JP2023073064A - Novel compounds, near-infrared absorbing dyes, near-infrared absorbing compositions, and optical filters - Google Patents

Abstract

To provide: compounds with high transmittance in the near-infrared region greater than 940 nm, excellent near-infrared cutting ability from 700 nm to 850 nm, and good heat resistance; and near-infrared absorbing dyes, near-infrared absorbing compositions and optical filters with good dispersion stability and heat resistance.SOLUTION: A compound represented by the general formula (1) or (2) is used.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to novel compounds, near-infrared absorbing dyes, near-infrared absorbing compositions, and optical filters.

Near-infrared absorbing materials include, for example, a near-infrared absorbing film that blocks heat rays, a near-infrared absorbing plate, a near-infrared absorbing film for agriculture that selectively uses sunlight, a recording medium that utilizes near-infrared absorption heat, and an electronic device. Used in a wide range of applications, such as near-infrared cut filters for cameras, near-infrared filters for photography, protective glasses, sunglasses, heat ray shielding films, dyes for optical recording, optical character reading and recording, confidential document copy prevention, electrophotographic photoreceptors, laser fusion bonding, etc. It is

Among them, solid-state imaging devices such as digital cameras and smartphones (CCD image sensors, CMOS image sensors, etc.) are sensitive to near-infrared rays. Certain near-infrared rays are cut with an optical filter to correct sensitivity.

In recent years, attempts have been made to add sensing functions (motion capture, spatial recognition, biometric authentication, etc.) using near-infrared rays to camera modules. may require the optical filter to be transparent for these detection wavelengths.

Thus, there is a need for a near-infrared absorbing material that selectively transmits visible light and a part of near-infrared rays, instead of uniformly cutting near-infrared rays like conventional materials.

Phthalocyanine dyes, cyanine dyes, diimmonium dyes, squarylium dyes, croconium dyes, indigo dyes, and the like are known as near-infrared absorbing dyes. Among these, particularly representative dyes include phthalocyanine dyes and cyanine dyes. Phthalocyanine dyes have a relatively robust structure, so they have good resistance to various types of dyes. Inferiority and invisibility. On the other hand, cyanine dyes, which are generally used as dyes in a dissolved state, have very high transparency and invisibility, but are remarkably poor in various resistances, particularly light resistance. Diimonium dyes, squarylium dyes, and croconium dyes also have similar characteristics to cyanine dyes.

As an indigo dye-based compound, Patent Document 1 discloses a boron compound. Further, Patent Document 2 discloses a palladium complex. However, these compounds were unable to achieve both absorption in the near-infrared region of 700 nm to 850 nm and dispersion stability.

JP 2012-224593 A JP 2013-87233 A

An object of the present invention is to provide a compound having high transmittance in the near-infrared region after 940 nm, excellent ability to cut near-infrared rays from 700 nm to 850 nm, and good heat resistance. Another object of the present invention is to provide a near-infrared absorbing colorant, a near-infrared absorbing composition, and an optical filter having good dispersion stability and heat resistance.

The present inventors have made intensive studies to solve the above problems, and as a result, the compound represented by the general formula (1) or general formula (2) has a high transmittance in the near-infrared region after 940 nm. , 700 nm to 850 nm, and have good heat resistance, leading to the present invention.

[式中、Ｘ_１～Ｘ_２２はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシル基、置換基を有していてもよいアリールオキシ基、置換基を有していてもよいアリールアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいアルキルチオ基、置換基を有していてもよいアリールチオ基、アミノ基、置換基を有していてもよいアルキルアミノ基、置換基を有していてもよいアリールアミノ基、シアノ基、ハロゲン原子、ニトロ基、水酸基、または、－ＳＯ₃Ｈ、－ＣＯＯＨ、これら酸性基の１価～３価の金属塩、もしくは、アルキルアンモニウム塩を表す。Ｘ_１～Ｘ_２２で示される基のうち隣り合う２個の基は、連結してそれぞれが結合する炭素原子と共に５員環又は６員環を形成してもよい。］ That is, the present invention relates to compounds characterized by being represented by general formula (1) or general formula (2).

[wherein X ₁ to X ₂₂ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted arylalkyl group, optionally substituted cycloalkyl group, optionally substituted optionally substituted alkylthio group, optionally substituted arylthio group, amino group, optionally substituted alkylamino group, optionally substituted arylamino group, cyano group, halogen atom , nitro group, hydroxyl group, --SO ₃ H, --COOH, monovalent to trivalent metal salts or alkylammonium salts of these acidic groups. Two adjacent groups among the groups represented by X ₁ to X ₂₂ may be linked to form a 5- or 6-membered ring together with the carbon atoms to which they are attached. ]

The present invention also relates to a near-infrared absorbing dye comprising the above compound.

The present invention also relates to a near-infrared absorbing composition comprising the near-infrared absorbing dye and a binder resin.

The present invention also relates to the near-infrared absorbing composition, wherein the water content in the near-infrared absorbing composition is 0.1 to 2.0% by mass relative to the entire near-infrared absorbing composition.

Further, the present invention contains a metal component containing a metal atom selected from Li, Na, Mg, K, Cs, Co, Ca, Fe, Si and Zr, and the near-infrared absorbing composition as a whole contains the above-mentioned It relates to the near-infrared absorbing composition, wherein the total amount of the metal atoms in the metal component is 1 to 1000 ppm by mass.

The present invention also relates to the near-infrared absorbing composition, which further contains a photopolymerizable monomer and/or a photopolymerization initiator.

The present invention also relates to the near-infrared absorbing composition, characterized by containing an organic dye having absorption in the range of 400 nm to 700 nm.

The present invention also relates to an optical filter comprising a substrate and a coating formed from the near-infrared absorptive composition.

The present invention provides a compound that has high transmittance in the near-infrared region after 940 nm and excellent ability to cut off near-infrared rays of 700 nm to 850 nm. Moreover, when the compound is used as a near-infrared absorbing dye, it is possible to provide a near-infrared absorbing composition having good dispersion stability and heat resistance, and an optical filter.

Terms used herein are defined. "(Meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" unless otherwise specified , “acryloyl and/or methacryloyl”, “acrylic and/or methacrylic”, “acrylic acid and/or methacrylic acid”, “acrylate and/or methacrylate”, or “acrylamide and/or methacrylamide”. References herein to "C.I." mean Color Index (C.I.). Pigments and colorants include pigments and dyes.

[式中、Ｘ_１～Ｘ_２２はそれぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシル基、置換基を有していてもよいアリールオキシ基、置換基を有していてもよいアリールアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいアルキルチオ基、置換基を有していてもよいアリールチオ基、アミノ基、置換基を有していてもよいアルキルアミノ基、置換基を有していてもよいアリールアミノ基、シアノ基、ハロゲン原子、ニトロ基、水酸基、または、－ＳＯ₃Ｈ、－ＣＯＯＨ、これら酸性基の１価～３価の金属塩、もしくは、アルキルアンモニウム塩を表す。Ｘ_１～Ｘ_２２で示される基のうち隣り合う２個の基は、連結してそれぞれが結合する炭素原子と共に５員環又は６員環を形成してもよい。］ <Compound Represented by General Formula (1) or General Formula (2)>
The compound represented by general formula (1) or general formula (2) of the present invention will be explained.

[wherein X ₁ to X ₂₂ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted arylalkyl group, optionally substituted cycloalkyl group, optionally substituted optionally substituted alkylthio group, optionally substituted arylthio group, amino group, optionally substituted alkylamino group, optionally substituted arylamino group, cyano group, halogen atom , nitro group, hydroxyl group, --SO ₃ H, --COOH, monovalent to trivalent metal salts or alkylammonium salts of these acidic groups. Two adjacent groups among the groups represented by X ₁ to X ₂₂ may be linked to form a 5- or 6-membered ring together with the carbon atoms to which they are attached. ]

The "alkyl group" of the alkyl group optionally having a substituent is, for example, 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. , n-octyl group, stearyl group, 2-ethylhexyl group, and other linear or branched alkyl groups. "Alkyl group having a substituent" includes, for example, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoro propyl group, 2-ethoxyethyl group, 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 and the like.

The "aryl group" of the aryl group optionally having a substituent includes, for example, a phenyl group, a naphthyl group, an anthryl group and the like.
"Aryl group having a substituent" includes, for example, p-methylphenyl group, 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 group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-amino Anthraquinonyl group and the like can be mentioned.

The "alkoxyl group" of the alkoxyl group which may have a substituent is, for example, 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, Linear or branched alkoxyl groups such as 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy and 2-ethylhexyloxy groups can be mentioned.
The "substituted alkoxyl group" includes, for example, a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditri fluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

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

"Optionally substituted arylalkyl group" includes, for example, benzyl group, 2-phenylpropan-yl group, styryl group, diphenylmethyl group, triphenylmethyl group and the like.

The "cycloalkyl group" of the cycloalkyl group which may have a substituent includes, for example, a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like. Examples of "substituted cycloalkyl group" include 2,5-dimethylcyclopentyl group, 4-tert-butylcyclohexyl group and the like.

The "alkylthio group" of the alkylthio group optionally having a substituent is, for example, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, an octadecylthio group, etc. is mentioned.
Examples of the "substituted alkylthio group" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, a phenylcarbonylaminoethylthio group and the like.

The "arylthio group" of the arylthio group optionally having a substituent includes, for example, a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group and the like.
"Arylthio group having a substituent" includes, for example, a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group, and the like. .

The "alkylamino group" of the optionally substituted alkylamino group includes, for example, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, Octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert -pentylamino group, tert-octylamino group, neopentylamino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1 -adamantamino group, 2-adamantamino group and the like.

The "arylamino group" of the arylamino group optionally having a substituent is, for example, anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4-biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group and the like.

Halogen atoms include fluorine, chlorine, bromine and iodine.

Examples of acidic groups include --SO ₃ H and --COOH, and examples of monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, and aluminum salts. mentioned. Examples of alkylammonium salts of acidic groups include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, palmityltrimethylammonium, lauryltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salts. and quaternary alkylammonium salts of.

Two adjacent groups among the groups represented by X ₁ to X ₂₂ may be linked to form a 5- or 6-membered ring together with the carbon atoms to which they are attached. The 5- or 6-membered ring may have a substituent. Such five-membered rings include cyclopentene ring, cyclopentadiene ring, imidazole ring, thiazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiophene ring, furan ring, pyrrole ring and the like. , cyclohexane ring, cyclohexene ring, cyclohexadiene ring, benzene ring, pyridine ring, piperazine ring, piperidine ring, morpholine ring, pyrazine ring, pyrone ring, pyrrolidine ring and the like.

Preferred substituents for X ₁ to X ₂₂ among the above substituents include a hydrogen atom, a methyl group, a chlorine atom and a bromine atom from the viewpoint of visible light transmittance.

(Method for synthesizing compound represented by general formula (1) or general formula (2))
Methods for synthesizing compounds represented by general formula (1) or general formula (2) are described below. The compound represented by general formula (1) can be obtained by reacting the compound represented by general formula (3) in a solvent in the presence of a boron compound and a Lewis acid. Further, the compound represented by general formula (2) can be obtained by reacting the compound represented by general formula (4) in a solvent in the presence of a boron compound and a Lewis acid. First, a method for synthesizing the compounds represented by general formulas (3) and (4) will be described.

[式中、Ｘ_２３～Ｘ_３６は、Ｘ_１～Ｘ_２２と同義である。］

[In the formula, X ₂₃ to X ₃₆ have the same definitions as X ₁ to X ₂₂ . ]

General formula (3) is obtained by reacting a compound having an indigo skeleton and a compound having an aniline skeleton in a solvent in the presence of aluminum chloride and 1,4-diazabicyclo[2.2.2]octane. be able to. The amount of aluminum chloride to be used is preferably 1.5 to 2.5 mol per 1 mol of the compound having an indigo skeleton.
The amount of the compound having an aniline skeleton to be used is preferably 1.0 to 2.0 mol per 1 mol of the compound having an indigo skeleton. The amount of 1,4-diazabicyclo[2.2.2]octane to be used is preferably 2.5 to 5.0 mol per 1 mol of the compound having an indigo skeleton. Although the reaction solvent is not particularly limited, examples thereof include toluene, xylene, chlorobenzene, bromobenzene and the like.

The compound represented by general formula (4) can be obtained according to the synthesis method described in JP-A-2012-224593.

Next, the process of synthesizing the compound represented by general formula (1) or general formula (2) from the compound represented by general formula (3) or general formula (4) will be described.

Although the reaction temperature is not particularly limited, it is preferably in the range of 100 to 200°C, more preferably 100 to 140°C.

Although the reaction solvent is not particularly limited, one in which the compound represented by general formula (3) or general formula (4) and the boron compound are dissolved is preferable. Specific examples include toluene, xylene, chlorobenzene, bromobenzene and the like.

The amount of the boron compound to be used is 1 mol or more, preferably 1.0 to 2.0 mol, per 1 mol of the compound represented by general formula (3) or general formula (4).

The boron compound used is preferably a borinic acid ester, particularly preferably 2-aminoethyl diphenylborate.

