₁₄ are all aryl groups or aryloxy groups. Further, preferably, both R ₁₃ and R ₁₄ are phenyl groups or phenoxy groups.

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

The dye (B) is C.I. I. Pigment blue 15: 3 (PB15: 3) is also preferred. PB15: 3 having an α-type crystal content of 7% or less and PB15: 3 having a free copper content of 2000 ppm or less are more preferable. By containing PB15: 3, blue and green light can be transmitted in a wide range of wavelengths and the detection sensitivity can be increased.

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

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

<Other pigments>
If necessary, the coloring composition of the present invention may contain other dyes as long as the spectral characteristics of the squarylium dye (A) and the dye (B) are not impaired. Hereinafter, the dye may be referred to as a pigment.

<Dye derivative>
A dye derivative can be used in the coloring composition of the present invention, if necessary. The dye derivative is a compound having an acidic group, a basic group, a neutral group and the like in the organic dye residue. The dye derivative has, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and a basic substituent such as an amine salt thereof, a sulfonamide group, or a tertiary amino group at the terminal. Examples thereof include compounds and compounds having a neutral substituent such as a phenyl group and a phthalimidealkyl group.
Organic pigments include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, and benzoiso. Examples thereof include indol pigments such as indole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, and azo pigments such as azo, disazo and polyazo.

Specifically, the diketopyrrolopyrrole dye derivative is JP-A-2001-22520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397, phthalocyanine-based. For dye derivatives, JP-A-2007-226161, WO2016 / 163351 pamphlet, JP-A-2017-165820, JP-A-5753266, and for anthraquinone-based dye derivatives, JP-A-63-246674, JP-A-09. -272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325 pamphlet, quinacridone-based dye derivatives are JP-A-48-54128, JP-A-48-54128. JP-A-03-9961, JP-A-2000-273383, JP-A-2011-162662 for dioxazine-based dye derivatives, JP-A-2007-314785 for thiazine indigo-based dye derivatives, Triazine-based dye derivatives. Is JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681. , Benzoisoindole-based dye derivatives are JP-A-2009-57478, and quinophthalone-based dye derivatives are JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012. -226110, naphthol-based dye derivatives are JP-A-2012-208329, JP-A-2014-5439, and azo-based dye derivatives are JP-A-2001-172520, JP-A-2012-1722092, acidic. Substituents are referred to in JP-A-2004-307854, and basic substituents are referred to in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. Examples include the described dye derivatives. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, and the like. A compound having a substituent such as a neutral group is synonymous with a dye derivative.

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

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 with respect to 100 parts by mass of the pigment.

By adding a dye derivative to the pigment and performing pigmentation treatments such as acid pacing, acid slurry, dry milling, salt milling, and solvent salt milling, the dye derivative is adsorbed on the pigment surface and the dye derivative is not added. In comparison, the primary particles of the pigment can be made finer.

By adding a dye derivative to the pigment and performing dispersion treatment such as wet dispersion using two rolls, three rolls, and beads, the dye derivative is adsorbed on the pigment surface and the pigment surface has polarity, and the resin type dispersant is adsorbed. Is promoted, compatibility with pigments, dye derivatives, resin-type dispersants, solvents, and other additives is improved, and dispersion stability and temporal viscosity stability when made into a coloring composition or a coloring curable composition are improved. do. Further, by improving the compatibility, the coating film is excellent in stability over time when the coloring curable composition is applied to a glass substrate or the like, and the waiting time from application to exposure of the coloring curable composition (PCD: Post Coating). Stability and characteristic dependence such as pattern shape with respect to Delay) and waiting time from exposure to heat treatment (PED: Post Exposure Delay), and line width sensitivity stability are improved. Further, by adsorbing and coating the pigment surface with the pigment 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 fired. Furthermore, variations in development time and development residues are suppressed.

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

In terms of resin-based dispersants, for example, urethane-based dispersants such as polyurethane, polycarbonic acid esters such as polyacrylates, unsaturated polyamides, polycarbonic acid, polycarbonic acid (partial) amine salts, and ammonium polycarbonic acid salts, Polycarbonic acid alkylamine salts, polysiloxanes, long-chain polyaminoamidophosphates, hydroxyl group-containing polycarbonic acid esters and their modifications; formed by the reaction of poly (lower alkyleneimine) with a polyester having a free carboxyl group. Amid and its salts; (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc .; polyester, modification Examples thereof include polyacrylates, ethylene oxide / propylene oxide addition compounds, and phosphate ester-based compounds.

In terms of ionicity, examples of the resin-type dispersant include an acidic resin-type dispersant and a basic resin-type dispersant.

The basic resin type dispersant has a nitrogen atom-containing graft copolymer and a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, etc. in the side chain, and has a nitrogen atom-containing acrylic block co-weight. Examples thereof include coalescing and urethane-based polymer dispersants.
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 adsorbing 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, manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti- SOLPERSE-3000, 9000, 13000, 13240, 13650, manufactured by Japan Lubrizol, such as Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324 or Lactimon, Lactimon-WS or Bykumen, etc. 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, etc. , 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Examples thereof include Ajispar PA111, PB711, PB821, PB822, PB824 manufactured by Fine Techno.

The resin-type dispersant can be used alone or in combination of two or more.

The content of the resin type dispersant is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to the total amount of the pigment. When an appropriate amount is contained, a film is easily formed.

<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 includes, for example, a thermoplastic resin, a thermosetting resin, an active energy ray curable resin, and the like. 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 at the time of producing a near-infrared cut filter, and an acidic group is required.

The binder resin can be used alone or in combination of two or more.

The content of the binder resin is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the colorant. When an appropriate amount is contained, a film can be easily formed and good color characteristics can be easily obtained.

<Thermoplastic resin>
The thermoplastic resin is, for example, an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, a polyvinyl acetate, a polyurethane resin, and the like. Examples thereof include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.
Examples of the alkali-soluble thermoplastic resin include resins having an acidic group such as a carboxyl group and a sulfone group. The alkali-soluble thermoplastic resin is, for example, an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, or an ethylene / (meth) acrylic acid copolymer. , Or isobutylene / (anhydrous) maleic acid copolymer and the like. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferable 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 methods (i) and (ii) shown below. Due to the effect of the active energy rays, the resin is three-dimensionally crosslinked to increase the crosslink density and improve the chemical resistance.

[Method (i)]
In method (i), for example, an ethylenically unsaturated monomer is added to a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another monomer. The carboxyl group of the unsaturated monobasic acid having a heavy bond is subjected to an addition reaction. Next, it is a method of introducing an ethylenically unsaturated double bond and a carboxyl group by reacting the generated hydroxyl group with a polybasic acid anhydride.

Ethylene unsaturated monomers having an epoxy group include, for example, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and the like. And 3,4-epoxycyclohexyl (meth) acrylates. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of reactivity with unsaturated monobasic acid.

Unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyls, halogens, nitros, cyano substituents and the like. Examples include carboxylic acid.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like. If necessary, such as by increasing the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic acid anhydride was used, or a tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride was used to remain. Anhydrous groups can also be hydrolyzed.

Examples of other monomers include the following. For example, 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) (Meta) acrylates such as acrylates, phenoxyethyl (meth) acrylates, phenoxydiethylene glycol (meth) acrylates, methoxypolypropylene glycol (meth) acrylates, or ethoxypolyethylene glycol (meth) acrylates,
Alternatively, (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholin. Acrylamides styrene or styrenes such as α-methyl styrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, vinyl acetate, fatty acid vinyls such as vinyl propionate. And so on.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide. Kumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4- Phenylened maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide Hexanoart, N-substituted maleimides such as N- [4- (2-benzoimidazolyl) phenyl] maleimide, 9-maleimideacridin, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl Acrylate, ethyleneoxide (EO) -modified (meth) acrylate of phenol, EO or propylene oxide (PO) -modified (meth) acrylate of paracumylphenol, EO-modified (meth) acrylate of nonylphenol, PO-modified (meth) acrylate of nonylphenol, etc. Can be mentioned.

As a method similar to the method (i), for example, an ethylenically unsaturated monomer having a carboxyl group and another monomer are copolymerized with a part of the side chain carboxyl group of the copolymer obtained. This is a method of introducing an ethylenically unsaturated double bond and a carboxyl group by subjecting an ethylenically unsaturated monomer having an epoxy group to an addition reaction.

[Method (ii)]
In the method (ii), the ethylenically unsaturated monomer having an isocyanate group is added to the side chain hydroxyl group of the copolymer obtained by copolymerizing the ethylenically unsaturated monomer having a hydroxyl group with another monomer. This is a method of reacting a monomeric isocyanate group.

The ethylenically unsaturated monomer having a hydroxyl group is, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and the like. Examples thereof include hydroxyalkyl methacrylates such as glycerol mono (meth) acrylates and cyclohexanedimethanol mono (meth) acrylates. Further, a polyether mono (meth) acrylate obtained by superpolymerizing hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, poly γ-valerolactone, poly ε-caprolactone, and / or poly. Polyester mono (meth) acrylate to which 12-hydroxystearic acid or the like is added can also be mentioned. 2-Hydroxyethyl methacrylate or glycerol mono (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film, and from the viewpoint of sensitivity, it is preferable to use one having 2 or more and 6 or less hydroxyl groups. Therefore, glycerol mono (meth) acrylate is more preferable.

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

Other monomers that can constitute the alkali-soluble resin include N-substituted maleimides, alkyleneoxy group-containing monomers, and phosphate ester group-containing ethylenically unsaturated monomers in addition to the other ethylenically unsaturated monomers described above. Examples thereof include monomers and carboxyl group-containing ethylenically unsaturated monomers.
N-substituted maleimides include, for example, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-. 4-Methyl-3-maleimidecoumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4-phenylenedi maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitro) Phenyl) Maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, Examples thereof include N-succinimidyl-6-maleimidehexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, and 9-maleimide acrydin. Examples of the alkyleneoxy group-containing monomer include EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenylacrylate, ethylene oxide (EO) -modified (meth) acrylate of phenol, and paracumylphenol. Examples thereof include EO or propylene oxide (PO) modified (meth) acrylate, EO-modified (meth) acrylate of nonylphenol, and PO-modified (meth) acrylate of nonylphenol.

As the carboxyl group-containing ethylenically unsaturated monomer, the monomer described above can be used.

The phosphoric acid 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 phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid. be.

<Alkali-soluble resin without ethylenically unsaturated double bond>
The coloring composition of the present invention may contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of curing of the film.

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 30,000 or less, preferably 4,000, in order to impart alkali development solubility. More preferably 20,000 or less. Further, the value of Mw / Mn is preferably 10 or less. When the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain. If it exceeds 40,000, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated.
The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg / g) in order to impart alkali development solubility, preferably 70 or more and 180 or less, and more preferably 90 or more and 170 or less. Is. When the acid value is less than 50, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated. If it exceeds 200, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain.

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

<Thermosetting compound>
In the present invention, the binder resin can be used in combination with a thermoplastic resin to further contain a thermosetting compound. When a color filter is produced using the coloring composition for a color filter of the present invention, the inclusion of a thermosetting compound causes a reaction during firing of the filter segment to increase the crosslink density of the coating film, and thus the heat resistance of the filter segment is increased. It is improved, pigment aggregation at the time of firing the filter segment is suppressed, and the effect of improving the contrast ratio can be obtained.

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, but are limited to, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. It is not something that is done. Epoxy compounds and oxetane compounds are preferably used in the coloring composition for color filters of the present invention.

<Polymerizable compound>
The coloring composition of the present invention can be made into a photosensitive coloring composition by containing a polymerizable compound and a photopolymerization initiator. The polymerizable compound includes a monomer or an oligomer that is cured by ultraviolet rays, heat, or the like to form a transparent resin. The photosensitive coloring composition may be simply referred to as a coloring composition.

The polymerizable compound is, for example, 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, Trimethylol propanthry (meth) acrylate, Phenoxytetra Ethylene 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, ditrimethylol propanetetra (meth) acrylate, 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, methylolation Various acrylic acid esters such as melamine (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol Examples thereof include trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

(Polymerizable compound having an acid group)
The polymerizable compound can contain a photopolymerizable monomer having an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

The photopolymerizable monomer having an acid group is, for example, an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyvalent carboxylic acid and a mono. Examples thereof include esterified products with hydroxyalkyl (meth) acrylates. Specific examples include monohydroxyoligoacrylates such as trimethylolpropanediacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. , Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid; propane-1,2,3-tricarboxylic acid (tricarboxylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxy Examples thereof include monohydroxymonoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates.

(Polymerizable compound with urethane bond)
The polymerizable compound can contain a monomer having an ethylenically unsaturated bond and a urethane bond. The monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional isocyanate being reacted with an alcohol and further reacting with a (meth) acrylate having a hydroxyl group. Examples thereof include polyfunctional urethane acrylate obtained by subjecting the mixture.

The (meth) acrylate having a hydroxyl group includes 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylol propanetri (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 , Gloxydimethacrylate, 2-hydroxy-3-acryloylpropylmethacrylate, a reaction product of an epoxy group-containing compound and a carboxy (meth) acrylate, a hydroxyl group-containing polyol polyacrylate and the like.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

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

The blending amount of the polymerizable compound is preferably 1 to 50% by mass, more preferably 2 to 40 parts by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is blended, the curability and developability are further improved.

