JP2023085680A - Near-infrared absorbing composition and optical filter - Google Patents

Abstract

To provide: a near-infrared absorbing composition with high transmittance in a specific region of near-infrared rays (900 nm to 1200 nm), excellent near-infrared cut ability from 700 nm to 800 nm, and good dispersion stability, light resistance and heat resistance; and an optical filter.SOLUTION: A near-infrared absorbing composition contains a near-infrared absorbing pigment (A) represented by general formula (1) in the figure, and a green pigment (G) represented by a specific general formula.SELECTED DRAWING: Figure 1

Description

The present invention relates to a near-infrared absorbing composition and an optical filter.

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.

Patent document 1 discloses a phthalocyanine compound and a naphthalocyanine compound having a substituent as near-infrared absorbing dyes excellent in heat resistance and light resistance. Patent Document 2 discloses a naphthalocyanine compound that cuts near-infrared rays of 800 nm to 1000 nm.

WO2020-071470 publication JP-A-10-78509

However, phthalocyanine compounds and naphthalocyanine compounds have problems such as poor dispersion stability due to association, high viscosity of the near-infrared absorbing composition, and insufficient near-infrared transmittance in specific regions due to pigment aggregation. In addition, the naphthalocyanine compound has a longer maximum absorption wavelength than the phthalocyanine compound due to the expansion of the π-conjugated system, and the transmittance at, for example, 900 nm and 940 nm is sometimes lowered.

The present invention has a high near-infrared transmittance in a specific region (900 nm to 1200 nm), excellent near-infrared cutting ability of 700 nm to 800 nm, dispersion stability, light resistance, a near-infrared absorbing composition having good heat resistance, and The object is to provide an optical filter.

The present inventors have made intensive studies to solve the above problems, and found that a near-infrared absorbing dye (A) represented by general formula (1) and general formula (101) or general formula (102) The present inventors have found that the problem can be solved by using a near-infrared absorbing composition containing a green dye (G) represented by ), resulting in the present invention.

[一般式（１）中、Ｘ_１～Ｘ_８、Ｙ_ｌ～Ｙ_８は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、ニトリル基、カルボキシル基、スルホン基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいシクロアルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいフタルイミドメチル基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、または、置換基を有してもよいスルファモイル基を表す。また、Ｘ_１～Ｘ_８は、それぞれ独立に、互いに結合して置換基を有してもよい芳香環を形成しても良い。ただし、Ｘ_１とＸ_２、Ｘ_３とＸ_４、Ｘ_５とＸ₆、Ｘ_７とＸ_８のいずれか１組以上は互いに結合して置換基を有してもよい芳香環を形成する。
Ｚ_１は、－ＯＰ（＝Ｏ）Ｒ_１Ｒ_２、または一般式（２）で表される単量体単位を含む重合体部位を表す。ここでＲ_１、Ｒ_２はそれぞれ独立に、水素原子、水酸基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基を表し、Ｒ_１とＲ_２は、互いに結合して環を形成しても良い。
一般式（２）中、Ｗは、－ＣＯＮＨ－Ｒ_４－、－ＣＯＯ－Ｒ_５－、－ＣＯＮＨ－Ｒ_６－Ｏ－、－ＣＯＯ－Ｒ_７－Ｏ－を表し、Ｒ_４～Ｒ_７は、炭素原子と炭素原子の間が、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯＮＨ－、または－ＮＨＣＯ－で連結されていても良いアルキレン基もしくはアリーレン基を表す。Ｒ_３は水素原子または、メチル基を表す。＊は、Ａｌとの結合手である。］ That is, the present invention comprises a near-infrared absorbing dye (A) represented by the following general formula (1) and a green dye (G) represented by the following general formula (101) or general formula (102). It relates to a near-infrared absorbing composition characterized by comprising:

[In general formula (1), X ₁ to X ₈ and Y ₁ to Y ₈ each independently have a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, or a substituent. Alkyl groups, optionally substituted aryl groups, optionally substituted cycloalkyl groups, optionally substituted heterocyclic groups, optionally substituted alkoxyl groups, aryloxy group optionally having substituent(s), alkylthio group optionally having substituent(s), arylthio group optionally having substituent(s), phthalimidomethyl group optionally having substituent(s), represents an optionally substituted alkylamino group, an optionally substituted arylamino group, or an optionally substituted sulfamoyl group. In addition, X ₁ to X ₈ may each independently combine with each other to form an aromatic ring which may have a substituent. However, one or more pairs of X ₁ and X ₂ , X ₃ and X ₄ , X ₅ and X ₆ , and X ₇ and X ₈ are bonded to each other to form an aromatic ring which may have a substituent.
Z ₁ represents —OP(=O)R ₁ R ₂ or a polymer moiety containing a monomer unit represented by general formula (2). Here, R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, It represents an aryloxy group which may have a substituent, and R ₁ and R ₂ may combine with each other to form a ring.
In general formula (2), W represents -CONH-R ₄ -, -COO-R ₅ -, -CONH-R ₆ -O-, -COO-R ₇ -O-, and R ₄ to R ₇ , represents an alkylene group or an arylene group in which carbon atoms may be linked by --O--, --CO--, --COO--, --OCO--, --CONH-- or --NHCO--. _R3 represents a hydrogen atom or a methyl group. * is a bond with Al. ]

[一般式（１０１）および（１０２）中、Ｒ_２７～Ｒ_４２は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、ニトリル基、置換基を有してもよいアルキル基、置換基を有してもよいシクロアルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいアルキルアミノ基、または、置換基を有してもよいアリールアミノ基を表す。Ｍ_１は、銅（Ｃｕ）、亜鉛（Ｚｎ）を表す。Ｍ_２は、アルミニウム（Ａｌ）を表す。
一般式（１０２）中、Ｚ_３は、－ＯＰ（＝Ｏ）Ｒ_１Ｒ_２、または一般式（２）で表される単量体単位を含む重合体部位を表す。ここでＲ_１、Ｒ_２はそれぞれ独立に、水素原子、水酸基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基を表し、Ｒ_１とＲ_２は、互いに結合して環を形成しても良い。］

[In general formulas (101) and (102), R ₂₇ to R ₄₂ each independently represent a hydrogen atom, a halogen atom, a nitro group, a nitrile group, an optionally substituted alkyl group, or a substituted optionally substituted cycloalkyl group, optionally substituted heterocyclic group, optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted It represents an alkylthio group, an arylthio group which may have a substituent, an alkylamino group which may have a substituent, or an arylamino group which may have a substituent. _M1 represents copper (Cu) and zinc (Zn). _M2 represents aluminum (Al).
In general formula (102), Z ₃ represents —OP(=O)R ₁ R ₂ or a polymer moiety containing a monomer unit represented by general formula (2). Here, R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, It represents an aryloxy group which may have a substituent, and R ₁ and R ₂ may combine with each other to form a ring. ]

［一般式（３）中、Ｙ_９～Ｙ_１６、Ｒ_８～Ｒ_２１は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、ニトリル基、カルボキシル基、スルホン基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいシクロアルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいフタルイミドメチル基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、または、置換基を有してもよいスルファモイル基を表す。
Ｚ_２は、－ＯＰ（＝Ｏ）Ｒ_１Ｒ_２、または一般式（２）で表される単量体単位を含む重合体部位を表す。ここでＲ_１、Ｒ_２はそれぞれ独立に、水素原子、水酸基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基を表し、Ｒ_１とＲ_２は、互いに結合して環を形成しても良い。
一般式（２）中、Ｗは、－ＣＯＮＨ－Ｒ_４－、－ＣＯＯ－Ｒ_５－、－ＣＯＮＨ－Ｒ_６－Ｏ－、－ＣＯＯ－Ｒ_７－Ｏ－を表し、Ｒ_４～Ｒ_７は、炭素原子と炭素原子の間が、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯＮＨ－、または－ＮＨＣＯ－で連結されていても良いアルキレン基もしくはアリーレン基を表す。Ｒ_３は水素原子または、メチル基を表す。＊は、Ａｌとの結合手である。］ That is, the present invention relates to the near-infrared absorbing composition, wherein the near-infrared absorbing dye (A) contains a near-infrared absorbing dye (A1) represented by the following general formula (3).