Although the Lewis acid used for synthesizing the compound represented by the general formula (1) from the compound represented by the general formula (3) is not particularly limited, titanium tetrachloride and aluminum chloride are preferred. The amount of the Lewis acid used is preferably 1.0 to 2.0 mol per 1 mol of the compound represented by formula (3).
Aluminum chloride is preferable as the Lewis acid used when synthesizing the compound represented by the general formula (2) from the compound represented by the general formula (4). When other Lewis acids are used, a compound represented by the following general formula (5) is produced as a by-product. If the compound represented by the general formula (5) is contained, the ability to cut near-infrared rays from 700 nm to 850 nm is inferior, which is not preferred.

[式中、Ｘ_３７～Ｘ_５２は、Ｘ_１～Ｘ_２２と同義である。］
general formula (5)

[In the formula, X ₃₇ to X ₅₂ have the same definitions as X ₁ to X ₂₂ . ]

Although the reaction time is not particularly limited, the progress of the reaction can be confirmed by MALDI TOF-MS spectrum or HPLC to confirm the disappearance of the raw materials.

The compound represented by general formula (1) or general formula (2) has absorption in a specific near-infrared region (700 nm to 850 nm), and has little absorption in the visible light region (480 nm to 650 nm). When used as an infrared absorbing dye, it has an excellent function as a near-infrared absorbing agent. Furthermore, since the transmittance at 940 nm is high, when an optical filter containing the compound is used when using a near-infrared LED with a wavelength of 940 nm as detection light for a sensor or the like, noise is generated while allowing the detection light to pass through well. You can cut the light.

Examples of compounds represented by general formula (1) or general formula (2) of the present invention include the following compounds, but the present invention is not limited thereto.

<Near-infrared absorbing dye>
The near-infrared absorbing dye of the present invention is characterized by containing a compound represented by general formula (1) or general formula (2).

<Other near-infrared absorbing dyes>
The near-infrared absorbing dye of the present invention can contain other near-infrared absorbing dyes in addition to the compound represented by general formula (1) or general formula (2). Thereby, the spectrum can be appropriately adjusted. Other near-infrared absorbing dyes include, for example, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, anthraquinone compounds, aminium compounds, diimmonium compounds, indigo compounds (represented by general formula (1) or general formula (2) (except for compounds that contain metals), croconium compounds, azo compounds, quinoid type complex compounds, dithiol metal complex compounds, and the like.

<Near-infrared absorbing composition>
The near-infrared absorptive composition of the present invention is characterized by comprising a near-infrared absorptive dye containing a compound represented by general formula (1) or general formula (2), and a binder resin.

The content of the compound represented by the general formula (1) or general formula (2) of the present invention is in the range of 2 to 70% by weight based on the total weight of the near-infrared absorbing composition (100% by weight). Preferably. Further, as the near-infrared absorbing dye, when other near-infrared absorbing dye is used in combination, the weight ratio of the other near-infrared absorbing dye/compound represented by general formula (1) or general formula (2) is preferably in the range of 5/95 to 50/50.

<Organic dye having absorption at 400 nm to 700 nm>
The near-infrared absorbing composition of the present invention can contain an organic dye having absorption at 400 nm to 700 nm other than the near-infrared absorbing dye of the present invention. The compound represented by the general formula (1) or general formula (2) contained in the near-infrared absorbing composition of the present invention has a strong absorption at 700 nm to 850 nm, for example, a black organic dye, a plurality of organic dyes. By including an organic dye that exhibits a black color in combination, it can be used as a near-infrared transmitting composition that blocks light of 400 nm to 850 nm and transmits light of 850 nm or more. In addition, by including an organic dye having absorption in a specific region of 400 nm to 700 nm according to the wavelength of the light source for sensing, as a near-infrared absorbing composition that blocks external unauthorized light and increases sensing accuracy. can be used. However, in order to secure the transmittance at 850 nm or more, it is necessary to use an organic dye that absorbs little at 850 nm or more.

Examples of the organic dyes having absorption at 400 nm to 700 nm include blue dyes, green dyes, yellow dyes, purple dyes, red dyes, and the like.
Organic pigments may be organic pigments, for example, diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthantrone, indane Anthraquinone-based pigments such as thorone, pyranthrone, or violanthrone, quinacridone-based pigments, perinone-based pigments, perylene-based pigments, thioindigo-based pigments, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, phthalocyanine pigments, threne-based pigments, or Metal complex pigments and the like are included.
In addition, dyes may be used as organic dyes, and examples thereof include anthraquinone dyes, monoazo dyes, disazo dyes, oxazine dyes, aminoketone dyes, xanthene dyes, quinoline dyes, and triphenylmethane dyes. mentioned. when using dyes. A method of incorporating a polar group of an anionic dye or cationic dye into a resin to impart solubility in an organic solvent is effective.

(blue pigment)
Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like.

As a blue dye, C.I. I. acid blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41:1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62, 62:1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 8485, 86, 88, 89, 90, 90:1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127: 1, 128, 129, 135, 137, 138, 143, 145, 147, 150, 155, 159, 169, 174, 175, 176, 183, 198, 203, 204, 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280 and the like.

Also, C.I. I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8:1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21:1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129130, 130:1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 243, 244, 253, 254, 260, 263 and the like.

(green pigment)
Examples of green pigments include C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62, C.I. I. Pigment Green 63 and the like.

As a green dye, C.I. I. Solvent Green 3, 20, 28, C.I. I. Acid Green 25, 27, 36, 37, 38, 41, 42, 44, C.I. I. bat greens 3, 6, 8 and the like.

(yellow pigment)
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 231, 233, 234, etc.

As a yellow dye, C.I. I. Acid yellow 2,3,4,5,6,7,8,9,9:1,10,11,11:1,12,13,14,15,16,17,17:1,18,20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 and the like.

Also, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44:1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 and the like.

(purple pigment)
Examples of purple pigments include C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like.

As a purple dye, C.I. I. acid violet 1, 2, 3, 4, 5, 5:1, 6, 7, 7:1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc. is mentioned.

Also, C.I. I. Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97 and the like.

(red pigment)
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 291, 295, 296, etc. be done.

Orange pigments that work similarly to red pigments include, for example, C.I. I. Orange pigments such as Pigment Orange 36, 38, 43, 51, 55, 59, 61, 73 can be used.

As a red dye, C.I. I. acid red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25:1, 26, 26:1, 26:2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388 and the like.

Also, C.I. I. Direct Red 1, 2, 2: 1, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26: 1, 28, 29, 31, 33, 33: 1, 34, 35, 36, 37, 39, 42, 43, 43: 1, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67:1, 68, 72, 72:1, 73, 74, 75, 77, 78, 79, 81, 81:1, 85, 86, 88, 89, 90, 97, 100, 101, 101:1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122:1, 124, 125, 127, 127:1, 127:2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238 and the like.

Also, C.I. I. Solvent Red 52, 135, 146, 149, 168, 179, 207 and the like are also included.

Although the dyes described above have good spectral characteristics and excellent color development properties, they have problems with light resistance and heat resistance, and their characteristics may not be sufficient for use in optical filters.
Therefore, in order to improve these drawbacks, in the case of the form of a basic dye, it is preferable to chlorinate it with an organic acid or perchloric acid before use. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid. Among them, it is preferable to use naphthalenesulfonic acid such as Tobias acid and perchloric acid in terms of resistance.
Moreover, it is preferable to use it after forming a salt with a resin having an anionic group, and it is also preferable to use it after forming a salt with a resin having a betaine structure and an organic acid.
In addition, in the case of anionic dyes including acid dyes and direct dyes, it is preferable to use a compound having a cationic group or a resin having a cationic group as a salt-forming compound using a counterion to improve heat resistance, light resistance, and solvent resistance. It is preferable in terms of sex.
In addition, it is preferable to form a salt with a resin having a cationic group for use, and more preferably to form a salt with a resin having a cationic group in its side chain and an organic acid.
It is also preferable from the standpoint of resistance to use sulfonamidated anionic dyes as sulfonamide compounds.
For coating applications, the blue dye is C.I. I. Pigment Blue 15:3 or C.I. I. Pigment Blue 15:6, yellow pigment is C.I. I. Pigment Yellow 139, red pigment is C.I. I. Pigment Red 254, C.I. I. Acid Red 52, or C.I. I. Acid Red 289, purple pigment is C.I. I. Pigment Violet 23 is preferably used. In molding applications, the blue dye is C.I. I. Pigment Blue 15:3 or C.I. I. Pigment Blue 15:6, yellow pigment is C.I. I. Pigment Yellow 147, red pigment is C.I. I. Solvent Red 52 is preferred.

<Specific metal atom>
The near-infrared absorbing composition of the present invention contains a small amount of Li, Na, Mg, K, Cs, Co, Ca in addition to the constituent components of the compound and the organic dye represented by the general formula (1) or general formula (2). , Fe, Si and Zr (hereinafter also referred to as specific metal atoms) may be present. When a large amount of metal components containing these specific metal atoms are present, the storage stability is inhibited, the heat resistance is lowered, and sensitivity is lowered when prepared in the form of a photosensitive near-infrared absorptive composition described later. Sometimes.
In addition, an optical filter produced using a near-infrared absorptive composition containing a large amount of metal components containing such specific metal atoms may generate foreign matter, resulting in a decrease in transmittance. The total content of specific metal atoms in the metal components contained in the near-infrared absorbing composition of the present invention is preferably 1 to 1000 mass ppm with respect to the entire near-infrared absorbing composition.

The total amount of specific metal atoms contained in the near-infrared absorptive composition of the present invention is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less, relative to the entire near-infrared absorptive composition. The lower limit of the total amount of specific metal atoms is not particularly limited, but is preferably 1 ppm by mass or more, more preferably 5 ppm by mass or more, relative to the entire near-infrared absorbing composition. Within the above range, it is possible to obtain a near-infrared absorptive composition capable of suppressing costs, excellent in storage stability, and capable of forming an optical filter with little generation of foreign matter and reduction in transmittance.

The content of each specific metal atom contained in the near-infrared absorbing composition of the present invention is preferably 100 ppm by mass or less, and 50 ppm by mass or less, relative to the entire near-infrared absorbing composition. is more preferred.

Various raw materials contained in the near-infrared absorbing composition or methods for removing metal atoms mixed in from the apparatus during the manufacturing process include JP-A-2010-83997, JP-A-2018-36521, and JP-A-7-198928. Japanese Patent Laid-Open Nos. 8-333521, 2009-7432, etc., a method of washing with water, and a method of removing magnetic foreign matter with a magnet described in Japanese Patent Laid-Open No. 2011-48736. Use method accordingly.

The content of specific metal atoms can be measured by inductively coupled plasma emission spectroscopy (ICP).

<Dye derivative>
The near-infrared absorptive composition of the present invention can contain a dye derivative, if necessary. A dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. Dye derivatives include, for example, compounds having acidic substituents such as sulfo, carboxy, or phosphate groups, and amine salts thereof, sulfonamide groups, or terminally basic substituents such as tertiary amino groups. compounds, and compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups.
Organic dyes include, for example, diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, phthalocyanine pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazineindigo-based pigments, triazine-based pigments, and benzimidazolone-based pigments. , indole-based pigments such as benzoisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, threne-based pigments, metal complex-based pigments, azo-based pigments such as azo, disazo and polyazo. mentioned.

Specifically, diketopyrrolopyrrole-based dye derivatives, JP 2001-220520, WO2009/081930, WO2011/052617, WO2012/102399, JP 2017-156397, phthalocyanine Dye derivatives are disclosed in JP-A-2007-226161, WO2016/163351, JP-A-2017-165820, and Japanese Patent No. 5753266. Anthraquinone-based dye derivatives are disclosed in JP-A-63-264674 and JP-A-09. -272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325, quinacridone dye derivatives, JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, dioxazine-based dye derivatives, JP-A-2011-162662, thiazineindigo-based dye derivatives, JP-A-2007-314785, triazine-based dye derivatives , JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681 , JP-A-2009-57478 for benzoisoindole-based dye derivatives, JP-A-2003-167112 for quinophthalone-based dye derivatives, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012 -226110, naphthol dye derivatives, JP 2012-208329, JP 2014-5439, azo dye derivatives, JP 2001-172520, JP 2012-172092, acidic Substituents, JP-A-2004-307854, basic substituents, JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404 The dye derivatives described are mentioned. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound. A compound having a substituent such as a neutral group is synonymous with a dye derivative.

These dye derivatives can be used singly 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, even more preferably 5 to 50 parts by mass, based on 100 parts by mass of the dye.

When the dye is a pigment, a dye derivative is added and subjected to a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, solvent salt milling, etc., so that the dye derivative is adsorbed on the surface of the pigment. , the primary particles of the pigment can be made finer than when the dye derivative is not added.