<Photopolymerization initiator>
The photopolymerization initiator is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1 -Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -1- [4- (4-morpholino) phenyl] -2- (Phenylmethyl) -1-butanone, or 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, etc. Acetphenone compounds; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone , 4-Benzoyl-4'-methyldiphenylsulfide, or benzophenone compounds such as 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone. , Isoxanthone compounds such as isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 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-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6- Triazine compounds such as triazine or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyl oxime)], or oxime esters such as etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) Compounds; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphinoxide or diphenyl-2,4,6-trimethylbenzoylphosphinoxide; 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone. Kinone-based compounds such as; borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanosen-based compounds and the like can be mentioned. Among these, oxime ester compounds are preferable.

The photopolymerization initiator can be used alone or in combination of two or more.

(Oxime ester compound)
The oxime ester compound breaks the NO bond of the oxime by absorbing ultraviolet rays, and produces an iminyl radical and an arcroxy radical. Since these radicals are further decomposed to generate highly active radicals, 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 be low and the curing degree of the coating film may be low, but the oxime ester compound is preferably used because it has high quantum efficiency. To.

The oxime ester compound is described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-0372223, JP-A-2010-215575, JP-A-2011-02998, and the like. Examples thereof include ester-based photopolymerization initiators.

The content of the photopolymerization initiator is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the colorant. When an appropriate amount is blended, the photocurability and developability are further improved.

<Sensitizer>
Further, the photosensitive coloring composition of the present invention may contain a sensitizer.
Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, aclysine derivatives, azine derivatives, thiadine derivatives, oxadin derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglycilate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4'- Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-bis (diethylamino) benzophenone.

Among the above sensitizers, examples of the sensitizer that can be particularly preferably sensitized include a thioxanthone derivative, a Michler ketone derivative, and a carbazole derivative. 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, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

More specifically, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " The sensitizer described in "Special Functional Materials" (1986, CMC) can be mentioned, but is not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

The sensitizer can be used alone or in combination of two or more.

The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the photopolymerization initiator. When an appropriate amount is contained, the curability and developability are further improved.

<Thiol chain transfer agent>
The photosensitive coloring composition of the present invention preferably contains a thiol-based chain transfer agent as the chain transfer agent. By using thiol together with a photopolymerization initiator, a chile radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation, so that the obtained coloring composition becomes highly sensitive. ..

Further, a polyfunctional aliphatic thiol bonded to an aliphatic group such as methylene or ethylene group having two or more thiol groups is preferable. More preferably, it is a polyfunctional aliphatic thiol having 4 or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and the pattern can be cured from the surface to the vicinity of the substrate.

Examples of the polyfunctional thiol include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropio. Nate, Trimethylol Propanetristhioglycolate, Trimethylol Protantithithiopropionate, Trimethylol Propanthris (3-mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetrakissthiopropionate, Trimercaptopropionic Acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s- Examples thereof include triazine, and preferred examples include ethylene glycol bisthiopropionate, trimethylolpropanetristhiopropionate, and pentaerythritol tetrakisthiopropionate.

The thiol chain transfer agent can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 0.1 to 10% by mass, 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 contained, the light sensitivity and the tapered shape are improved, and wrinkles are less likely to occur on the surface of the coating film.

<Polymerization inhibitor>
The photosensitive coloring composition may contain a polymerization inhibitor. As a result, the exposure due to the diffracted light of the mask can be suppressed during the exposure of the photolithography method, so that a pattern having a desired shape can be easily obtained.

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-. Propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4- Alkyl catechol compounds such as tert-butyl catechol and 3,5-di-tert-butyl catechol, 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl Alkyl resorcinol compounds such as resorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, Alkylhydroquinone compounds such as 2,5-di-tert-butylhydroquinone, phosphin compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide and the like. Examples thereof include phosphine oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol and fluoroglucin.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass in 100% by mass of the non-volatile content of the photosensitive coloring composition. In this range, the effect of the polymerization inhibitor is increased, and the linearity of the taper, wrinkles of the coating film, pattern resolution, and the like are improved.

<UV absorber>
The photosensitive coloring composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples thereof 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 ultraviolet absorber is preferably 5 to 70% by mass based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount is contained, the resolution after development is further improved.

The total content of the photopolymerization initiator and the ultraviolet 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 film is further improved, and good resolution can be obtained.

Examples of benzotriazole compounds include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, and 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-benzotriazole-2-yl)-(1,1-dimethyl)-(1,1-dimethyl) Ethyl) -4-hydroxy, a mixture of C7-9 side chains and linear alkyl esters, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3-( Reaction product of 2H-benzotriazole-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300, 2- (2H-benzotriazole-2-yl) -4- (1,1) , 3,3-Tetramethylbutyl) Phenol, 2,2'-Methylenebis [6- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2 -(2H-benzotriazole-2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazole-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-benzotriazole-2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-) 2H-benzotriazole-2-yl) phenyl] propionate can be mentioned. In addition, oligomer-type and polymer-type compounds having a benzotriazole structure can also be used.

Examples of 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, 2- (2,4-dihydroxyphenyl) ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate ester reaction product, 2,4-bis "2-hydroxy-4- Butoxyphenyl "-6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- (hexyl) Oxy) phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 2,4,6-tris (2-Hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine and the like can be mentioned. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

Examples of the benzophenone compound include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, and the like. 2,2'-Dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadesiloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2 , 2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like. In addition, oligomer-type and polymer-type compounds having a benzophenone structure can also be used.

Examples of the salicylic acid ester compound include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate. In addition, oligomer-type and polymer-type compounds having a salicylic acid ester structure can also be used.

<Antioxidant>
The photosensitive coloring composition of the present invention may contain an antioxidant. Antioxidants are used to reduce the transmittance of the coating film in order to prevent the photopolymerization initiator and thermosetting compound contained in the photosensitive coloring composition from oxidizing and yellowing due to the thermal process during thermal curing or ITO annealing. Can be improved. In particular, when the colorant concentration of the coloring composition is high, the amount of the cross-linking component of the coating film decreases, so that the yellowing of the thermal process becomes stronger due to the use of a highly sensitive cross-linking component and the increase in the amount of the photopolymerization initiator. Can be seen. Therefore, by containing an antioxidant, it is possible to prevent yellowing due to oxidation during the heating step and obtain a high transmittance of the coating film.

Examples of the antioxidant 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, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant are preferable from the viewpoint of achieving both the transmittance and the sensitivity of the coating film.

The antioxidant can be used alone or in combination of two or more.

Further, the content of the antioxidant is more preferably 0.5 to 5.0% by mass in 100% by mass of the solid content of the coloring composition because the transmittance, the spectral characteristics and the sensitivity are good.