[In the general formula (3), Y ₉ to Y ₁₆ and R ₈ to R ₂₁ each independently have a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, or a substituent. Alkyl groups, optionally substituted aryl groups, optionally substituted cycloalkyl groups, optionally substituted heterocyclic groups, optionally substituted alkoxyl groups, aryloxy group optionally having substituent(s), alkylthio group optionally having substituent(s), arylthio group optionally having substituent(s), phthalimidomethyl group optionally having substituent(s), represents an optionally substituted alkylamino group, an optionally substituted arylamino group, or an optionally substituted sulfamoyl group.
Z ₂ represents —OP(=O)R ₁ R ₂ or a polymer moiety containing a monomer unit represented by general formula (2). Here, R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, It represents an aryloxy group which may have a substituent, and R ₁ and R ₂ may combine with each other to form a ring.
In general formula (2), W represents -CONH-R ₄ -, -COO-R ₅ -, -CONH-R ₆ -O-, -COO-R ₇ -O-, and R ₄ to R ₇ , represents an alkylene group or an arylene group in which carbon atoms may be linked by --O--, --CO--, --COO--, --OCO--, --CONH-- or --NHCO--. _R3 represents a hydrogen atom or a methyl group. * is a bond with Al. ]

Further, in the present invention, the green dye (G) is 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, and C.I. I. Pigment Green 63, comprising at least one selected from the group consisting of Pigment Green 63.

The present invention also relates to the near-infrared absorbing composition, wherein the green dye (G) contains a pigment having an acidic group amount of 100 to 600 μmol.

Further, in the present invention, the mass ratio of the near-infrared absorbing dye (A) and the green dye (G) in the near-infrared absorbing composition is 95/5 to 60/40. It relates to absorbent compositions.

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 absorptive composition, characterized by containing an organic dye having absorption in the range of 400 nm to 700 nm (excluding the green dye (G)).

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

According to the present invention, a near-infrared absorbing dye having high transmittance of near-infrared light (900 nm to 1200 nm) in a specific region, excellent near-infrared cutting ability of 700 nm to 800 nm, good dispersion stability, light resistance, and heat resistance, and near-infrared light Absorbent compositions and optical filters can be provided.

FIG. 1 is the X-ray diffraction pattern of the near-infrared absorbing dye (AA-1). FIG. 2 is the X-ray diffraction pattern of the near-infrared absorbing dye (AA-49). FIG. 3 is an X-ray diffraction pattern of Reference Material 1'.

Terms used herein are defined. In this specification, the compound represented by general formula (1) is called phthalocyanine. Further, the ring structural site of the compound represented by the general formula (1) excluding the axial ligand _Z1 is called a phthalocyanine site. "(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.). Colorants include pigments and dyes.

<Near-infrared absorbing dye (A)>
The near-infrared absorbing composition of the present invention is characterized by containing a near-infrared absorbing dye (A) represented by the following general formula (1). The near-infrared absorbing dye (A) has one or more aromatic rings which may have a substituent so as to expand the π-conjugated system of the phthalocyanine skeleton having high heat resistance and light resistance, so that it has a wavelength of 700 nm to 800 nm. absorbs near-infrared rays well. In addition, since it has no absorption in the wavelength region longer than 900 nm, it has a spectral characteristic of being well transmitted.

In general, phthalocyanine dyes are strongly aggregated by association of aromatic rings and often exist in a crystal structure. In that case, since it becomes difficult to dissolve in an ordinary solvent, it is dispersed using a dispersant or the like and used as a dispersion. However, a film produced from this dispersion has low transmittance in the region of 480 nm to 650 nm, which is a region of high relative luminosity, due to association-derived absorption. On the other hand, the near-infrared absorbing dye (A) has a polymer moiety containing -OP(=O)R ₁ R ₂ or a monomer unit represented by the general formula (2) in aluminum as the central metal. The coordination weakens the absorption from the association and improves the transmission from 480 nm to 650 nm.