By adding a dye derivative to the pigment and performing a dispersion treatment such as wet dispersion using two rolls, three rolls, or beads, the dye derivative is adsorbed on the pigment surface, and the pigment surface becomes polar 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 viscosity stability over time of the near-infrared absorbing composition are improved. Further, by improving the compatibility, the coating film has excellent stability over time when the near-infrared absorbing composition is applied to a glass substrate or the like, and the waiting time from application of the near-infrared absorbing composition to exposure (PCD: Post Coating Delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay), stability and characteristic dependency of pattern shape, and line width sensitivity stability are improved. In addition, since the surface of the pigment is adsorbed and coated with the pigment derivative and the resin-type dispersant, it is possible to suppress the precipitation of crystals due to aggregation and sublimation of the pigment when the coating film is heated and baked. Further, variation in development time and development residue are suppressed.

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

Resin-type dispersants, in terms of resin systems, include, for example, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; poly(lower alkyleneimine) and polyesters having free carboxyl groups Amide and its salts formed by the reaction of; (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl Pyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphate esters, and the like.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165, 166 manufactured by BYK-Chemie Japan. or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324 or Lactimon, Lactimon-WS or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240 manufactured by Nippon Lubrizol, 13650,13940,16000,17000,18000,20000,21000,24000,26000,27000,28000,31845,32000,32500,32550,33500,32600,34750,35100,36600,3 8500, 41000, 41090, 53095, 55000, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408 manufactured by BASF, such as 56000, 76500 ,4300,4310,4320,4330,4340,450,451,453,4540,4550,4560,4800,5010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc. , Ajinomoto Fine-Techno Co., Inc. Ajisper PA111, PB711, PB821, PB822, PB824, and the like.

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

The content of the resin-type dispersant is preferably 0.1 to 200 parts by mass, more preferably 0.1 to 150 parts by mass, per 100 parts by mass of the dye. Good dispersibility can be obtained when used in an appropriate amount.

<Binder resin>
The near-infrared absorbing 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 range of 400-700 nm. Note that the transmittance is preferably 95% or more. In terms of curing properties, binder resins include, for example, thermoplastic resins, thermosetting resins, active energy ray-curable resins, and the like. In addition, the active energy ray-curable resin may have an active energy ray-reactive functional group in a thermoplastic resin or a thermosetting resin. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. Alkali solubility is for imparting development solubility in the alkali development process during optical filter production, and an acidic group is required.

Binder resin can be used individually or in combination of 2 or more types.

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

(Thermoplastic resin)
Thermoplastic resins include, for example, acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, Examples include polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.
Alkali-soluble thermoplastic resins include, for example, resins having acidic groups such as carboxyl groups and sulfone groups. Alkali-soluble thermoplastic resins include, for example, acrylic resins having acidic groups, α-olefin/(anhydride) maleic acid copolymers, styrene/styrenesulfonic acid copolymers, and ethylene/(meth)acrylic acid copolymers. , or isobutylene/(anhydride) maleic acid copolymer. Among these, an acrylic resin having an acidic group and a styrene/styrenesulfonic acid copolymer are preferred from the standpoint 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. Ethylenically unsaturated double bonds can be introduced, for example, by methods (i) and (ii) shown below. The resin is three-dimensionally crosslinked by the effect of the active energy ray, thereby increasing the crosslink density and improving the chemical resistance.

[Method (i)]
Method (i) is, for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another monomer, and adding an ethylenically unsaturated divalent A carboxyl group of unsaturated monobasic acid having a double bond is subjected to an addition reaction. Then, the produced hydroxyl group is reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group.

Ethylenically 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 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acid.

Unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and α-position haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid. Carboxylic acid etc. are mentioned.

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

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)acrylate (meth)acrylates such as acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate;
Alternatively, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or (meth)acrylamide such as acryloylmorpholine Styrenes such as acrylamides styrene or α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, fatty acid vinyls such as vinyl acetate or vinyl propionate etc.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4- Phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimide Hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, N-substituted maleimides such as 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, phenyl ethoxylate Acrylates, ethylene oxide (EO)-modified (meth)acrylates of phenol, EO- or propylene oxide (PO)-modified (meth)acrylates of paracumylphenol, EO-modified (meth)acrylates of nonylphenol, PO-modified (meth)acrylates of nonylphenol, etc. is mentioned.

As a method similar to method (i), for example, an ethylenically unsaturated monomer having a carboxyl group and a part of the side chain carboxyl group of a copolymer obtained by copolymerizing another monomer 2) is a method of subjecting an ethylenically unsaturated monomer having an epoxy group to an addition reaction to introduce an ethylenically unsaturated double bond and a carboxyl group.

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

Ethylenically unsaturated monomers having a hydroxyl group are, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, Hydroxyalkyl methacrylates such as glycerol mono(meth)acrylate or cyclohexanedimethanol mono(meth)acrylate can be mentioned. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to hydroxyalkyl (meth)acrylate, poly γ-valerolactone, poly ε-caprolactone, and/or poly Polyester mono(meth)acrylates to which 12-hydroxystearic acid or the like is added are also included. 2-Hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred from the viewpoint of suppressing foreign matter on the coating film, and from the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups. is preferred, and glycerol mono(meth)acrylate is more preferred.

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

Other monomers that can constitute the alkali-soluble resin include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimides, alkyleneoxy group-containing monomers, and phosphate ester group-containing ethylenically unsaturated monomers. monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like.
N-substituted maleimides include, for example, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy- 4-methyl-3-maleimidocoumarin, 4,4′-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N′-1,3-phenylenedimaleimide, N, N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitro phenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine and the like. Examples of alkyleneoxy group-containing monomers include EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, and paracumylphenol. Examples include EO- or propylene oxide (PO)-modified (meth)acrylates, nonylphenol EO-modified (meth)acrylates, nonylphenol PO-modified (meth)acrylates, and the like.

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

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

(Alkali-soluble resin having no ethylenically unsaturated double bond)
The near-infrared absorbing composition of the present invention can contain an alkali-soluble resin having no ethylenically unsaturated double bonds in order to adjust the degree of curing of the film.

The weight-average molecular weight (Mw) of the alkali-soluble resin in the invention is preferably 4,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less, in order to impart solubility in alkali development. Also, the value of Mw/Mn is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 4,000, the adhesiveness to the substrate is lowered and the exposed pattern is less likely to remain. If it exceeds 100,000, the solubility in alkali development will be lowered, and a residue will be generated to deteriorate the linearity of the pattern.
The acid value of the alkali-soluble resin in the present invention is from 50 to 200 (KOHmg/g), preferably from 20 to 300, more preferably from 90 to 170, in order to impart solubility in alkali development. is. If the acid value is less than 50, the solubility in alkali development is lowered, and residues are generated, which deteriorates the linearity of the pattern. If the acid value is excessively high, 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, it is preferable that the binder resin is used in combination with the thermoplastic resin and further contains a thermosetting compound. For example, when an optical filter is produced using the near-infrared absorbing composition of the present invention, the inclusion of a thermosetting compound reacts when the filter segment is baked to increase the crosslink density of the coating film, thereby increasing the heat resistance of the filter segment. It is possible to obtain the effect of suppressing a decrease in transmittance in the range of 480 nm to 650 nm, which is a region with high relative luminosity, by suppressing dye aggregation during baking of the filter segment.

The thermosetting compound may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin.
Examples of thermosetting compounds include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds, but the present invention is limited thereto. not to be Epoxy compounds and oxetane compounds are preferably used in the near-infrared absorbing composition of the present invention.

Epoxy compounds include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted polycondensates of various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), phenol polymers with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones Polycondensates with (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol , α,α,α',α'-biphenyldimethanol, etc.), polycondensation products of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.) , polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, and the like.

The content of the thermosetting compound is preferably 0.5 to 300% by mass, more preferably 1.0 to 50% by mass, based on 100% by mass of the dye. Appropriate heat resistance can be obtained by using an appropriate amount.

The near-infrared absorbing composition can contain a curing agent and a curing accelerator to assist curing of the thermosetting compound. Curing agents include, for example, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like. Curing accelerators include, for example, amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl -N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2- ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4 -diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.) mentioned.

The contents of the curing agent and the curing accelerator are preferably 0.01 to 15% by mass, respectively, based on 100% by mass of the thermosetting compound.

<Polymerizable compound>
The near-infrared absorbing composition of the present invention can be made into a photosensitive near-infrared absorbing composition by containing a polymerizable compound and a photopolymerization initiator. Polymerizable compounds include monomers or oligomers that are cured by ultraviolet rays, heat, or the like to form transparent resins.

Polymerizable compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) Acrylates, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetra Ethylene glycol (meth)acrylate, phenoxyhexaethyleneglycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A Diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methylolated Various acrylic and methacrylic esters such as melamine (meth)acrylate, epoxy (meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile and the like.

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

Photopolymerizable monomers having an acid group include, for example, polyhydric alcohols and (meth)acrylic acid esters of free hydroxyl group-containing poly(meth)acrylates and dicarboxylic acids; Examples thereof include esterified products with hydroxyalkyl (meth)acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. , malonic acid, succinic acid, glutaric acid, free carboxyl group-containing monoesters with dicarboxylic acids such as phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic 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 Monohydroxy monoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, and the like can be mentioned.

(Polymerizable compound having 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 polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, or reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth)acrylate having a hydroxyl group. and polyfunctional urethane acrylates obtained by

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

Polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate and the like.

A polymerizable compound can be used individually or in combination of 2 or more types.

The blending amount of the polymerizable compound is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on 100% by mass of non-volatile matter in the near-infrared absorbing composition. Curability and developability are further improved when blended in an appropriate amount.

<Photoinitiator>
Photoinitiators include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1 -hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-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. Acetophenone compounds; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone , 4-benzoyl-4'-methyldiphenyl sulfide, or benzophenone compounds such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone , 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-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6- Triazine, or triazine compounds such as 2,4-trichloromethyl-(4′-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O- benzoyloxime)], or oxime ester compounds such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); Phosphine compounds such as (2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Quinones such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. Among these, oxime ester compounds are preferred.

A photoinitiator can be used individually or in combination of 2 or more types.

(Oxime ester compound)
In oxime ester-based compounds, the absorption of ultraviolet light causes cleavage of the NO bond of the oxime to produce iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the dye concentration of the near-infrared absorbing composition is high, the ultraviolet transmittance of the coating film may be low and the degree of curing of the coating film may be low. be.

Oxime ester compounds are oximes described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. Ester-based photopolymerization initiators can be mentioned.

The content of the photopolymerization initiator is preferably 2 to 200 parts by mass, more preferably 2 to 150 parts by mass, per 100 parts by mass of the dye. When blended in an appropriate amount, the photocurability and developability are further improved.

<Sensitizer>
Furthermore, the near-infrared absorbing composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as 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, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives , naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxyesters , acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3′ or 4,4′- tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone and the like.

Among the above sensitizers, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives can be mentioned as sensitizers capable of particularly suitable sensitization. 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, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al. Special Functional Materials" (1986, CMC), but are not limited to these. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be included.

A 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, based on 100 parts by mass of the photopolymerization initiator. When contained in an appropriate amount, curability and developability are further improved.

<Thiol chain transfer agent>
The near-infrared absorbing composition of the present invention preferably contains a thiol chain transfer agent as a chain transfer agent. By using a thiol together with a photopolymerization initiator, in the process of radical polymerization after light irradiation, it acts as a chain transfer agent and generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen. becomes sensitivity.

Moreover, polyfunctional aliphatic thiols bonded to aliphatic groups such as methylene and ethylene groups having two or more thiol groups are preferred. More preferred are polyfunctional aliphatic thiols having 4 or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and it is possible to cure from the surface of the pattern to the vicinity of the substrate.

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

A thiol-based 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 20% by mass, more preferably 0.1 to 10% by mass, based on 100% by mass of the non-volatile matter of the near-infrared absorbing composition. When contained in an appropriate amount, the photosensitivity and tapered shape are improved, and wrinkles are less likely to occur on the coating surface.

<Polymerization inhibitor>
The near-infrared absorbing composition of the present invention can contain a polymerization inhibitor. This makes it possible to suppress exposure due to diffracted light from the mask during photolithographic exposure, making it easier to obtain a pattern of a desired shape.

Examples of polymerization inhibitors include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2- Propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4- Alkylcatechol compounds such as tert-butylcatechol and 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propyl Alkylresorcinol 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, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine and tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide, etc. phosphine oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, phloroglucine and the like.

The content of the polymerization inhibitor is preferably 0.01 to 0.4% by mass based on 100% by mass of non-volatile matter in the near-infrared absorbing composition. Within this range, the effect of the polymerization inhibitor is increased, and the straightness of the taper, the wrinkles of the coating film, the pattern resolution, etc. are improved.

<Ultraviolet absorber>
The near-infrared absorbing composition of the invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorption function, and includes 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 weight based on the total 100% by weight of the photopolymerization initiator and the ultraviolet absorber. When contained in an appropriate amount, the resolution after development is further improved.

Moreover, 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 matter of the near-infrared absorbing composition. When contained in an appropriate amount, the adhesion between the substrate and the film is further improved, and good resolution can be obtained.