<Leveling agent>
It is preferable to add a leveling agent to the coloring composition of the present invention for the purpose of improving the coatability of the composition on the transparent substrate and the drying property of the colored film. As the leveling agent, various surfactants such as silicone-based surfactants, fluorine-based 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% by mass, more preferably, with respect to the total solid content of the composition of the present invention. Is 0.005 to 1.0% by mass. 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 of surfactant. When two or more types are included, it is preferable that the total amount is 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 the storage stabilizer include quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphorous acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Examples thereof include organic phosphine and phosphite. The storage stabilizer can 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 improving agent such as a silane coupling agent in order to enhance the adhesion to the substrate. By improving the adhesion by the adhesion improver, the reproducibility of fine lines is improved and the resolution is improved.

Examples of the adhesion improver include vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-. (Meta) acrylic silanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxy Silane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-) Aminosilanes such as butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropylmethyldimethoxy Melcaptos such as silane, 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureids such as 3-ureidopropyltriethoxysilane, and sulfides such as bis (triethoxysilylpropyl) tetrasulfide. , 3-Silane Coupling agents such as isocyanates such as propyltriethoxysilane and the like can be mentioned. 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 with respect to 100 parts by mass of the colorant in the coloring composition. It is more preferable because the effect is large within this range and the balance between adhesion, resolution and sensitivity is good.

<Manufacturing method of coloring composition>
The coloring composition contained in the present invention comprises kneading a colorant in a dispersant, a colorant carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid (dye derivative or surfactant). It can be finely dispersed and produced by using various dispersion means such as 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 kinds of colorants and the like may be dispersed in the colorant carrier at the same time, or separately dispersed in the colorant carrier may be mixed. If the colorant such as a dye is highly soluble, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is confirmed, it is manufactured by finely dispersing it as described above. No need.

When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent-developing type or alkali-developing type coloring composition. The solvent-developed or alkaline-developed coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and if necessary, a solvent, other dispersion aids, and additives. Etc. can be mixed and adjusted. 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 coloring composition of the present invention contains a solvent so as to be applied on a substrate such as glass so that the dry film thickness is 0.2 to 5 μm to facilitate the formation of a coloring film. The solvent is selected in consideration of the solubility of each component of the coloring composition and the safety in addition to the good coatability of the coloring composition.

As the solvent, a solvent usually used in the art can be used, and in consideration of performance such as boiling point, SP value, evaporation rate, viscosity, etc., it may be used alone or as appropriate according to the coating conditions (speed, drying conditions, etc.). Used as a mixture.

Examples of the solvent used include an ester solvent (solvent containing -COO- in the molecule and not containing -O-) and an ether solvent (solvent containing -O- in the molecule and not containing -COO-). , Ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule but not -COO-), alcohol solvent (OH in the molecule) Included, -O-, -CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Among the above solvents, it is preferable to include an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm from the viewpoint of coatability and drying property. 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 and the like are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferable.

<Removal of coarse particles>
The colored composition of the present invention has coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0. It is preferable to remove coarse particles of 5 μm or more and mixed dust. As described above, it is preferable that the coloring composition does not contain particles having a size of 0.5 μm or more. It is more preferably 0.3 μm or less.

<Manufacturing method of near infrared cut filter>
The near-infrared cut filter of the present invention can be manufactured by a printing method or a photolithography method. Since the formation of the filter segment by the printing method can be patterned by printing and drying the coloring composition, the filter manufacturing method is low cost and excellent in mass productivity. Furthermore, with the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted by using a dispersant or an extender pigment.

When forming a filter segment by a photolithography method, a colored composition prepared as a solvent-developed or alkali-developed resist material is applied onto a substrate by a spray coating, spin coating, slit coating, roll coating or other coating method. Apply so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a solvent or alkaline developer or spraying the developer with a spray to remove the uncured part to form a desired pattern, the same operation is repeated for other colors to manufacture a filter. Can be done. Further, in order to promote the polymerization of the resist material, heating can be applied as needed. According to the photolithography method, a filter with higher accuracy than the above printing method can be manufactured.

The substrate is not particularly limited, but a sheet-shaped, film-shaped, or plate-shaped transparent base material can be used as the shape. Colors are also colorless and colored, and are not particularly limited. The material of the transparent base material is a highly transparent material, for example, a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), or triacetyl cellulose (TAC). Examples thereof include acrylic resins such as methyl methacrylate-based copolymers, styrene resins, polysulfone resins, polyethersulfone resins, polycarbonate resins, vinyl chloride resins, polymethacrylicimide resins, and glass plates.

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

The near-infrared cut filter of the present invention can be manufactured by an electrodeposition method, a transfer method, an inkjet method, or the like in addition to the above method.

<Use>
The coloring composition of the present invention can be used, for example, for a sensor for biometric authentication (fingerprint authentication or vein authentication), or a touch sensor or touch panel incorporating the sensor.
For example, smartphones, tablet PCs, etc., bank ATMs, multimedia terminals, etc. are equipped with biometric authentication functions such as fingerprint authentication and finger vein authentication for security protection. In particular, the development of fingerprint authentication technology used for smartphones and tablet PCs is rapid, and as the authentication range increases to the screen size (full screen), fingerprint authentication sensors with built-in displays have been developed for organic EL displays, liquid crystal displays, etc. There is.
However, since many fingerprint sensors with a built-in display irradiate the fingerprint with various light sources installed in the display and sense the reflected light, illegal external light (such as sunlight or LED lighting) is used. When a sensor has a wide range of wavelengths and is subject to strong light), there is a problem of noise during imaging, and there is some concern about accuracy when using it outdoors. The coloring composition of the present invention is effective in solving these problems by absorbing and preventing the incident of an external illegal light on the sensor.
Further, since the coloring composition of the present invention has excellent heat resistance, it can be preferably used in terms of a process for manufacturing a sensor, a touch sensor incorporating the sensor, and a touch panel.
In addition, 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 in particular, light of 650 nm to 800 nm overflows in the living space, so it is possible to cut light in this wavelength region. Increase the accuracy of biometric authentication.

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

(Method for identifying squarylium dye (A))
The MALDI TOF-MS spectrum was used for identification of the near-infrared absorbing pigment used in the present invention. For the MALDI TOF-MS spectrum, the obtained compound was identified by matching the molecular ion peak of the obtained mass spectrum with the mass number obtained by calculation using the MALDI mass spectrometer autoflex III manufactured by Bruker Daltonics. rice field.

(Acid value of resin type dispersant and binder resin)
The acid value of the resin type dispersant and the binder resin was determined by a potentiometric titration method using a 0.1 N potassium hydroxide / ethanol solution. The acid value of the resin and the resin type dispersant indicates the acid value of the non-volatile component.

(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 GPC (Tosoh, HLC-8120GPC) equipped with a RI detector using a TSKgel column (manufactured by Tosoh), and THF is used as a developing solvent. It is a polystyrene-equivalent weight average molecular weight (Mw) measured in the above.

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

(Quaternary ammonium salt value of resin type dispersant)
The quaternary ammonium salt value of the resin-type dispersant was determined by titrating with a 0.1 N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted to an equivalent amount of potassium hydroxide. The quaternary ammonium salt value of the resin type dispersant below indicates the quaternary ammonium salt value of the non-volatile component.