[一般式（１）中、Ｘ_１～Ｘ_８、Ｙ_ｌ～Ｙ_８は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、ニトリル基、カルボキシル基、スルホン基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいシクロアルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいフタルイミドメチル基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、または、置換基を有してもよいスルファモイル基を表す。また、Ｘ_１～Ｘ_８は、それぞれ独立に、互いに結合して置換基を有してもよい芳香環を形成しても良い。ただし、Ｘ_１とＸ_２、Ｘ_３とＸ_４、Ｘ_５とＸ₆、Ｘ_７とＸ_８のいずれか１組以上は互いに結合して置換基を有してもよい芳香環を形成する。
Ｚ_１は、－ＯＰ（＝Ｏ）Ｒ_１Ｒ_２、または一般式（２）で表される単量体単位を含む重合体部位を表す。ここでＲ_１、Ｒ_２はそれぞれ独立に、水素原子、水酸基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基を表し、Ｒ_１とＲ_２は、互いに結合して環を形成しても良い。
一般式（２）中、Ｗは、－ＣＯＮＨ－Ｒ_４－、－ＣＯＯ－Ｒ_５－、－ＣＯＮＨ－Ｒ_６－Ｏ－、－ＣＯＯ－Ｒ_７－Ｏ－を表し、Ｒ_４～Ｒ_７は、炭素原子と炭素原子の間が、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯＮＨ－、または－ＮＨＣＯ－で連結されていても良いアルキレン基もしくはアリーレン基を表す。Ｒ_３は水素原子または、メチル基を表す。＊は、Ａｌとの結合手である。］ Therefore, it is possible to provide a near-infrared absorptive dye which is excellent in heat resistance, light resistance, near-infrared absorption in the range of 700 nm to 800 nm, and transmittance in the wavelength range of 480 nm to 650 nm and longer than 900 nm.

[In general formula (1), X ₁ to X ₈ and Y ₁ to Y ₈ each independently have a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, or a substituent. Alkyl groups, optionally substituted aryl groups, optionally substituted cycloalkyl groups, optionally substituted heterocyclic groups, optionally substituted alkoxyl groups, aryloxy group optionally having substituent(s), alkylthio group optionally having substituent(s), arylthio group optionally having substituent(s), phthalimidomethyl group optionally having substituent(s), represents an optionally substituted alkylamino group, an optionally substituted arylamino group, or an optionally substituted sulfamoyl group. In addition, X ₁ to X ₈ may each independently combine with each other to form an aromatic ring which may have a substituent. However, one or more pairs of X ₁ and X ₂ , X ₃ and X ₄ , X ₅ and X ₆ , and X ₇ and X ₈ are bonded to each other to form an aromatic ring which may have a substituent.
Z ₁ represents —OP(=O)R ₁ R ₂ or a polymer moiety containing a monomer unit represented by general formula (2). Here, R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, It represents an aryloxy group which may have a substituent, and R ₁ and R ₂ may combine with each other to form a ring.
In general formula (2), W represents -CONH-R ₄ -, -COO-R ₅ -, -CONH-R ₆ -O-, -COO-R ₇ -O-, and R ₄ to R ₇ , represents an alkylene group or an arylene group in which carbon atoms may be linked by --O--, --CO--, --COO--, --OCO--, --CONH-- or --NHCO--. _R3 represents a hydrogen atom or a methyl group. * is a bond with Al. ]

The near-infrared absorbing dye (A) is a weight containing a phthalocyanine moiety (PC1) and —OP(=O)R ₁ R ₂ (phosphorus compound moiety), or a monomer unit represented by general formula (2). Consists of united parts. The phthalocyanine moiety (PC1) is preferably made from a phthalocyanine represented by the following general formula (4).

(Phthalocyanine site (PC1))

general formula (4)

In general formula (4), X ₁ to X ₈ and Y 1 _to Y ₈ have the same meanings as X ₁ to X 8 and Y _{1 to} Y ₈ in general formula (1).