Benzotriazole compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5 -bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy- 5′-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethyl ethyl)-4-hydroxy, a mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-( 2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol-2-yl)-4-(1,1 ,3,3-tetramethylbutyl)phenol, 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2 -(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5 -di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert- Butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro- 2H-benzotriazol-2-yl)phenyl]propionate and the like. In addition, oligomer type and polymer type compounds having a benzotriazole structure can also be used.

Triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6 -bis(2,4-dimethylphenyl)-1,3,5-triazin-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-triazin-2-yl)-5-(hexyl oxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-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. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.

Benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2 , 2′,4,4′-tetrahydroxybenzophenone, 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.

Salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tertbutylphenyl salicylate. In addition, oligomer type and polymer type compounds having a salicylic acid ester structure can also be used.

<Antioxidant>
The near-infrared absorbing composition of the present invention can contain an antioxidant. Antioxidants prevent the photopolymerization initiators and thermosetting compounds contained in the near-infrared absorbing composition from oxidizing and yellowing due to the heat process during thermosetting and ITO annealing. can be improved. Especially when the dye concentration of the near-infrared absorbing composition is high, the amount of the coating film cross-linking component is reduced, so measures such as using a highly sensitive cross-linking component and increasing the amount of the photopolymerization initiator will cause yellowing during the heat process. phenomena can be seen. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and to obtain a high transmittance of the coating film.

Antioxidants include, for example, hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present invention, the antioxidant is preferably a compound containing no halogen atoms.

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

An antioxidant can be used individually or in combination of 2 or more types.

Further, the content of the antioxidant is more preferably 0.5 to 5.0% by mass based on 100% by mass of the solid content of the near-infrared absorbing composition, since the transmittance, spectral characteristics, and sensitivity are good. .

<Amine compound>
The near-infrared absorbing composition can contain an amine-based compound to reduce dissolved oxygen.
Amine compounds include, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl p-toluidine and the like.

<Leveling agent>
The near-infrared absorbing composition can contain a leveling agent to improve the leveling properties of the composition during coating. The leveling agent is preferably, for example, dimethylsiloxane having a polyether structure or polyester structure in its main chain. Examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK Chemie. Examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. A dimethylsiloxane having a polyether structure in its main chain and a dimethylsiloxane having a polyester structure in its main chain can be used in combination. The content of the leveling agent is preferably 0.003 to 0.5% by mass based on 100% by mass of non-volatile matter in the near-infrared absorbing composition.

A leveling agent is, for example, a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, and is a compound that has a hydrophilic group but has low solubility in water and can lower the surface tension. A dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used as the leveling agent. Polyalkylene oxide units include, for example, polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane is a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of dimethylpolysiloxane, a terminal modified type in which the terminal is bonded to the terminal of dimethylpolysiloxane, and a dimethylpolysiloxane. It may be of any linear block copolymer type with alternating repeating bonds. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray, for example FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ- 2207 can be mentioned.

Anionic, cationic, nonionic, or amphoteric surfactants can be added to the leveling agent as auxiliaries. Two or more kinds of surfactants may be mixed and used.

Examples of anionic surfactants that are added to the leveling agent are polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, and alkyldiphenyl ether disulfones. monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphorus and acid esters.

Cationic surfactants added to the leveling agent include, for example, alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent are, for example, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monosterate. Alkylbetaines such as betaine alkyldimethylaminoacetate; amphoteric surfactants such as alkylimidazoline; and fluorine-based and silicone-based surfactants.

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

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

Examples of adhesion improvers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- (Meth)acrylsilanes 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-aminopropylmethyldimethoxysilane Silane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl- butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, aminosilanes such as hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxy mercaptos such as silane, 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureides such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide and silane coupling agents such as isocyanates such as , 3-isocyanatopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the dye in the near-infrared absorbing composition. Within this range, the effect is enhanced and the balance between adhesion, resolution, and sensitivity is good, which is more preferable.

<Organic solvent>
The near-infrared absorbing composition can contain an organic solvent. This facilitates adjustment of the viscosity of the composition.

Organic solvents include, for example, ethyl lactate, butyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1, 4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate , 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m -xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-Diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol mono Isopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether , ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, Cyclopentanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene Glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene Glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate , isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, and the like.

Among the above organic solvents, in the case of coating applications, 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 coating properties and drying properties. 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, cyclohexanone, cyclopentanone and the like are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, cyclohexanone, cyclopentanone and the like are more preferred.

<Method for producing near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention is prepared by dispersing a dye in a dye carrier such as a dispersant or a binder resin and/or an organic solvent, preferably together with a dispersing aid (a dye derivative or a surfactant), using a kneader, It can be produced by finely dispersing using various dispersing means such as a two-roll mill, three-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor (dye dispersion). At this time, two or more kinds of dyes and the like may be dispersed in the dye carrier at the same time, or those dispersed in the dye carrier separately may be mixed. If the pigment such as a dye has high solubility, specifically, if it has high solubility in the organic solvent used, and if it is dissolved by stirring and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. No need.

When used as a photosensitive near-infrared absorptive composition (resist material), it can be prepared as a solvent-developable or alkali-developable near-infrared absorptive composition. The solvent-developable or alkali-developable near-infrared absorbing composition comprises the dye dispersion, a photopolymerizable monomer and/or a photopolymerization initiator, and optionally a solvent, other dispersing aids, and It can be prepared by mixing additives and the like. The photopolymerization initiator may be added at the stage of preparing the near-infrared absorbing composition, or may be added later to the prepared near-infrared absorbing composition.

<Removal of coarse particles>
The near-infrared absorptive composition of the present invention is produced by means of centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or a membrane filter, etc., to obtain coarse particles of 5 μm or more, preferably 1 μm or more, more preferably coarse particles of 1 μm or more. It is preferable to remove coarse particles of 0.5 μm or more and mixed dust. As such, the near-infrared absorbing composition preferably does not substantially contain particles of 0.5 µm or more. More preferably, it is 0.3 μm or less.

<Amount of water in the near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention preferably has a water content of 0.1 to 2.0% by mass based on the entire near-infrared absorbing composition.

When the water content is within the above range, the near-infrared absorbing composition is excellent in dispersion stability and sensitivity even after being stored for a long time.

The content of water is preferably 1.8% by mass or less, more preferably 1.6% by mass or less, relative to the total amount of the near-infrared absorbing composition. If the water content is sufficiently small within this range, problems with the dispersion stability and sensitivity of the near-infrared absorbing composition are less likely to occur even after long-term storage.

A method for controlling the water content is not particularly limited, and a known method can be used. Examples thereof include a method of producing a near-infrared absorbing composition while blowing in a dry inert gas, and a method of adding molecular sieves and dehydrating after production. Among them, the method of manufacturing while blowing dry inert gas is preferable.

The water content can be measured by a known method such as the Karl Fischer method.

<Amount of toluene in near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention may contain toluene, and when it contains toluene, the toluene content is preferably 0.1 to 10 mass ppm. The upper limit of the toluene content is preferably 9 mass ppm or less, more preferably 8 mass ppm or less, and even more preferably 7 mass ppm or less. The lower limit is preferably 0.2 ppm by mass or more, more preferably 0.3 ppm by mass or more, and even more preferably 0.4 ppm by mass or more.

<Application>
The near-infrared absorbing composition of the present invention can be used for, for example, the following applications.

(optical filter)
The optical filter of the present invention is characterized by having a coating formed from the near-infrared absorbing composition of the present invention. The optical filter of the present invention includes a near-infrared cut filter and a near-infrared transmissive filter. The near-infrared cut filter is mainly composed of a near-infrared absorbing dye and has a role of blocking near-infrared rays and transmitting visible light. On the other hand, the near-infrared transmission filter is composed of pigments that absorb visible light in addition to near-infrared absorbing pigments. It has the role of transmitting near-infrared wavelengths.

[Near-infrared cut filter]
A near-infrared cut filter is used for the following applications, for example.

<<Digital camera>>
A digital camera recognizes colors by separating the light it receives when taking an image with red, green, and blue filters and sending it to photodiodes that convert the light into electrical signals. However, since the photodiode also reacts to near-infrared rays and converts them into electric signals, a near-infrared cut filter can be used to block this. It is important that a filter that cuts off near-infrared rays has little absorption in the visible region. If there is much absorption in the visible region, the received light is colored, which adversely affects the color recognition of the photodiode. Since the near-infrared absorbing dye of the present invention has little absorption in the visible region and is highly invisible, it has little adverse effect on the color recognition of the photodiode.

<<Biometric sensor>>
Smartphones, tablet computers, 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 in smartphones and tablet computers has been dizzying, and as photodiodes have changed from inorganic to organic, the range of authentication has increased to the screen size (full screen), organic EL displays, liquid crystal displays, etc. A fingerprint authentication sensor with a built-in display has been developed.

However, many of the fingerprint sensors with built-in displays are optical methods that illuminate the fingerprint with various light sources installed in the display and sense the reflected light, so it is difficult to detect external light sources such as sunlight and LED lighting. If strong light with a wide range of wavelengths is incident on the sensor, there is a problem of noise during imaging, and there is some concern about accuracy when used outdoors.For bank ATMs and multimedia terminals. The same is true for finger vein authentication, and countermeasures such as wearing covers to block external light are taken at stores with strong lighting and stores with good sunlight.

The near-infrared cut filter is effective in solving these problems by absorbing and preventing the entrance of unauthorized external light to the sensor.

For example, when it is set on the front panel of a smartphone or tablet computer, it is necessary to have a good design, but the optical filter of the present invention has no absorption in the visible region and is invisible, that is, it is highly transparent, so it can be used favorably. be. In addition, since the near-infrared absorbing composition of the present invention has excellent heat resistance, it can be preferably used in the process of manufacturing a sensor, a touch sensor incorporating the sensor, or a touch panel.

In addition, external light that becomes noise in biometric authentication applications is light of 650 nm to 1000 nm that penetrates the living body, and in particular, light of 650 nm to 800 nm is abundant in the living space, so it is possible to cut light in this wavelength range. Improve the accuracy of biometric authentication. By combining a blue dye or green dye that absorbs from 650 nm to 700 nm with a near-infrared absorbing dye, the invisibility is lowered, but the accuracy of biometric authentication can be improved.

Blue dyes include, for example, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:1 and the like. Green dyes include, for example, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62, C.I. I. Pigment Green 63 and the like.

<<Display>>
A near-infrared cut filter can also be incorporated into the display. Specifically, there is a liquid crystal display with a touch panel function like an electronic blackboard. This liquid crystal display with a touch panel function has three functions: display, writing, and storage. The noise caused by outside light mentioned above was a problem. Liquid crystal displays with a touch panel function are often used in schools and the like, so accuracy and good response to touch are important. By incorporating the optical filter of the present invention into a display, it is possible to cut outside light that causes noise, which is preferable.
Further, the optical filter of the present invention can be preferably used as an antireflection film for various displays using liquid crystal, organic EL, Mini-LED and Micro-LED. By suppressing the reflection of not only visible light but also light in the near-infrared region, there is an advantage that the black display on the display can be made blacker. Since the near-infrared absorptive composition of the present invention is excellent in heat resistance, it can be preferably used in terms of the resistance of the steps required in display production.

[Near-infrared transmission filter]
LEDs with wavelengths of 900 nm, 940 nm, etc. have become widespread, and are used for distance measurement and biometric authentication (fingerprint authentication, iris authentication, face authentication, vein authentication, etc., or their combination) in automatic driving, and light detection in various sensors. ing. However, since light rays of all wavelengths, such as ultraviolet rays, visible light, and near-infrared rays, exist in the atmosphere, a filter is required to block light of wavelengths other than those to be detected. By combining a near-infrared absorbing dye with a dye that absorbs visible light, an ultraviolet absorber, etc., it is possible to transmit only light with wavelengths longer than the absorption wavelength of the near-infrared absorbing dye and block light with shorter wavelengths. can. Specifically, it is preferable to combine the near-infrared absorbing dye of the present invention with a blue dye and a yellow dye, or a red or purple dye.

[Method for producing an optical filter]
The optical filter of the present invention can be manufactured by a printing method or a photolithography method. Formation of the filter segment by the printing method enables patterning by printing and drying the near-infrared absorbing composition, so the method for manufacturing the filter is low cost and excellent in mass productivity. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to have a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, it is also important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted by using a resin-type dispersant or an extender.

When forming a filter segment by photolithography, a near-infrared absorbing composition prepared as a solvent-developable or alkali-developable resist material is applied onto a substrate by spray coating, spin coating, slit coating, roll coating, or the like. Depending on the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact or non-contact with this film. After that, the film is immersed in a solvent or alkaline developer or sprayed with a developer to remove the uncured portion to form a desired pattern, and then the same operation is repeated for other colors to produce a filter. can be done. Furthermore, in order to promote polymerization of the resist material, heating may be applied as necessary. The photolithographic method can produce filters with higher precision than the printing method.

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

For development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoaming agent or a surfactant can be added to the developer. In order to increase the UV exposure sensitivity, after coating and drying the above resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin was coated and dried to form a film that prevents polymerization inhibition by oxygen. Afterwards, ultraviolet exposure can also be performed.

The optical filter of the present invention can be manufactured by an electrodeposition method, a transfer method, an ink jet method, or the like, in addition to the above methods.