<Manufacturing of miniaturized squarylium dye (P)>
(Synthesis of squarylium pigment (A2-1))
400 parts of toluene is 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 is heated and stirred in an atmosphere of nitrogen gas. It was refluxed for hours. The water produced during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, 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 to create an atmosphere of nitrogen gas. The mixture was heated and stirred inside, and the mixture was refluxed for 8 hours. The water produced during the reaction was removed from the reaction system by azeotropic distillation.
After completion of the reaction, the solvent was distilled and 200 parts of hexane was added while stirring the obtained reaction mixture. The obtained black-brown precipitate was filtered off, washed successively with hexane, ethanol and acetone, and dried under reduced pressure to obtain 61.9 parts (yield: 92%) of squarylium dye (A2-1). rice field. As a result of mass spectrometry by TOF-MS, it was identified as a squarylium dye (A2-1).

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

(Synthesis of squarylium pigment (A2-3))
The same operation as the synthesis of the squarylium dye (A2-1) was performed except that 28.6 parts of 4-methylcyclohexanone was used instead of the 25.1 parts of cyclohexanone used in the synthesis of the squarylium dye (A2-1). , 67.2 parts (yield: 95%) of squarylium dye (A2-3) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a squarylium dye (A2-3).

(Synthesis of squarylium pigment (A3-1))
400 parts of toluene was 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 an atmosphere of nitrogen gas. It was refluxed for 3 hours. The water produced during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, 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 to create an atmosphere of nitrogen gas. The mixture was heated and stirred inside, and the mixture was refluxed for 8 hours. The water produced during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the solvent was distilled and 200 parts of hexane was added while stirring the obtained reaction mixture. The obtained 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 squarylium dye (A3-1). rice field. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a squarylium dye (A3-1).

(Synthesis of squarylium pigment (A3-2))
Squalylium dye (60.7 parts of 2,7-bis (trifluoromethyl) -9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the synthesis of squalylium dye (A3-1). The same operation as in the synthesis of A3-1) was carried out to obtain 109.8 parts (yield: 91%) of the squarylium dye (A3-2). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a squarylium dye (A3-2).

(Synthesis of squarylium dye (A3-3))
With the synthesis of squarylium dye (A3-1), 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). The same operation was carried out to obtain 83.9 parts (yield: 92%) of squarylium dye (A3-3). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a squarylium dye (A3-3).

(Solvent treatment and miniaturization of squarylium dye (A))
[Solvent treatment process]
50 parts of squarylium dye (A2-1) was mixed with 250 parts of N-methylpyrrolidone, and the mixture was stirred at 23 ° C. for 24 hours. Then, the mixture was filtered, washed with 150 parts of methanol, taken out, and dried at 80 ° C. for 24 hours 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 placed in a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 12 hours. Next, the kneaded mixture is put into warm water, stirred for 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water to remove salt and diethylene glycol, and then dried at 80 ° C. for 24 hours and crushed. As a result, 9.4 parts of a finely divided slurryyl dye (P2-1) was obtained.
[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 micrograph. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle size of the pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating it to a cube having the obtained particle size, and the volume average particle size was taken as the average primary particle size. The electron microscope used was a transmission type (TEM).
As a result of measurement by this method, the average primary particle size was 50 nm.
[Component ratio]
5.0 mg of squarylium dye (P2-1) was placed in a 100 ml volumetric flask, THF for HPLC was added, and ultrasonic waves were irradiated for 30 minutes to dissolve the mixture, and a 100 ml THF solution was prepared. Using this solution, HPLC measurement of dye compound B was carried out under the above equipment and the above conditions.
The HPLC measurement was analyzed by reverse phase liquid chromatography under the condition of using a mixed solution of acetonitrile and water in a volume ratio of 8: 2 as a mobile phase.
As a result, multiple peaks were shown.
Specifically, a peak with a retention time of 12 ± 1 minute (peak 1), a peak with a retention time of 42 ± 1 minute (peak 2), and a peak with a retention time of 46 ± 2 minutes (peak 3). It is composed of a peak with a retention time of 50 ± 2 minutes (peak 4) and a peak with a retention time of 57 ± 2 minutes (peak 5).
The area of peak 5 was 70% of the total area of peaks 1-5.

The squarylium dyes (A2-2) and (A2-3) were treated with a solvent and refined in the same manner as the squarylium dye (A2-1) to obtain micronized squarylium dyes (P2-2) and (P2-3). .. The squarylium dyes (A3-1) to (A3-3) were not treated with a solvent and were only miniaturized to obtain miniaturized squarylium dyes (P3-1) to (P3-3). Table 1 shows the refined squarylium dye (P).

<Other squarylium dyes (X)>
The G pigment SQ-R1 used in the examples of Patent Document WO2020 / 013089 was used as another squarylium dye (X), and miniaturized in the same manner as the squarylium dye (A2-1). The refined squarylium dye (X) is referred to as a miniaturized squarylium dye (PX).

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

<Manufacturing of dye (B)>
(Manufacturing of dye (B-1))
To 1250 parts of n-amyl alcohol in the reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were added and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was 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. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid in the reaction vessel at room temperature. The sulfuric acid solution was injected into 24,000 parts of cold water at 3 ° C. with stirring at 40 ° C. for 3 hours. 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).

反応容器中でメタノール１０００部に、上記式（６）で表されるアルミニウムフタロシアニン顔料を１００部と、ジフェニルホスフィン酸を４３．２部とを加え、４０℃に加熱し、８時間反応させた。これを室温まで冷却後、生成物をろ過し、メタノールで洗浄後、乾燥させて、色素（Ｂ－１）を１１２部を得た。
続いて、得られた色素（Ｂ－１）を１００部と、塩化ナトリウムを１２００部と、ジエチレングリコール１２０部とをステンレス製１ガロンニーダー（井上製作所製）に仕込み、７０℃で６時間混練した。この混練物を３０００部の温水に投入し、７０℃に加熱しながら１時間撹拌してスラリー状とし、濾過、水洗を繰り返して塩化ナトリウムおよびジエチレングリコールを除いた後、８０℃で一昼夜乾燥し、微細化された色素（Ｂ－１）を得た。平均一次粒子径は２９.５ｎｍであった。 Equation (6)

In a reaction vessel, 100 parts of an aluminum phthalocyanine pigment represented by the above formula (6) and 43.2 parts of diphenylphosphine acid were added to 1000 parts of methanol, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol and dried to obtain 112 parts of dye (B-1).
Subsequently, 100 parts of the obtained dye (B-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This kneaded product is put into 3000 parts of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours and finely. A modified dye (B-1) was obtained. The average primary particle size was 29.5 nm.