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 "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 "heterocyclic group" of the heterocyclic group optionally having a substituent includes a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group and the like. ” includes a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrolyl group, and the like.

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 optionally having a substituent includes, for example, a phenoxy group, a naphthoxy group, an anthryloxy group, etc.
"Aryloxy group having a substituent" includes, for example, p-methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4- A chlorophenoxy group and the like can be mentioned.

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, and the like. 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. .

Examples of the "substituted phthalimidomethyl group" include a 4-nitrophthalimidomethyl group, a 3-chlorophthalimidomethyl group, a tetrafluorophthalimidomethyl group and the like.

The "alkylamino group" of the alkylamino group optionally having a substituent is, for example, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, octylamino group, decylamino group, dodecylamino group, octadecylamino group, cyclohexylamino group, stearylamino group, dimethylamino group, diethylamino group, dibutylamino group and the like. Examples of "substituted alkylamino group" include N,N-di(2-hydroxyethyl)amino group and the like.

The "arylamino group" of the arylamino group optionally having a substituent includes, for example, a phenylamino group, a naphthylamino group, a diphenylamino group and the like. Examples of "substituted arylamino group" include 4-tert-butylphenylamino group, N-phenyl-N-ethylamino group and the like.

A "sulfamoyl group having a substituent" includes, for example, a 3-(diethylamino)propylaminosulfamoyl group, a stearylaminosulfamoyl group, a dibutylaminosulfamoyl group, a 2-(piperidino)ethylaminosulfamoyl group, and the like. is mentioned.

The substituents of the aromatic ring which may have a substituent include a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an alkyl group which may have a substituent, and a substituent which may have aryl group, optionally substituted cycloalkyl group, optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted alkylthio group, substituted An arylthio group optionally having a group is exemplified.

(—OP(=O)R ₁ R ₂ (phosphorus compound moiety))
One form of the near-infrared absorbing dye (A) represented by the general formula (1) is a phosphate group in the phosphorus compound moiety represented by —OP(=O)R ₁ R ₂ and Aluminum cations form salts.
The raw material of the phosphorus compound portion is a phosphorus compound represented by general formula (5).

general formula (5)

In general formula (5), R ₅₀ and R ₅₁ each independently represent a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted It represents an alkoxyl group or an optionally substituted aryloxy group, and R ₅₀ and R ₅₁ may combine with each other to form a ring.
V represents a hydroxy group or a chlorine atom.

"Alkyl group" of alkyl group optionally having substituent(s), "aryl group" of aryl group optionally having substituent(s), "alkoxyl group" of alkoxyl group optionally having substituent(s), substituent Examples of the "aryloxy group" of the aryloxy group which may have are the same as those exemplified in the explanation of the general formula (4).

In the phosphorus compound represented by the general formula (5), at least one of R ₂₀ and R ₂₁ has an optionally substituted aryl group or a substituent from the viewpoint of dispersibility and color characteristics. It is preferably an aryloxy group that may be substituted, more preferably both R ₂₀ and R ₂₁ are an aryl group or an aryloxy group, and both R ₂₀ and R ₂₁ are a phenyl group or a phenoxy group. is more preferred.

Representative examples of phosphorus compounds include the structures shown below, but the present invention is not limited thereto.

(Polymer portion containing a monomer unit represented by general formula (2))
One form of the near-infrared absorbing dye (A) represented by the general formula (1) is a phosphate group in the polymer moiety containing a monomer unit represented by the general formula (2), and in the phthalocyanine moiety is a salt formed from the aluminum cation of
The polymer portion is obtained by vinyl-polymerizing the raw material monomer represented by the general formula (6). For the polymer portion, the monomer represented by the general formula (6) and other monomers besides the monomer represented by the general formula (6) can be used.

general formula (6)

In general formula (6), W is -CONH-R ₂₃ -, -COO-R ₂₄ -, -CONH-R ₂₅ -O-, -COO-R ₂₆ -O-, R ₂₃ to R ₂₆ are carbon atoms represents an alkylene group or an arylene group which may be linked by -O-, -CO-, -COO-, -OCO-, -CONH- or -NHCO- between and a carbon atom.
Examples of the alkylene group include methylene group, ethylene group, propylene group and butylene group. Arylene groups include, for example, phenylene, naphthylene, biphenylene, terphenylene and anthrylene groups. Examples of R ₂₃ to R ₂₆ include methylene group, ethylene group, propylene group and butylene group.
_R22 represents a hydrogen atom or a methyl group.