(for molding)
The near-infrared absorbing dye of the present invention can also be used in molding applications. In addition, the molding application is an application for producing a film or a three-dimensional body by a method other than coating.
When the near-infrared absorbing composition is used for molding, it is preferably a melt-kneaded product of a near-infrared absorbing dye and a thermoplastic resin.

[Thermoplastic resin]
Thermoplastic resins contained in the near-infrared absorbing composition for molding include, for example, polyolefin resins, acrylic resins, polystyrene resins, polyester resins, polyamide resins, polycarbonate resins, cycloolefin resins, and polyetherimide resins.

<<polyamide resin>>
A polyamide resin is a crystalline resin, and can be synthesized, for example, by subjecting a carboxylic acid component and a compound (Am) having two or more amino groups to a dehydration condensation reaction.

Carboxylic acid components include, for example, adipic acid, sebacic acid, isophthalic acid, and terephthalic acid. A compound having 3 or more carboxyl groups can be used as the carboxylic acid component.
Known compounds (Am) having two or more amino groups can be used, for example, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylene Aliphatic polyamines such as tetramine; isophoronediamine, dicyclohexylmethane-4,4'
-aliphatic polyamines including cycloaliphatic polyamines such as diamines; aromatic polyamines such as phenylenediamine and xylylenediamine; 1,3-diamino-2-propanol, 1,4-diamino-2-butanol, 1-amino- 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-ol, 4-(2-aminoethyl)-4,7,10-triazadecan-2-ol, 3-(2-hydroxypropyl)- Diaminoalcohols such as o-xylene-α,α'-diamine are included.
Examples of commercially available polyamide resins include nylon 6 (manufactured by Toray Industries, Inc.), nylon 66 (manufactured by Toray Industries, Inc.), and nylon 610.

<<Polycarbonate Resin>>
A polycarbonate resin is an amorphous resin, and is synthesized by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene or carbonic acid diester. In the case of synthesis reactions using phosgene, for example, interfacial methods are preferred. Moreover, in the case of a synthetic reaction using a carbonic acid diester, a transesterification method in which the reaction is performed in a molten state is preferred.

Aromatic dihydroxy compounds are, for example, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2 , 2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl) Propane, 1,1-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3, bis(hydroxyaryl)alkanes such as 5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1, bis(hydroxyaryl)cycloalkanes such as 1-bis(4-hydroxyphenyl)cyclohexane; dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; ,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide and other dihydroxydiaryl sulfides, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 dihydroxydiarylsulfoxides such as '-dimethyldiphenylsulfoxide; dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone; Also, piperazine, dipiperidylhydroquinone, resorcinol, and 4,4'-dihydroxydiphenyls may be mixed and used.

Examples of the carbonate precursor include phosgene, diaryl carbonates such as diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

The viscosity average molecular weight of the polycarbonate resin is preferably 15,000 to 30,000, more preferably 16,000 to 27,000. The viscosity-average molecular weight in this specification is a value converted from solution viscosity measured at a temperature of 25° C. using methylene chloride as a solvent.

Commercially available polycarbonate resins include, for example, Iupilon H-4000 (manufactured by Mitsubishi Engineering-Plastics, viscosity average molecular weight 16,000), Iupilon S-3000 (Mitsubishi Engineering-Plastics, viscosity average molecular weight 23,000), and Iupilon E-2000. (manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 27,000).

<<Cycloolefin Resin>>
A cycloolefin resin is an amorphous resin having an alicyclic structure in its main chain and/or side chains. Types of alicyclic structures include, for example, norbornene polymers, monocyclic cyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Among these, the norbornene polymer is preferred because of its excellent moldability and transparency. Norbornene monomers include, for example, bicyclo[2.2.1]hept-2-ene (common name: norbornene), tricyclo[4.3.0.12,5]deca-3,7-diene ( Common name: dicyclopentadiene), 7,8-benzotricyclo[4.3.0.12,5]dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo[4.4.0.12, 5, 17,10]dodeca-3-ene (common name: tetracyclododecene) and the like.
Examples of commercially available cycloolefin resins include Topas (manufactured by Polyplastics) and APEL (manufactured by Mitsui Chemicals, Inc.).

<<Polyetherimide Resin>>
A polyetherimide resin is an amorphous resin having a glass transition temperature of more than 180° C., and has good transparency, high strength, high heat resistance, high elastic modulus, and broad chemical resistance. As such, they are widely used in diverse applications such as automotive, telecommunications, aerospace, electrical/electronics, transportation and healthcare.
One process for producing polyetherimide resins is by polymerization of alkali metal salts of dihydroxyaromatic compounds, such as bisphenol A disodium salt (BPA.Na2), and bis(halophthalimide). The molecular weight of the resulting polyetherimide resin can be controlled in two ways. The first method is to use a molar excess of bis(halophthalimide) to the alkali metal salt of the dihydroxyaromatic compound. A second method is to prepare the bis(halophthalic anhydride) in the presence of a monofunctional compound such as phthalic anhydride which forms an endcapping agent. Phthalic anhydride reacts with some of the organic diamines to form monohalo-bis(phthalimides). Monohalo-bis(phthalimides) serve as end-capping agents in the polymerization step by reacting with phenoxide end groups in growing polymer chains.
Commercially available polyetherimide resins include ULTEM (manufactured by Saudi Basic Industries Corporation).

The thermoplastic resin is preferably a crystalline resin with a melting point of 100 to 500°C or an amorphous resin with a glass transition temperature of 60 to 300°C. Both the melting point and the glass transition temperature can be measured with a differential scanning calorimeter, a thermogravimetric differential thermal analyzer, or the like.

The near-infrared absorbing composition for molding can contain additives in addition to the near-infrared absorbing dye and the thermoplastic resin. Additives include, for example, ultraviolet absorbers, light stabilizers, antioxidants, colorants, dispersants, and the like. These additives are compounds known for molding applications.

UV absorbers are used to impart UV resistance to molded articles. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, triazine-based, and salicylate-based. The content of the ultraviolet absorber is preferably 0.01 to 5% by mass based on 100% by mass of the composition.

Light stabilizers are used to impart UV resistance to molded articles, and are preferably used in combination with UV absorbers. The light stabilizer is preferably, for example, a hindered amine light stabilizer. The content of the light stabilizer is preferably 0.01 to 5% by mass based on 100% by mass of the composition.

Antioxidants are used to reduce degradation of the molded article when exposed to natural or artificial light and subject to high temperatures. Antioxidants are preferably monophenol-based, bisphenol-based, polymeric phenol-based, sulfur-based, phosphoric acid-based, and the like. The content of the antioxidant is preferably 0.01 to 5% by mass based on 100% by mass of the composition.

A dispersant is used to more uniformly disperse the near-infrared absorbing pigment in the molded article. The dispersant is preferably polyolefin wax, fatty acid wax, fatty acid ester wax, partially saponified fatty acid ester wax, saponified fatty acid wax, or the like. The content of the dispersing agent is preferably 50 to 250 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye.

[Preparation of near-infrared absorbing composition for molding]
A near-infrared absorbing composition for molding can be produced by melt-kneading a near-infrared absorbing dye and a thermoplastic resin. The melt-kneading temperature varies depending on the resin, but is preferably 230°C or higher, more preferably 270°C or higher. In addition, it is preferable to cool after melt-kneading. The upper limit of the melt-kneading temperature is not limited because it varies depending on the type of thermoplastic resin. The upper limit is preferably 500° C. or less, more preferably 450° C. or less. Moreover, the upper limit must be less than the sublimation temperature or the decomposition temperature of the near-infrared absorbing dye of the present invention.

Examples of the melt-kneading apparatus include single-screw kneading extruders, twin-screw kneading extruders, and tandem-type twin-screw kneading extruders.

The resin composition is preferably produced as a so-called masterbatch. When a masterbatch is prepared and then melt-kneaded with a diluted resin (thermoplastic resin) to prepare a molded article, the near-infrared absorbing dye of the present invention is compared with a molded article prepared without the masterbatch. It is easily dispersed uniformly in the molded article, and can suppress aggregation of the near-infrared absorbing dye. This improves the transparency of the molded article. The masterbatch is preferably produced by molding into pellets using a pelletizer after the melt-kneading.
When it is produced as a masterbatch, the content of the near-infrared absorbing dye is preferably 0.01 to 20% by mass, more preferably 0.05 to 2% by mass, based on 100% by mass of the composition.

(Optical recording medium)
The near-infrared absorbing composition of the present invention can be used as an optical recording medium. When a film or molded article formed from a near-infrared absorbing composition is irradiated with near-infrared rays, the crystal state of the dye changes, and the refractive index of the film or molded article changes. This principle is used in recording media such as optical discs.

(laser welding materials, laser marking materials)
The near-infrared absorbing composition of the present invention can be used as a laser welding material or laser marking material. When a coating or molded article formed from a near-infrared absorbing composition is irradiated with a laser having a wavelength that is absorbed by the near-infrared absorbing dye, the dye absorbs the laser light and generates heat, thereby melting and carbonizing the resin. When it melts, it can be welded with another resin, so marking becomes possible.

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

(Compound identification method)
Identification of the compounds used in the present invention was carried out by comparing molecular ion peaks in the mass spectrum with mass numbers (theoretical values) obtained by calculation. Measurement of the molecular ion peak of the mass spectrum was performed using Waters ACQUITY UPLS H-Class (column used: ACQUITY UPLC BEH C18 Column 130 Å, 1.7 μm, 2.1 mm×50 mm)/Ms TAP XEVO TQD.
Furthermore, using a 2400 CHN Element Analyzer manufactured by Perkin-Elmer, the ratio of each element obtained was identified by agreement with the theoretical value.

(Method for measuring water content of near-infrared absorbing composition)
The water content (mg) was measured using a Karl Fischer titrator (Mitsubishi Chemical Co., Ltd. KF-06 volumetric titration type water measuring device), and the water content (%) was calculated according to the following formula.
Moisture content (%) = [moisture content (mg) / measurement sample amount (mg)] × 100

(Method for measuring specific metal atom in near-infrared absorbing composition)
The amount of specific metal atoms in the near-infrared absorbing composition is measured by an ICP emission spectrometer Varian 720-ES manufactured by Agilent Technologies after decomposing the powder obtained by drying the near-infrared absorbing composition at 180° C. with microwaves. bottom.

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

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

(Weight average molecular weight (Mw) of basic resin type dispersant)
The weight-average molecular weight (Mw) of the basic resin-type dispersant was determined by GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation), and 3 mM triethylamine and 10 mM LiBr as developing solvents. is a polystyrene-equivalent weight average molecular weight (Mw) measured using an N,N-dimethylformamide solution of

(Amine value of resin type dispersant)
The amine value of the resin-type dispersant was obtained by potentiometric titration using a 0.1N hydrochloric acid aqueous 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 matter.

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

[Example 1]
(Production of compound (a))
In a reactor, 10.7 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. After that, 95.2 parts of a 1 mol/l toluene solution of titanium tetrachloride was added dropwise. After dropping, 10.0 parts of indigo was added and refluxed for 10 hours. After completion of the reaction, methanol was added and filtered to obtain a green powder. 14.6 parts of compounds (1) were obtained by liquid-separating this with a dichloromethane and water and concentrating an organic layer.

[Compound (1)]

In a reaction vessel, 13.5 parts of compound (1), 11.0 parts of 2-aminoethyl diphenylborinate, 6.7 parts of aluminum chloride and 100 parts of toluene were mixed and stirred, and heated under reflux for 3 hours in a nitrogen atmosphere. . After cooling to room temperature, it was poured into 300 parts of methanol with stirring to obtain a blue slurry. This slurry was filtered, washed with 300 parts of methanol and then with 500 parts of water, and dried to obtain 15.2 parts of compound (a). As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (a).

compound (a)

[Example 2]
(Production of compound (b))
Compound (a) except that 11.0 parts of 2-aminoethyl diphenylborinate used in the production of compound (a) was changed to 11.6 parts of 2-bis(p-tolyl)boranyloxyethanamine. 15.5 parts of compound (b) was obtained by performing the same operation as in the production. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (b).

Compound (b)

[Example 3]
(Production of compound (c))
Compound (a) except that 11.0 parts of 2-aminoethyl diphenylborinate used in the production of compound (a) was changed to 12.9 parts of 2-bis(4-chlorophenyl)boranyloxyethanamine. 15.5 parts of compound (c) was obtained by performing the same operation as in the production. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (c).

compound (c)

[Example 4]
(Production of compound (d))
The same operation as in the synthesis of compound (1) was performed except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 18.5 parts of 2,3-dichloroaniline to obtain compound (2). 17.8 parts were obtained.

[Compound (2)]

In a reaction vessel, 13.5 parts of compound (2), 11.0 parts of 2-aminoethyl diphenylborinate, 8.4 parts of titanium tetrachloride and 100 parts of xylene were mixed and stirred, and heated under reflux for 3 hours in a nitrogen atmosphere. bottom. After cooling to room temperature, it was poured into 300 parts of methanol with stirring to obtain a blue slurry. This slurry was filtered, washed with 300 parts of methanol, washed with 500 parts of water, and dried to obtain 15.0 parts of compound (d). As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (d).

compound (d)

[Example 5]
(Production of compound (e))
The same procedure as in the synthesis of compound (1) was performed except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 14.6 parts of 3,4-difluoroaniline to obtain compound (3). 16.2 parts were obtained.