(Manufacturing of dye (B-2))
To 1000 parts of methanol in a reaction vessel, 100 parts of an aluminum phthalocyanine pigment represented by the above formula (6) and 49.5 parts of diphenyl phosphate were added, heated to 40 ° C., and reacted for 8 hours. This was cooled to room temperature, the product was filtered, washed with methanol and dried to give 114 parts of dye (B-2).
The obtained dye (B-2) was subjected to the same salt milling treatment method as that of the dye (B-1) to obtain a finely divided dye (B-2). The average primary particle size was 31.2 nm.

(Manufacturing of dye (B-3))
To a three-necked flask, add 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), and stir. The reaction was carried out at 20 ° C. for 4 hours. Then, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added, and the mixture was stirred at 80 ° C. for 1 hour. Then, the mixture was collected by filtration, washed with water, and dried to obtain a pigment in which 8.0 bromine atoms were substituted on the phthalocyanine ring on average.
Next, to a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 8.0 bromine atoms substituted on the obtained phthalocyanine ring, and 18.2 parts of diphenyl phosphate were added, and 90 parts were added. The mixture was heated to ° C. and reacted for 8 hours. This was cooled to room temperature, the product was filtered, washed with methanol and dried to give the dye (B-3). The average primary particle size was 27 nm.

Equation (7)

(Manufacturing of dye (B-4))
Except for changing the 104.4 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) used in the production of the dye (B-3) to 129.3 parts and the reaction time of 4 hours to 6 hours. The same operation as in the production of the dye (B-3) was carried out to obtain a pigment in which an average of 10.1 bromine atoms were substituted on the phthalocyanine ring.
Next, to a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment in which an average of 10.1 bromine atoms were substituted on the obtained phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added, and 90 parts were added. The mixture was heated to ° C. and reacted for 8 hours. This was cooled to room temperature, the product was filtered, washed with methanol and dried to give the dye (B-4). The average primary particle size was 27 nm.

(Manufacturing of dye (B-5))
250 parts of aluminum chloride, 60 parts of sodium chloride and 2.25 parts of iodine were added to a three-necked flask, and the mixture was stirred at 150 ° C. for 30 minutes. 50 parts of the aluminum phthalocyanine pigment represented by the above formula (6) was added thereto, and the mixture was stirred at 155 ° C. for 30 minutes and dissolved. Further, 58.5 parts of trichloroisocyanuric acid was added, and the mixture was stirred at 190 ° C. for 5 hours. Then, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added, and the mixture was stirred at 80 ° C. for 1 hour. Then, the mixture was collected by filtration, 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, to a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment in which an average of 8.1 chlorine atoms were substituted in the obtained phthalocyanine ring, and 22.6 parts of diphenyl phosphate were added, and 90 parts were added. It was heated to ° C. and reacted for 8 hours. This was cooled to room temperature, the product was filtered, washed with methanol and dried to give the dye (B-5). The average primary particle size was 29 nm.

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

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

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

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

（式（８）中、ＣｕＰｃは、銅フタロシアニン構造残基である。） Equation (8)

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

<Manufacturing of dispersant solution>
(Manufacturing of 1 solution of basic resin type dispersant)

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

Equation (9)

In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 15.7 parts of methyl methacrylate, 47.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and 50 parts were flowed with nitrogen. The mixture was stirred at ° C. for 1 hour, 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 make the first block. Polymerization was started. 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 in terms of the non-volatile content.
Next, 25 parts of PGMAc and 30.3 parts of the above compound [b] as a second block monomer were put into this reaction vessel, and the mixture was stirred while maintaining a nitrogen atmosphere at 110 ° C. to continue the reaction. Two hours after the addition of the compound [b] represented by the above formula (9), the polymerization solution is sampled and the solid content is measured, and the polymerization conversion rate of the second block is 98% or more in terms of the non-volatile content. It was confirmed.
Further, 6.8 parts of benzyl chloride was added to this reaction device, and the mixture was stirred for 3 hours while maintaining the atmosphere of 110 ° C. and nitrogen, and then cooled.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by weight. In this way, the basic resin type dispersant 1 having an amine value of 70 mgKOH / g per solid content, a quaternary ammonium salt value of 30 mgKOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by weight. A solution was obtained.

(Manufacturing of other dispersant 2 solutions)
In a reaction vessel equipped with a gas introduction tube, temperature, condenser, and stirrer, 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 are charged, and nitrogen gas is charged. Replaced with. The inside of the reaction vessel was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and the reaction was carried out for 7 hours while adding a solution of 0.1 part of 2,2'-azobisisobutyronitrile added to 90 parts of propylene glycol monomethyl ether acetate. It was confirmed by solid content measurement that 95% had reacted.
Add 19 parts of pyromellitic acid anhydride, 50 parts of propylene glycol monomethyl ether acetate, and 0.4 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst, and react at 100 ° C. for 7 hours. rice field. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the reaction was terminated, and propylene glycol monomethyl ether acetate was added to dilute the acid so that the solid content was 40% by measuring the solid content. Two other dispersant solutions having a value of 70 mgKOH / g and a mass average molecular weight of 8500 were obtained.

<Manufacturing of binder resin solution>
(Manufacturing of 1 solution of binder resin)
A reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then the dropping tube was used. N-butyl methacrylate 13.3 parts, 2-hydroxyethyl methacrylate 4.6 parts, methacrylic acid 4.3 parts, paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) 7.4 parts, A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl is prepared so that the non-volatile content is 20% by mass in the previously synthesized resin solution. Ether acetate was added to prepare a binder resin 1 solution.

(Manufacturing of binder resin 2 solution)
370 parts of cyclohexanone was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, the temperature was raised to 80 ° C., the inside of the flask was replaced with nitrogen, and then the dropping tube was used. A mixture of 18 parts of cyclopentanyl 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. .. After the dropping, the reaction was further carried out at 100 ° C. for 3 hours, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the above container at 120 ° C. The reaction was continued for 6 hours, and when the solid acid value reached 0.5, the reaction was terminated to obtain a solution of acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were subsequently added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content is 20% by mass in the previously synthesized resin solution. Acetate was added to prepare a binder resin 2 solution. The weight average molecular weight (Mw) was 19000.

<Manufacturing of coloring composition (S)>

(Manufacturing of Coloring Composition (S-1))
After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed in an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a diameter of 0.5 μm to obtain the colored composition (S-1). Made.
Miniaturized 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

(Manufacturing of Coloring Compositions (S-2) to (S-7))
Hereinafter, the coloring compositions (S-2) to (S-) are the same as those of the coloring composition (S-1) except that the miniaturized squarylium dye (P2-1) is changed to the miniaturized squarylium dye shown in Table 1. 7) was produced.