Monomers represented by the general formula (6) include, for example, (2-(meth)acryloyloxyethyl)acid phosphate, (2-(meth)acryloyloxypropyl)acid phosphate, (2-(meth)acryloyloxyisopropyl) acid phosphates;

Other monomers include, for example, (meth)acrylic acid esters, crotonic acid esters, vinyl esters, maleic diesters, fumaric acid diesters, itaconic acid diesters, (meth)acrylamides, vinyl ethers, and vinyl alcohol. Examples thereof include esters, styrenes, (meth)acrylonitrile, acid group-containing monomers, thermally crosslinkable group-containing monomers, and the like.

(Meth)acrylic acid esters, 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, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , t-octyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, acetoxyethyl (meth)acrylate, phenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ( Meth) 2-methoxyethyl acrylate, 2-ethoxyethyl (meth) acrylate, 2-(2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, (meth) ) benzyl acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, (meth) Polyethylene glycol monomethyl ether acrylate, polyethylene glycol monoethyl ether (meth)acrylate, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth) ) dicyclopentenyloxyethyl acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (meth)acrylate Examples include tribromophenyl acrylate and tribromophenyloxyethyl (meth)acrylate.

Examples of crotonates include butyl crotonate and hexyl crotonate.

Vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, and vinyl benzoate. Maleic acid diesters include, for example, dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of fumarate diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(Meth)acrylamides include, for example, (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Nn- butylacryl(meth)amide, Nt-butyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N, N-diethyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-benzyl(meth)acrylamide, (meth)acryloylmorpholine, diacetoneacrylamide and the like.

Vinyl ethers include, for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Styrenes include, for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene , hydroxystyrene protected with a group (eg, t-Boc) that can be deprotected by an acidic substance, methyl vinylbenzoate, α-methylstyrene, and the like.

Acid group-containing monomers include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride; , Unsaturated dicarboxylic acids such as citraconic acid, citraconic anhydride, and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono(2-acryloyloxyethyl), Divalent or higher polyvalent carboxylic acid mono [(meth ) acryloyloxyalkyl] esters; mono(meth)acrylates of both carboxy-terminated polymers such as ω-carboxy-polycaprolactone monoacrylate and ω-carboxy-polycaprolactone monomethacrylate;

The thermally crosslinkable group in the thermally crosslinkable group-containing monomer becomes, for example, a crosslink point of the near-infrared absorbing dye and contributes to improving the heat resistance of the near-infrared absorbing dye. Thermally crosslinkable groups include, for example, hydroxyl groups, carboxylic acid anhydrides, primary or secondary amino groups, imino groups, oxetanyl groups, tert-butyl groups, epoxy groups, mercapto groups, isocyanate groups and the like. Among these, hydroxyl group, carboxyl group, oxetanyl group, tert-butyl group, isocyanate group, and (meth)acryloyl group are preferred in terms of storage stability and reactivity, and hydroxyl group is more preferred.
Examples of hydroxyl group-containing monomers include, but are not limited to, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, 4 -hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate or caprolactone adducts of these monomers (1 to 5 moles). Among these, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred from the viewpoint of heat resistance.

Oxetanyl group-containing monomers, for example, 3-(acryloyloxymethyl) 3-methyloxetane, 3-(methacryloyloxymethyl) 3-methyloxetane, 3-(acryloyloxymethyl) 3-ethyloxetane, 3-(methacryloyloxymethyl ) 3-ethyloxetane, 3-(acryloyloxymethyl)3-butyloxetane, 3-(methacryloyloxymethyl)3-butyloxetane, 3-(acryloyloxymethyl)3-hexyloxetane and 3-(methacryloyloxymethyl)3 - hexyl oxetane and the like.