[Compound (3)]

The same operation as in the production of compound (a) was performed except that 13.5 parts of compound (1) used in the production of compound (a) was changed to 14.7 parts of compound (3) to obtain compound (e). 15.9 parts of As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (e).

Compound (e)

[Example 6]
(Production of compound (f))
The same operation as in the synthesis of compound (1) was performed except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 19.8 parts of 4-bromoaniline, and 20.2 parts of compound (4) was obtained. 0 copies were obtained.

[Compound (4)]

The same operation as in the production of compound (a) was performed except that 13.5 parts of compound (1) used in the production of compound (a) was changed to 19.7 parts of compound (4) to obtain compound (f). 21.2 parts of As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (f).

Compound (f)

[Example 7]
(Production of compound (g))
The same procedure as in the synthesis of compound (1) was performed except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 13.9 parts of 2,6-dimethylaniline to obtain compound (5). 14.9 parts obtained.

[Compound (5)]

The same operation as in the production of compound (a) was performed except that 13.5 parts of compound (1) used in the production of compound (a) was changed to 14.8 parts of compound (5) to obtain compound (g). 16.1 parts of As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (g).

compound (g)

[Example 8]
(Production of compound (h))
The same operation as in the synthesis of compound (1) was performed except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 16.0 parts of 4-(methylthio)aniline to obtain compound (6). 16.4 parts were obtained.

[Compound (6)]

The same operation as in the production of compound (a) was performed except that 13.5 parts of compound (1) used in the production of compound (a) was changed to 15.0 parts of compound (6) to obtain compound (h). 16.2 parts of As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (h).

compound (h)

[Example 9]
(Production of compound (i))
The same operation as in the synthesis of compound (1) was performed except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 16.5 parts of 1-naphthylamine. I got it.

[Compound (7)]

The same procedure as in the production of compound (a) was performed except that 13.5 parts of compound (1) used in the production of compound (a) was changed to 16.8 parts of compound (7) to obtain compound (i). 17.1 parts of As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (i).

compound (i)

[Example 10]
(Production of compound (j))
The same procedure as in the synthesis of compound (1) was performed except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 14.2 parts of 4-amino-2-methylphenol, and compound (8 ) was obtained.

[Compound (8)]

The same operation as in the production of compound (a) was performed except that 13.5 parts of compound (1) used in the production of compound (a) was changed to 14.5 parts of compound (8) to obtain compound (j). 14.6 parts of As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (j).

compound (j)

[Example 11]
(Production of compound (k))
The same operation as in the synthesis of compound (1) was performed except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 14.2 parts of 3-methoxyaniline, and compound (9) was obtained in 17. Got 3 copies.

[Compound (9)]

The same operation as in the production of compound (a) was performed except that 13.5 parts of compound (1) used in the production of compound (a) was changed to 14.5 parts of compound (9) to obtain compound (k). 15.0 parts were obtained. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (k).

compound (k)

[Example 12]
(Production of compound (L))
Compound (10) was synthesized in the same manner as in the synthesis of compound (1) except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 21.3 parts of 4-phenoxyaniline. Obtained 8 copies.

[Compound (10)]

The same operation as in the production of compound (a) was performed except that 13.5 parts of compound (1) used in the production of compound (a) was changed to 16.5 parts of compound (10) to obtain compound (L). 16.2 parts of As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (L).

Compound (L)

[Example 13]
(Production of compound (m))
The same procedure as in the synthesis of compound (1) was performed except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 18.8 parts of N,N-diethyl-1,4-phenylenediamine. , to obtain 18.8 parts of compound (11).

[Compound (11)]

The same operation as in the production of compound (a) was performed except that 13.5 parts of compound (1) used in the production of compound (a) was changed to 15.7 parts of compound (11) to obtain compound (m). 14.5 parts of As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (m).

Compound (m)

[Example 14]
(Production of compound (n))
The same procedure as in the synthesis of compound (1) was performed except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 13.7 parts of 4-cyanoaniline. 0 copies were obtained.

[Compound (12)]

The same operation as in the production of compound (a) was performed except that 13.5 parts of compound (1) used in the production of compound (a) was changed to 15.2 parts of compound (12) to obtain compound (n). 15.0 parts were obtained. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (n).

compound (n)

[Example 15]
(Production of compound (o))
The same operation as in the synthesis of compound (1) was performed except that 10.0 parts of indigo used in the synthesis of compound (1) was changed to 22.0 parts of Bat Blue 5, and 24.4 parts of compound (13) was obtained. I got it.

[Compound (13)]

The same operation as in the production of compound (a) was performed except that 13.5 parts of compound (1) used in the production of compound (a) was changed to 23.9 parts of compound (13) to obtain compound (o). 22.8 parts of As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (o).

compound (o)

[Example 16]
(Production of compound (p))
In a reactor, 7.1 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. After that, 8.7 parts of aluminum chloride and 10.0 parts of indigo were added and refluxed for 10 hours. After completion of the reaction, methanol was added and filtered to obtain a green powder. This was separated with dichloromethane and water, and the organic layer was concentrated to obtain 11.8 parts of compound (14).

compound (14)

In a reaction vessel, 10.0 parts of compound (14), 16.7 parts of 2-aminoethyl diphenylborinate, 11.2 parts of titanium tetrachloride and 100 parts of toluene were mixed and stirred, and heated under reflux for 3 hours in a nitrogen atmosphere. bottom. After cooling to room temperature, it was poured into 300 parts of methanol with stirring to obtain a blue slurry. This slurry was filtered, washed with 300 parts of methanol, washed with 500 parts of water, and dried to obtain 11.2 parts of compound (p). As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (p).

compound (p)

[Example 17]
(Production of compound (q))

The same operation as in the synthesis of compound (14) was performed except that 7.1 parts of aniline used in the synthesis of compound (14) was changed to 12.3 parts of 3,5-dichloroaniline to obtain compound (15). 14.0 parts were obtained.

Compound (15)

The same operation as in the production of compound (p) was performed except that 10.0 parts of compound (14) used in the production of compound (p) was changed to 12.6 parts of compound (15) to obtain compound (q). 13.4 parts of As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (q).

compound (q)

[Example 18]
(Production of compound (r))

The same operation as in the synthesis of compound (14) was performed except that 7.1 parts of aniline used in the synthesis of compound (14) was changed to 10.9 parts of 1-naphthylamine, and compound (16) was obtained at 13.5 parts. I got it.

compound (16)

In a reaction vessel, 13.5 parts of compound (16), 16.7 parts of 2-aminoethyl diphenylborinate, 6.1 parts of aluminum chloride and 100 parts of toluene were mixed and stirred, and heated under reflux for 3 hours in a nitrogen atmosphere. . After cooling to room temperature, it was poured into 300 parts of methanol with stirring to obtain a blue slurry. This slurry was filtered, washed with 300 parts of methanol, washed with 500 parts of water, and dried to obtain 14.5 parts of compound (r). As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as compound (r).

compound (r)

[Example 19]
(Production of compound (s))
The same operation as in the synthesis of compound (14) was performed except that 7.1 parts of aniline used in the synthesis of compound (14) was changed to 8.2 parts of p-toluidine, and compound (17) was obtained in 11.7 parts. I got it.

compound (17)

In a reaction vessel, 10.8 parts of compound (17), 16.7 parts of 2-aminoethyl diphenylborinate, 7.5 parts of aluminum chloride and 100 parts of toluene were mixed and stirred, and heated under reflux for 3 hours in a nitrogen atmosphere. . After cooling to room temperature, it was poured into 300 parts of methanol with stirring to obtain a blue slurry. The slurry was filtered, washed with 300 parts of methanol, then with 500 parts of water, and dried to obtain 12.3 parts of compound (s). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as compound (s).

compound (s)

Table 1 shows the results of mass spectrometry and elemental analysis of the compounds produced in Examples 1 to 19.

[Example 20]
(Production of compound (a2))
200 parts of compound (a), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 8 hours. Next, this kneaded product is put into warm water and stirred for 1 hour while heating to about 70° C. to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. 189 parts of compound (a2) were obtained.

[Comparative Example 1]
(Production of comparative compound (t))
A comparative compound (t) having the following structure was obtained according to JP-A-2012-224593.

Compound (t)

<Method for producing binder resin solution>
(Production of binder resin 1 solution)
70.0 parts of cyclohexanone was charged into a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirring device, and the temperature was raised to 80°C. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toagosei 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 dropwise addition, the reaction was continued for an additional 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. A binder resin 1 solution was prepared by adding ether acetate.

(Production of binder resin 2 solution)
A separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and after replacing the inside of the flask with nitrogen, the distillate was added from the dropping tube. 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 dropwise addition, the mixture was further reacted at 100°C for 3 hours, then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile 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 changed to air exchange, and 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl groups), and the mixture was heated at 120°C. The reaction was continued for 6 hours, and when the solid content acid value reached 0.5, the reaction was terminated to obtain a solution of an acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were 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 was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. A binder resin 2 solution was prepared by adding acetate. The weight average molecular weight (Mw) was 19,000.

(Production of binder resin 3 solution)
207 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and the inside of the reaction vessel was replaced with nitrogen. After that, from a dropping tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix (registered trademark) M110” manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and the total amount of the copolymer solution obtained was stirred while injecting dry air for 1 hour. After cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Showa Denko Co., Ltd. A mixture of 6.5 parts of Karenz (registered trademark) MOI"), 0.08 part of dibutyl tin laurate and 26 parts of propylene glycol monomethyl ether acetate was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. A binder resin 3 solution was prepared by adding ether acetate. The weight average molecular weight (Mw) was 18,000.

<Method for producing resin-type dispersant solution>

(Production of basic resin-type dispersant 1 solution)
A reaction vessel equipped with a stirrer and a thermometer was charged with 41 parts of N,N-dimethylpropanediamine and 120 parts of chloroform, 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 the completion of the reaction by ¹ H-NMR, the reaction solution was washed successively with 300 parts of ion-exchanged water and 200 parts of saturated brine, and 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 with a rotary evaporator to obtain 58 parts of compound [B] represented by the following formula (18) as a pale yellow transparent liquid (yield 85%). Identification of the obtained compound was carried out by ¹ H-NMR.

Equation (18)

15.7 parts of methyl methacrylate, 47.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer, and the mixture was stirred for 50 minutes while flowing nitrogen. The mixture was stirred at ℃ 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 referred to as PGMAc) are charged, and the temperature is raised to 110° C. under a nitrogen stream to form the first block. started to polymerize. After polymerization for 4 hours, the polymerization solution was sampled and solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile matter.
Next, 25 parts of PGMAc and 30.3 parts of the above compound [B] as a second block monomer were added to the reactor, and the mixture was stirred while maintaining the temperature at 110° C. under a nitrogen atmosphere to continue the reaction. Two hours after the addition of the compound [B] represented by the above formula (18), the polymerization solution was sampled and the solid content was measured. It was confirmed.
Further, 6.8 parts of benzyl chloride was added to the reactor, stirred for 3 hours while maintaining the temperature at 110° C. under a nitrogen atmosphere, and then cooled.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by weight. Thus, a basic resin type dispersant 1 having an amine value per solid content of 70 mgKOH/g, a quaternary ammonium salt value of 30 mgKOH/g, a weight average molecular weight (Mw) of 9,800, and a nonvolatile content of 40% by weight was obtained. A solution was obtained.

(Production of basic resin type dispersant 2 solution)
60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C for 1 hour while flowing nitrogen. After stirring, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were added to the reactor, and the mixture was stirred while maintaining the temperature at 110° C. under a nitrogen atmosphere to continue the reaction. Two hours after the addition of dimethylaminoethyl methacrylate, the polymerization solution was sampled and the nonvolatile content was measured to confirm that the polymerization conversion rate of the second block was 98% or more in terms of the nonvolatile content. Polymerization was stopped by cooling.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. Thus, a basic resin-type dispersant 2 solution having an amine value per non-volatile content of 71.4 mgKOH/g, a weight average molecular weight of 9,900 (Mw), and a non-volatile content of 40% by mass was obtained.

(Production of basic resin-type dispersant 3 solution)
60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C for 1 hour while flowing nitrogen. After stirring, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 25.6 parts of an aqueous solution of methacryloyloxyethyltrimethylammonium chloride as a second block monomer ("Acryester DMC78" manufactured by Mitsubishi Rayon Co., Ltd.) were added to the reactor, and the temperature was maintained at 110°C under a nitrogen atmosphere. The reaction was continued while stirring. Two hours after the addition of methacryloyloxyethyltrimethylammonium chloride, the polymerization solution was sampled and the nonvolatile content was measured. Polymerization was terminated by cooling to room temperature.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. Thus, a basic resin-type dispersant 3 solution having an amine value per non-volatile content of 29.4 mgKOH/g, a weight average molecular weight of 9,800 (Mw), and a non-volatile content of 40% by mass was obtained.