<Measurement of maximum absorption wavelength of coloring composition (S)>
Obtained coloring composition (S): 60.0 parts, binder resin 1 solution: 15.0 parts, PGMAC: 25.0 parts After uniformly stirring and mixing, a spin coater was placed on a glass substrate having a thickness of 1.1 mm. The substrate was spin-coated to a film thickness of 1.0 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 results of the maximum absorption wavelength are shown in Table 1.

<Manufacturing of coloring composition (C)>

(Manufacturing of Coloring Composition (C-1))
After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed in an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a filter having a diameter of 0.5 μm to obtain the colored composition (C-1). Made.
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 Coloring Compositions (C-2) to (C-9))
Hereinafter, the coloring compositions (C-2) to (C-9) were prepared in the same manner as the coloring composition (C-1) except that the dye (B-1) was changed to the dye shown in Table 2.

<Evaluation of spectral characteristics of coloring composition (C)>
After uniformly stirring and mixing the obtained coloring composition (C): 50.0 parts, binder resin 1 solution: 25.0 parts, and PGMAC: 25.0 parts, a spin coater was placed on a glass substrate having a thickness of 1.1 mm. Was spin-coated 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 or not the spectral characteristics satisfy the following conditions (1) and (2). The results are shown in Table 3.

(1) When the coating film is formed so that the transmittance at 680 nm is 1%, the minimum value (T1) of the transmittance at 400 to 450 nm is 20% or more (2) The transmittance at 680 nm becomes 1%. When the coating film is formed as described above, 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 the above conditions (1) and (2). There is. On the other hand, the PG58 and PG36 used in the coloring composition (C-7) and (C-8) do not satisfy the above condition (1), and PB15: 6 used in the coloring composition (C-9). Is a spectral characteristic that does not satisfy the above condition (2).

<Manufacturing of coloring composition (D)>
(Examples 1 to 38: coloring compositions (D-1) to (D-38),
Comparative Examples 1 to 5: Production of Coloring Compositions (D-39) to (D-43))
Hereinafter, the coloring compositions (D-1) to (D-) are the same as those of the coloring composition (C-1) except that the dyes and dispersants are changed to the compositions and amounts shown in Tables 4-1 to 4-3. 43) was prepared.

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

<Evaluation of spectral characteristics of colored composition>
After uniformly stirring and mixing the obtained coloring composition (D) or coloring composition (C-2): 31.0 parts, binder resin 1 solution: 44.0 parts, and PGMAC: 25.0 parts, 1. A substrate was prepared by spin-coating a 1 mm thick glass substrate with a spin coater so that the coating film thickness was 1.5 μm, drying at 60 ° C. for 5 minutes, and then heating at 230 ° C. for 20 minutes. .. 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 following criteria. The evaluation results are shown in Tables 4-1 to 4-3.

Spectral characteristics 1: 450 nm to 550 nm
◯: 75% ≦ (T)
Δ: 65% ≤ (T) <75%
×: (T) <65%

Spectral characteristics 2: 600 nm to 750 nm
〇: (T) ≤ 10%
Δ: 10% <(T) ≤ 15%
×: 15% <(T)

Spectral characteristics 3: 750 nm to 850 nm
〇: (T) ≤ 10%
Δ: 10% <(T) ≤ 15%
×: 15% <(T)

Spectral characteristics 4: 550 nm-600 nm
〇: (T) ≤ 20%
Δ: 20% <(T) ≤ 65%
×: 65% <(T)

<Evaluation of filterability of colored composition>
10 g of the obtained coloring composition (D) or coloring composition (C-2) is passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number; 39115221) at a nitrogen pressure (0.3 MPa), and obtained through the filter. The amount was measured and evaluated according to the following criteria.
The evaluation results are shown in Tables 4-1 to 4-3.
〇: 5.0 g ≤ Filtration amount △: 3.0 g ≤ Filtration amount <5.0 g
×: Filtration amount ≤ 3.0 g

By including 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 satisfying the above conditions (1) and (2), for example, a fingerprint. We were able to obtain a colored composition that has high transmittance of blue and green light used for detection such as authentication (spectroscopic characteristics 1) and cuts red light and near infrared rays that cause noise (spectroscopic characteristics 2 and 3). .. It was also confirmed that the inclusion of the dye (B-6) can cut red light that becomes noise from the shorter wavelength side (spectral characteristic 4). Furthermore, it was confirmed that the filtration property was improved by containing the squarylium dye (A) and the dye (B).

<Manufacturing of Photosensitive Coloring Composition (R)>
(Example 39: Production of photosensitive coloring composition (R-1))
A mixture having the following composition was uniformly stirred and mixed, and then filtered through a 0.5 μm filter to prepare a photosensitive coloring composition (R-1).
Coloring composition (D-1): 31.3 parts Binder resin 2 solution: 8.5 parts Thermocurable compound (E): 0.8 parts Polymerizable compound (F): 4.5 parts Photopolymerization initiator ( G): 0.7 part Sensitizer (H): 0.1 part Thiol-based chain transfer agent (I): 0.2 part Polymerization inhibitor (J): 0.2 part 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 copies

(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, in the same manner as the photosensitive coloring composition (R-1) except that the coloring composition (D-1) is changed to the coloring composition shown in Table 5, the photosensitive coloring compositions (R-2) to ( R-8) was produced.

The details of the material used for producing the photosensitive coloring composition (R) are as follows.

[Thermosetting compound (E)]
-Epoxy compound (E-1)
(E-1-1) 1,2-Epoxy-4- (2-oxylanyl) 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 the same amount to prepare an epoxy compound (E-1).
-Oxetane compound (E-2):
3-Ethyl-3-[(3-ethyloxetane-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 Co., Ltd.)]

(F-5) Pentaerythritol triacrylate (432 g, hexamethylene diisocyanate 84 g) was charged in a reaction vessel having a polyfunctional urethane acrylate content of 1 liter and 5 mouths according to the following, and reacted at 60 ° C. for 8 hours to form a (meth) acryloyl group. A product containing the polyfunctional urethane acrylate (F-5) having the above was obtained. The proportion of the polyfunctional urethane acrylate (F-5) in the product was 70% by mass, and the balance was other photopolymerizable. It is occupied by monomer. It was confirmed by IR analysis that the isocyanate group was not present in the reaction product.

(F-6) Bifunctional 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.)]
As described above, (F-1) to (F-7) were mixed in the same amount to obtain a photopolymerizable monomer (E).

[Photopolymerization Initiator (G)]
(G-1) 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one
[Omnirad 907 (manufactured by 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
[Viimidazole (manufactured by Kurokin Kasei Co., Ltd.)]
(G-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine)]
(G-6) Ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-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)]
As described above, (G-1) to (G-8) were mixed in the same amount to obtain a photopolymerization initiator (G).

[Sensitizer (H)]
(H-1) 2,4-Diethylthioxanthone
[Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(H-2) 4,4'-bis (diethylamino) benzophenone
[CHEMARK DEABP (manufactured by Chemark Chemical)]
As described above, (H-1) and (H-2) were mixed in the same amount to obtain a sensitizer (H).