(Production of acidic resin-type dispersant 4 solution)
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 were charged into a reaction vessel equipped with a gas inlet tube, temperature, condenser, and stirrer, and nitrogen gas was added. replaced with The inside of the reaction vessel was heated to 50° C. with stirring, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90° C., and the mixture was reacted for 7 hours while adding a solution obtained by adding 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. Solid content measurement confirmed that 95% had reacted.
19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst are added and reacted at 100° C. for 7 hours. rice field. After confirming that 98% or more of the acid anhydride is half-esterified by measuring the acid value, the reaction is terminated. An acidic resin type dispersant 4 solution having a molecular weight of 70 mgKOH/g and a weight average molecular weight of 8500 (Mw) was obtained.

(Production of resin-type dispersant 5 solution)
DISPER-BYK111 (manufactured by BYK-Chemie Japan; acid value: 129 mgKOH/g, solid content: 95%) was diluted in the same manner as the resin type dispersant 1 solution to prepare a resin type dispersant 5 solution.

<Production of near-infrared absorbing composition>
[Example 21]
(Near-infrared absorbing composition (D-1))
After uniformly stirring and mixing a mixture having the following composition, zirconia beads having a diameter of 0.5 mm were dispersed in an Eiger mill for 3 hours, and then filtered through a 0.5 μm filter to prepare a near-infrared absorbing composition. .
Compound (a): 10.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.5 parts Near infrared absorbing composition (D-1) for the whole , the water content was 1.3%, and the total amount of specific metal atoms was 210 ppm.

[Example 22]
(Near-infrared absorbing composition (D-2))
After uniformly stirring and mixing a mixture having the following composition, zirconia beads having a diameter of 0.5 mm were dispersed in an Eiger mill for 3 hours, and then filtered through a 0.5 μm filter to prepare a near-infrared absorbing composition. .
Compound (a): 10.0 parts Resin-type dispersant 1 solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 46.5 parts Deionized water: 1.0 parts Near-infrared absorbing composition ( D-2) With respect to the whole, the water content was 2.4%, and the total amount of specific metal atoms was 205 ppm.

[Example 23]
(Near-infrared absorbing composition (D-3))
A molecular sieve was added to the near-infrared absorbing composition (D-1), and the mixture was allowed to stand for 24 hours and filtered to obtain a near-infrared absorbing composition (D-3).
The water content was 0.1% and the total content of specific metal atoms was 183 ppm with respect to the entire near-infrared absorbing composition (D-3).

<Purification 1 of compound (a)>
15.0 parts of compound (a) and 1,000 parts of ion-exchanged water were placed in a beaker, heated and stirred at 60° C. for 1 hour, filtered, washed with 2,000 parts of ion-exchanged water, and dried.

<Purification 2 of compound (a)>
15.0 parts of compound (a) and 500 parts of N,N-dimethylformamide were placed in a beaker, heated and stirred at room temperature for 1 hour, filtered, washed with 500 parts of methanol and 2000 parts of deionized water, and dried.

<Purification 3 of compound (a)>
Example 1 except that in the production of compound (a), washing with 500 parts of methanol, washing with 500 parts of water, and washing with 500 parts of water were changed to washing with 500 parts of water instead of washing with methanol. performed the same operation.

[Example 24]
(Near-infrared absorbing composition (D-4))
A near-infrared absorbing composition (D-4) was prepared in the same manner as the near-infrared absorbing composition (D-1), except that the compound (a) was changed to the compound obtained in purification 1 of compound (a). ) was prepared.
The water content was 0.9% and the total amount of specific metal atoms was 110 ppm with respect to the entire near-infrared absorbing composition (D-4).

[Example 25]
(Near-infrared absorbing composition (D-5))
A near-infrared absorbing composition (D-5) was prepared in the same manner as the near-infrared absorbing composition (D-1), except that the compound (a) was changed to the compound obtained in purification 2 of compound (a). ) was prepared.
The water content was 1.0% and the total content of specific metal atoms was 45 ppm with respect to the entire near-infrared absorbing composition (D-5).

[Example 26]
(Near-infrared absorbing composition (D-6))
A near-infrared absorbing composition (D-6) was prepared in the same manner as the near-infrared absorbing composition (D-1), except that the compound (a) was changed to the compound obtained in purification 3 of compound (a). ) was prepared.
The water content was 1.3% and the total amount of specific metal atoms was 1150 ppm with respect to the entire near-infrared absorbing composition (D-6).

[Examples 27 to 62, 95 to 100, Comparative Example 2]
(Near-infrared absorbing compositions (D-7) to (D-42), (D-75) to (D-81))
A near-infrared absorbing composition is prepared in the same manner as in the near-infrared absorbing composition (D-1), except that the compound, resin-type dispersant solution, binder resin solution, and solvent are changed to the compositions and amounts shown in Table 2. (D-7) to (D-42) and (D-75) to (D-81) were prepared.

[Example 63]
(Near-infrared absorbing composition (D-43))
After uniformly stirring and mixing a mixture having the following composition, zirconia beads having a diameter of 0.5 mm were dispersed in an Eiger mill for 3 hours, and then filtered through a 0.5 μm filter to prepare a near-infrared absorbing composition. .
Compound (b): 7.0 parts Other near-infrared absorbing dye (X-1): 3.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.0 parts 5 copies

[Examples 64 to 90]
(Near-infrared absorbing composition (D-44) to (D-70))
Below, the near-infrared absorbing composition (D-43) was prepared in the same manner as the near-infrared absorbing composition (D-43) except that the near-infrared absorbing dye, resin-type dispersant solution, binder resin solution, and PGMAc were changed to the compositions and amounts shown in Table 2. Absorbent compositions (D-44) to (D-70) were prepared. (X-1) to (X-14) are other near-infrared absorbing dyes shown below.

[Example 91]
(Near-infrared absorbing composition (D-71))
After uniformly stirring and mixing a mixture having the following composition, zirconia beads having a diameter of 0.5 mm were dispersed in an Eiger mill for 3 hours, and then filtered through a 0.5 μm filter to prepare a near-infrared absorbing composition. .
Compound (a): 9.0 parts Dye derivative (G-1): 1.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.5 parts

[Examples 92-94]
(Near-infrared absorbing composition (D-72) to (D-74))
Below, in the same manner as the near-infrared absorbing composition (D-71), except that the near-infrared absorbing dye, resin-type dispersant solution, binder resin solution, and PGMAc were changed to the compositions and amounts shown in Table 2, the near-infrared Absorbent compositions (D-72) to (D-74) were prepared. Compounds represented by the following structural formulas (G-1) and (G-2) were used as dye derivatives.

(G-1)

(G-2)

Table 2 shows the compositions of the near-infrared absorbing compositions (D-1 to 81). The water content of (D-7 to 81) is 0.1 to 2.0% by mass relative to the total amount of the near-infrared absorbing composition, and the content of the specific metal atom is relative to the total amount of the near-infrared absorbing composition. It was 1 to 1000 mass ppm.

<Evaluation of near-infrared absorbing composition>
The near-infrared absorbing compositions (D-1 to D-81) obtained in Examples and Comparative Examples were tested for dispersion stability, spectral characteristics and heat resistance by the following methods. Table 3 shows the results.

(Evaluation of dispersion stability)
The viscosity of the obtained near-infrared absorbing composition immediately after preparation and after storage at 10° C. for one month was measured using an E-type viscometer. The ratio of (viscosity after storage for one month)/(viscosity immediately after preparation) was calculated and evaluated according to the following criteria. In addition, ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level not suitable for practical use.
◎: Viscosity ratio is 1.00 or more and less than 1.02 ○: Viscosity ratio is 1.02 or more and less than 1.05 △: Viscosity ratio is 1.05 or more and less than 1.10 ×: Viscosity ratio is 1.10 that's all

(Evaluation of spectral characteristics)
The resulting near-infrared absorbing composition (D) is coated on a glass substrate of 100 mm × 100 mm and 1.1 mm thick using a spin coater, and baked in an oven at 230 ° C. for 20 minutes to form a coating film after heat treatment. A coated substrate was prepared so that the film thickness of was 1.0 μm. The film thickness was measured using DEKTAK. Using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation), the absorption spectrum of the obtained substrate was measured in the wavelength range of 400 to 1200 nm.
The average transmittance (T) in each range was calculated from the measured absorption spectrum and evaluated according to the following criteria. Table 3 shows the evaluation results.

Spectral characteristic 1: 480 nm to 650 nm
○: 40% ≤ (T)
△: 25% ≤ (T) < 40%
x: (T) < 25%

Spectral characteristic 2: 700 nm to 850 nm
○: (T) ≤ 5%
△: 5% < (T) ≤ 10%
×: 10% < (T)

Spectral characteristic 3: 940 nm to 1200 nm
○: 80% ≤ (T)
△: 60% ≤ (T) < 80%
×: (T) < 60%

(Heat resistance test)
A test substrate was prepared in the same procedure as the spectral characteristic evaluation, and additionally heated at 210° C. for 20 minutes as a heat resistance test. The absorbance at the spectral maximum absorption wavelength of the near-infrared absorbing film was measured, the residual ratio to that before the heat resistance test was determined, and the heat resistance was evaluated according to the following criteria. The residual ratio was calculated using the following formula.
Residual rate = (absorbance after heat resistance test) / (absorbance before heat resistance test) x 100
◎: Residual rate is 95% or more ○: Residual rate is 90% or more and less than 95% ×: Residual rate is less than 90%

From the results in Table 3, the near-infrared absorbing composition containing the compound of the present invention has a high near-infrared cutting ability from 700 nm to 850 nm (spectral property 2), and transmits the visible light region from 480 nm to 650 nm and 940 nm or later. (spectral characteristics 1 and 3), good dispersion stability, and excellent heat resistance.

<Production of photosensitive near-infrared absorbing composition>
[Example 101]
(Photosensitive near-infrared absorbing composition (R-1))
The following mixture was uniformly stirred and mixed, and filtered through a 1.0 μm filter to obtain a photosensitive near-infrared absorbing composition (R-1).
Near-infrared absorbing composition (D-1): 50.0 parts Binder resin 2 solution: 7.5 parts Photopolymerization initiator (manufactured by Toagosei Co., Ltd. "Aronix M-402"): 2.0 parts Photopolymerization initiation Agent ("OXE-02" manufactured by BASF Japan): 1.5 parts PGMAc: 39.0 parts

[Examples 102 to 111 and Comparative Example 3]
(Photosensitive near-infrared absorbing composition (R-2) to (R-12))
Hereinafter, a photosensitive near-infrared absorbing composition in the same manner as the photosensitive near-infrared absorbing composition (R-1) except that the near-infrared absorbing composition was changed to the type of near-infrared absorbing composition shown in Table 4. Products (R-2) to (R-12) were obtained.

<Evaluation of photosensitive near-infrared absorbing composition>
The photosensitive near-infrared absorbing compositions (R-1) to (R-12) obtained in Examples and Comparative Examples were tested for dispersion stability, spectral characteristics and heat resistance by the following methods. Table 4 shows the results.

(Evaluation of dispersion stability)
The viscosity of the resulting photosensitive near-infrared absorbing composition (R) immediately after preparation and after storage at 10° C. for one month was measured using an E-type viscometer. The ratio of (viscosity after storage for one month)/(viscosity immediately after preparation) was calculated and evaluated according to the following criteria. In addition, ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level not suitable for practical use.
◎: Viscosity ratio is 1.00 or more and less than 1.02 ○: Viscosity ratio is 1.02 or more and less than 1.05 △: Viscosity ratio is 1.05 or more and less than 1.10 ×: Viscosity ratio is 1.10 that's all

(Spectral characteristic evaluation)
The obtained photosensitive near-infrared absorbing composition (R) was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater, dried at 60° C. for 5 minutes, and then coated using an ultra-high pressure mercury lamp. It is irradiated with ultraviolet rays of 100 mJ/cm ² , spray-developed with an alkaline developer consisting of a 0.2% by mass sodium carbonate aqueous solution, and then baked at 230° C. for 20 minutes to give a coating film thickness of 1.0 μm after heat treatment. A coated substrate was produced so as to be The film thickness was measured using DEKTAK. Using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation), the absorption spectrum of the obtained substrate was measured in the wavelength range of 400 to 1200 nm.
The average transmittance (T) in each range was calculated from the measured absorption spectrum, and evaluated according to the same criteria as in the evaluation of the spectral characteristics of the near-infrared absorbing composition (D). Table 4 shows the evaluation results.

(Heat resistance test)
A test substrate was prepared in the same procedure as the spectral characteristic evaluation, and additionally heated at 210° C. for 20 minutes as a heat resistance test. The absorbance at the spectral maximum absorption wavelength of the near-infrared absorbing film was measured, the residual ratio to that before the heat resistance test was determined, and the heat resistance was evaluated according to the following criteria. The residual ratio was calculated using the following formula.
Residual rate = (absorbance after heat resistance test) / (absorbance before heat resistance test) x 100
◎: Residual rate is 95% or more ○: Residual rate is 90% or more and less than 95% ×: Residual rate is less than 90%

From the results in Table 4, in the case of the photosensitive near-infrared absorbing composition (R), the results are similar to those of the near-infrared absorbing composition (D), and the near-infrared cutting ability up to 700 nm to 850 nm is high (spectral characteristics 2 ), transmits the visible light region of 480 nm to 650 nm and 940 nm and beyond (spectral characteristics 1 and 3), has good dispersion stability, and is excellent in heat resistance.

<Production of near-infrared cut filter>
[Examples 112 to 115]
(Near infrared absorption cut filter (F-1) to (F-4))
A glass substrate having a thickness of 1.1 mm was coated with the photosensitive near-infrared absorbing composition (R-1) of the present invention by a spin coater, and pre-baked by heat treatment on a hot plate at 100° C. for 1 minute.
Then, using an ultra-high pressure mercury lamp USH-200DP (manufactured by Ushio Inc.), pattern exposure was performed through a photomask at an exposure amount of 1000 mJ/cm ² in order to form a 100 μm square near-infrared absorption cut filter. .
The uncured portion of the exposed film was removed by a shower development method using a 0.2% by weight sodium carbonate aqueous solution as a developer at a developer pressure of 0.1 mPa to form a pattern of 400 μm×400 μm. After that, it was post-baked at 100° C. for 120 minutes. The film thickness of the near-infrared absorption cut filter (F-1) after heat treatment was 1.0 μm.
For the photosensitive near-infrared absorbing composition (R) shown in Table 5, near-infrared cut filters (F-2) to (F-4) were used in the same manner as the near-infrared cut filter (F-1). Obtained.

<Evaluation of near-infrared cut filter>
The near-infrared cut filters (F-1) to (F-4) were tested for spectral characteristics and heat resistance in the same manner as in the evaluation of the photosensitive near-infrared absorbing composition. Table 5 shows the results.

From the results in Table 5, Examples 112 to 115 had excellent spectral characteristics. It has high transmittance in the visible light region from 480 nm to 650 nm and after 940 nm (spectral characteristics 1 and 3), has excellent near-infrared absorptivity from 700 nm to 850 nm (spectral characteristics 2), and is excellent in heat resistance. Therefore, it is suitable for a near-infrared cut filter.

<Production of near-infrared absorptive composition (visible region absorptive composition) containing organic dye having absorption at 400 nm to 700 nm>

(Blue colored composition)
After uniformly stirring and mixing a mixture having the following composition, zirconia beads with a diameter of 0.5 mm were used to disperse the mixture with an Eiger mill for 3 hours, followed by filtration through a 0.5 μm filter to prepare a blue colored composition.
C. I. Pigment Blue PB15: 6: 10.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.5 parts

(Purple colored composition)
After uniformly stirring and mixing a mixture having the following composition, zirconia beads with a diameter of 0.5 mm were used to disperse the mixture with an Eiger mill for 3 hours, followed by filtration through a 0.5 μm filter to prepare a purple colored composition.
C. I. Pigment Violet PV23: 10.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.5 parts

(Yellow colored composition)
After uniformly stirring and mixing a mixture having the following composition, zirconia beads with a diameter of 0.5 mm were used to disperse the mixture with an Eiger mill for 3 hours, followed by filtration through a 0.5 μm filter to prepare a yellow colored composition.
C. I. Pigment yellow PY139: 10.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.5 parts

[Example 116]
(Visible light region absorbing composition (P-1))
The following mixture was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to obtain a visible light absorbing composition (P-1).
Near-infrared absorbing composition (D-1): 10.0 parts Blue pigment composition: 20.0 parts Purple pigment composition: 10.0 parts Yellow pigment composition: 10.0 parts Binder resin 1 solution: 7. 5 parts photopolymerizable compound (manufactured by Toagosei Co., Ltd. "Aronix M-402"): 2.0 parts photopolymerization initiator (manufactured by BASF Japan "OXE-02"): 1.5 parts PGMAc: 39.0 parts

[Examples 117 to 120]
(Visible light region absorbing compositions (P-2) to (P-5))
Hereinafter, a visible light region absorbing composition ( P-2) to (P-5) were obtained.

<Evaluation of Visible Light Region Absorbing Composition>
The resulting visible light region absorbing composition was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater so as to have a film thickness of 2.0 μm, dried at 60° C. for 5 minutes, and then dried at 230° C. was heated for 5 minutes to prepare a substrate.
The function of the filter is, for example, whether or not near-infrared rays can be transmitted, and whether or not light rays in other wavelength regions can be cut.
Below, the transmittance of 940 to 1200 nm and the absorption in the wavelength range of 400 to 850 nm were evaluated.

(400-850 nm absorption)
Using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation), the transmission spectrum of the obtained substrate was measured in a wavelength range of 400 to 850 nm.
○: transmittance of less than 2% in the entire 400 to 850 nm region △: transmittance of 2% or more in a partial region of 400 to 850 nm ×: transmittance of 2% or more in the entire region of 400 to 850 nm

(940-1200nm transparency)
The obtained substrate was measured for transmittance at 940 nm to 1200 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
○: Transmittance of 80% or more in the entire region of 940 to 1200 nm △: 40% or more and less than 80% in the partial region of 940 to 1200 nm ×: Less than 40% in the partial region of 940 to 1200 nm

(Heat resistance test)
The obtained substrate was additionally heated at 210° C. for 20 minutes as a heat resistance test. After that, a transmission spectrum in a wavelength range of 400 to 850 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
○: transmittance of less than 2% in the entire 400 to 850 nm region △: transmittance of 2% or more in a partial region of 400 to 850 nm ×: transmittance of 2% or more in the entire region of 400 to 850 nm

From the results in Table 6, Examples 116 to 120 absorb light in the entire range of 400 to 850 nm by including both a near-infrared absorbing dye and a dye that absorbs visible light in the range of 400 to 700 nm, and absorbs light in the entire range of 940 nm to 1200 nm. It can transmit near-infrared rays. Furthermore, it has excellent heat resistance.

<Production of near-infrared absorbing composition for molding>
(Thermoplastic resin (E))
(E-1) Polyester MA-2101M (polyester resin, manufactured by Unitika Ltd., crystalline resin, melting point 264° C.)
(E-2) Amilan CM3001-N (polyamide resin, manufactured by Toray Industries, crystalline resin, melting point 265° C.)
(E-3) Iupilon S-3000 (polycarbonate resin, manufactured by Mitsubishi Engineering-Plastics, amorphous resin, glass transition temperature 145 ° C.)
(E-4) Topas (cycloolefin resin, manufactured by Polyplastics, amorphous resin, glass transition temperature 78 ° C.)
(E-5) APEL (cycloolefin resin, manufactured by Mitsui Chemicals, amorphous resin, glass transition temperature 135 ° C.)
(E-6) ULTEM (polyetherimide resin, manufactured by Saudi Basic Industries Corporation, amorphous resin, glass transition temperature 217° C.)

[Example 121]
(Manufacturing of masterbatch)
1 part of the compound (a) and 99 parts of the thermoplastic resin (E-1) are fed from the same supply port into a twin-screw extruder with a screw diameter of 30 mm (manufactured by Japan Steel Works, Ltd.) and melt-kneaded at 300 ° C. After that, it was cut into pellets using a pelletizer to prepare a masterbatch (M-1).

(Film molding)
Mix 5 parts of the obtained masterbatch (M-1) with 95 parts of the thermoplastic resin (E-1) of the diluted resin, and use a T-die molding machine (manufactured by Toyo Seiki) at a temperature of 300 ° C. to form a film (Q-1) having a thickness of 250 μm.

[Examples 122 to 140, Comparative Example 4]
Films (Q-2) to (Q-21) having a thickness of 250 μm were formed using the materials shown in Table 7 in the same manner as in Example 121.

<Evaluation of near-infrared absorbing composition for molding>

(Spectral characteristic evaluation)
The absorption spectrum in the wavelength range of 400 to 1200 nm was measured for the obtained film using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). The average transmittance (T) in each range was calculated from the measured absorption spectrum and evaluated according to the following criteria. Table 8 shows the evaluation results.

Spectral characteristic 1: 480 nm to 650 nm
○: 40% ≤ (T)
△: 25% ≤ (T) < 40%
x: (T) < 25%

Spectral characteristic 2: 700 nm to 850 nm
○: (T) ≤ 5%
△: 5% < (T) ≤ 10%
×: 10% < (T)
Spectral characteristic 3: 940 nm to 1200 nm
○: 80% ≤ (T)
△: 60% ≤ (T) < 80%
×: (T) < 60%

(transparency)
The transparency of the resulting film was visually evaluated.
O: Turbidity is not recognized at all.
Δ: Slight turbidity is observed.
x: Turbidity is clearly observed.

From the results in Table 8, Examples 121 to 140 have high transmission in the visible light region of 480 nm to 650 nm (spectral characteristics 1), and excellent near-infrared absorption ability from 700 nm to 850 nm (spectral characteristics 2), 940 nm or later. of near-infrared light (spectral characteristics 3), and has excellent transparency and light resistance.

<Production of visible light region absorbing composition for molding>
[Example 141]
(Manufacturing of masterbatch)
1 part of compound (a), 1 part of pigment blue 15:3, 1 part of pigment yellow 147, 1 part of solvent red 52, 96 parts of thermoplastic resin (E-1) from the same supply port with a screw diameter of 30 mm The mixture was put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.), melt-kneaded at 300° C., and cut into pellets using a pelletizer to prepare a masterbatch (MP-1).

(Film molding)
Mix 5 parts of the obtained masterbatch (MP-1) with 95 parts of the thermoplastic resin (E-1) of the diluted resin, and use a T-die molding machine (manufactured by Toyo Seiki) at a temperature of 300 ° C. to form a film (QP-1) with a thickness of 250 μm.

[Examples 142 to 152]
Films (QP-2) to (QP-12) having a thickness of 250 μm were formed using the materials shown in Table 9 in the same manner as in Example 141.

The suitability of the near-infrared filter was evaluated for the obtained film. The function of the filter is, for example, whether or not near-infrared rays can be transmitted, and whether or not light rays in other wavelength regions can be cut.
Below, the transmittance of 940 to 1200 nm and the absorption in the wavelength range of 400 to 850 nm were evaluated.

(400-850 nm absorption)
Using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation), the transmission spectrum in the wavelength range of 400 to 850 nm was measured for the obtained film.
○: transmittance of less than 2% in the entire 400 to 850 nm region △: transmittance of 2% or more in a partial region of 400 to 850 nm ×: transmittance of 2% or more in the entire region of 400 to 850 nm

(940-1200nm transparency)
The transmittance of the obtained film at 940 to 1200 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
○: Transmittance of 80% or more in the entire region of 940 to 1200 nm △: 40% or more and less than 80% in the partial region of 940 to 1200 nm ×: Less than 40% in the partial region of 940 to 1200 nm

(transparency)
The transparency of the resulting film was visually evaluated.
O: Turbidity is not recognized at all.
Δ: Slight turbidity is observed.
x: Turbidity is clearly observed.

From the results in Table 10, Examples 141 to 152 absorb light in the entire range of 400 to 850 nm by including both a near-infrared absorbing dye and a dye that absorbs visible light in the range of 400 to 700 nm, and absorbs light in the entire range of 940 to 1200 nm. It can transmit near-infrared rays. Furthermore, it is excellent in transparency.

Claims (8)

A compound characterized by being represented by the following general formula (1) or general formula (2).

[wherein X ₁ to X ₂₂ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted arylalkyl group, optionally substituted cycloalkyl group, optionally substituted optionally substituted alkylthio group, optionally substituted arylthio group, amino group, optionally substituted alkylamino group, optionally substituted arylamino group, cyano group, halogen atom , nitro group, hydroxyl group, --SO ₃ H, --COOH, monovalent to trivalent metal salts or alkylammonium salts of these acidic groups. Two adjacent groups among the groups represented by X ₁ to X ₂₂ may be linked to form a 5- or 6-membered ring together with the carbon atoms to which they are attached. ] A near-infrared absorbing dye comprising the compound according to claim 1 . A near-infrared absorbing composition comprising the near-infrared absorbing dye according to claim 2 and a binder resin. 4. The near-infrared absorbing composition according to claim 3, wherein the water content in the near-infrared absorbing composition is 0.1 to 2.0% by mass with respect to the entire near-infrared absorbing composition. . The near-infrared absorbing composition contains a metal component containing metal atoms selected from Li, Na, Mg, K, Cs, Co, Ca, Fe, Si and Zr, and the entire near-infrared absorbing composition is 5. The near-infrared absorbing composition according to claim 3, wherein the total amount of said metal atoms in said metal component is 1 to 1000 mass ppm. 6. The near-infrared absorbing composition according to any one of claims 3 to 5, further comprising a photopolymerizable monomer and/or a photopolymerization initiator. The near-infrared absorptive composition according to any one of claims 3 to 6, further comprising an organic dye having absorption at 400 nm to 700 nm. An optical filter comprising a film formed from the near-infrared absorbing composition according to any one of claims 3 to 7.