[Thiol chain transfer agent (I)]
(I-1) Trimethylolethane ethanetris (3-mercaptobutyrate)
[TEMB (manufactured by Showa Denko)]
(I-2) Trimethylolpropanetris (3-mercaptobutyrate)
[TPMB (manufactured by 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.)]
As described above, (I-1) to (I-5) were mixed in the same amount 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 and (J-1) to (J-3) are mixed in the same amount, respectively, and a polymerization inhibitor is used. It was designated as (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
[TINUVIN400 (manufactured by BASF Japan)]
(K-2) 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol
[TINUVIN900 (manufactured by BASF Japan)]
As described above, (K-1) and (K-2) were mixed in the same amount to obtain an ultraviolet absorber (K).

[Antioxidant (L)]
(L-1) Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (L-2) 3,3'-dioctadecylthiodipropanoate (L-3) tris [2] , 4-Di- (tert) -butylphenyl] Phenylphosphite (L-4) bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (L-5) salicylic acid p-octylphenyl or higher, ( L-1) to (L-5) were mixed in the same amount to prepare an antioxidant (L).

[Leveling agent (M)]
1 part of "Megafuck F-551: Fluorine-containing lipophilic group-containing oligomer" manufactured by DIC Corporation,
"BYK-330: Polyether-modified Polydimethylsiloxane" manufactured by Big Chemie, 1 part,
A mixed solution in which 1 part of "Emargen 103: Polyoxyethylene lauryl ether" manufactured by Kao Corporation is 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 Hokuko Chemical Industry Co., Ltd.)
As described above, (N-1) and (N-2) were mixed in the same amount 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.)]
As described above, (O-1) to (O-4) were mixed in the same amount 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) Cyclo Hexanol acetate 10 parts (P-6) Dipropylene glycol methyl ether acetate 10 parts or more, (P-1) to (P-6) were mixed by the above mass parts to prepare a solvent (P).

<Evaluation of spectral characteristics of photosensitive coloring composition>
The obtained photosensitive coloring composition (R) was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater so that the coating film thickness was 1.5 μm, and dried at 60 ° C. for 5 minutes. Then, the substrate is irradiated with ultraviolet rays of 100 mJ / cm ² using an ultra-high pressure mercury lamp, spray-developed with an alkaline developer consisting of a 0.2 mass% sodium carbonate aqueous solution, and then heated at 230 ° C. for 20 minutes. Made. 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 the colored composition (D) was evaluated according to the same criteria as the spectral characteristic evaluation. The evaluation results are shown in Table 5.

<Evaluation of filterability of photosensitive coloring composition>
The obtained photosensitive coloring composition (R) 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 result is the same as that of the coloring composition, that is, the squalylium dye (A) having a maximum absorption wavelength in the range of 400 to 1000 nm between 700 and 900 nm, and the above conditions (1) and (2). By containing the dye (B) having spectral characteristics that satisfy the conditions, for example, the transmittance of blue and green light used for detection such as fingerprint authentication is high (spectral characteristic 1), and red light and near infrared rays that cause noise are cut off. (Spectroscopic characteristics 2, 3) It was possible to obtain a colored composition. It was also confirmed that the inclusion of the dye (B-6) can cut red light that becomes noise from the shorter wavelength side (spectral characteristic 4). Furthermore, it was confirmed that the filtration property was improved by containing the squarylium dye (A) and the dye (B).

Claims (8)

It is characterized by containing 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 satisfying the following conditions (1) and (2). Coloring composition to be.
(1) When the coating film is formed so that the transmittance at 680 nm is 1%, the minimum value (T1) of the transmittance at 400 to 450 nm is 20% or more. (2) The transmittance at 680 nm becomes 1%. When the coating film is formed as described above, the transmittance (T2) at 530 nm is 50% or more. The coloring composition according to claim 1, wherein the dye (B) is a phthalocyanine pigment. The coloring composition according to claim 2, wherein the dye (B) is an aluminum phthalocyanine pigment. The coloring composition according to claim 3, 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 are independently an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent. It has 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, or a substituent. Represents a optionally arylthio group.
Y _l to Y ₄ independently represent a halogen atom, a nitro group, a phthalimide methyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
M represents Al.
Z represents −OP (= O) R ₁₃ R ₁₄ , where R ₁₃ and R ₁₄ independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, and a substituent. It represents a good aryl group, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and R ₁₃ and R ₁₄ may be bonded to each other to form a ring.
m ₁ , m ₂ , m ₃ , m ₄ , n ₁ , n ₂ , n ₃ , and n ₄ independently represent integers from 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ respectively. + N ₃ , m ₄ + n ₄ are 0 to 4, respectively, and may be the same or different. ) The coloring composition according to any one of claims 1 to 4, wherein the squarylium dye (A) is at least one of the compounds represented by the following general formulas (2) and (3).
General formula (2)

(In the general formula (2), X ₁₀₁ to X ₁₁₀ each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. May have an aryl group, 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 , represents a nitro group, a cyano group or a halogen atom. R ₁₀₁ and R ₁₀₂ may independently have a hydrogen atom and a substituent, respectively. Represents an alkyl group. In X ₁₀₁ to X ₁₁₀ , substituents may be bonded to each other to form a ring.)

General formula (3)

(In the general formula (3), Q ₁ , Q ₄ , Q ₅ and Q ₈ independently represent a carbon atom or a nitrogen atom. When Q ₁ , Q ₄ , Q ₅ or Q ₈ are nitrogen atoms, It is assumed that there are no X ₂₀₁ , X ₂₀₄ , X ₂₀₅ or X ₂₀₈ .
R ₁ to R ₅ independently represent a hydrogen atom, a sulfo group, -SO ₃ ^- M ⁺ , or a halogen atom. M ⁺ represents an inorganic or organic cation.
Each of X ₂₀₁ to X ₂₀₈ independently contains 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, and a substituent. Aralkyl group which may have, alkoxy group which may have substituent, aryloxy group which may have substituent, hydroxyl group, amino group, -NR ₆ R ₇ , sulfo group, -SO ₂ NR ₈ R ₉ , -COOR ₁₀ , -CONR ₁₁ R ₁₂ , represents a nitro group, a cyano group or a halogen atom. X ₂₀₁ to X ₂₀₈ may be coupled to each other to form a ring.
R ₆ to R ₁₂ independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, and an acyl group or a substituent which may have a substituent. Represents a pyridinyl group that may have. R ₆ and R ₇ , R ₈ and R _{9, and} R ₁₁ and R ₁₂ may be coupled to each other to form a ring. ) The coloring composition according to any one of claims 1 to 5, further comprising a basic resin-type dispersant. The coloring composition according to claim 6, further comprising a photopolymerization initiator. A near-infrared cut filter comprising the coloring composition according to any one of claims 1 to 7.