Examples of tert-butyl group-containing monomers include tert-butyl acrylate and tert-butyl methacrylate.

Examples of isocyanate group-containing monomers include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 4-isocyanatobutyl methacrylate, 4-isocyanatobutyl acrylate and the like. In addition, the isocyanate group includes, for example, a blocked isocyanate group. A blocked isocyanate group is a functional group that, under normal conditions, protects the isocyanate group with another functional group to suppress the reactivity of the isocyanate group, while deprotecting the isocyanate group by heating to regenerate the active isocyanate group. is the base.

Commercial products of blocked isocyanate group-containing monomers include, for example, 2-[(3,5-dimethylpyrazolyl)carboxyamino]ethyl methacrylate (KarenzuMOI-BP, manufactured by Showa Denko); methacrylic acid 2-(O-[1' -methylpropylideneamino]carboxyamino)ethyl (Karenzu MOI-BM, manufactured by Showa Denko KK) and the like.

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

The amount of the monomer represented by general formula (6) used to synthesize the polymer moiety is preferably 1 to 30% by mass, more preferably 5 to 15% by mass, based on 100% by mass of the total monomers. When used in an appropriate amount, optical properties are improved.

The amount of the thermally crosslinkable group-containing monomer used is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, based on 100% by mass of the total monomers. Heat resistance is improved when used in an appropriate amount.

Methods for synthesizing the polymer moiety include, for example, anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, living radical polymerization and the like. Among these, free radical polymerization or living radical polymerization is preferred.

Free radical polymerization methods use polymerization initiators. Examples of polymerization initiators include azo compounds and organic peroxides.
Azo compounds include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane 1-carbonitrile), 2, 2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4′-azobis(4-cyanovaleric acid), 2,2′-azobis(2-hydroxymethylpropionitrile), or 2,2′-azobis[2-(2-imidazolin-2-yl) propane] and the like. Organic peroxides are, for example, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate. carbonate, tert-butylperoxyneodecanoate, tert-butylperoxybivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionylperoxide, diacetylperoxide and the like.

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

The polymerization temperature is preferably 40 to 150°C, more preferably 50 to 110°C. The polymerization time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

The living radical polymerization method can synthesize a block polymer or a polymer with a narrow molecular weight distribution because side reactions that occur in general radical polymerization are suppressed and polymerization growth occurs uniformly.

Among various polymerization methods, the living radical polymerization method is preferably an atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as a polymerization initiator and a transition metal complex as a catalyst. This method is preferable in that monomers having various structures can be polymerized and a polymerization temperature adaptable to existing equipment can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in References 1 to 8 below.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al., J. Am. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) WO96/030421 (Reference 6) WO97/018247 (Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

It is preferable to use an organic solvent for synthesizing the polymer portion. Organic solvents include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate. , ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, or diethylene glycol monobutyl ether acetate.

The weight average molecular weight of the polymer portion is preferably 5,000 to 20,000, more preferably 8,000 to 15,000. Having an appropriate molecular weight improves optical properties and heat resistance.

The glass transition temperature (Tg) of the polymer portion is preferably -50 to 150°C, more preferably 20 to 80°C. An appropriate Tg improves optical properties.

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

(X-ray diffraction pattern)
The near-infrared absorbing dye (A) in the present invention has at least Bragg angles 2θ (±0.3°) = 6.3°, 8.8°, 23.6°, and 24° in the powder X-ray diffraction spectrum. It preferably has a diffraction peak at 4°. The above-described near-infrared absorbing dye (A) controlled to a crystal form has a controlled interplanar spacing in the stacking direction of molecules, weakens intermolecular interactions, and as a result has excellent dispersibility and dispersion stability. A method for measuring the powder X-ray diffraction spectrum will be described later.

［一般式（３）中、Ｙ_９～Ｙ_１６、Ｒ_８～Ｒ_２１は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、ニトリル基、カルボキシル基、スルホン基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいシクロアルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいフタルイミドメチル基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいアリールアミノ基、または、置換基を有してもよいスルファモイル基を表す。
Ｚ_２は、－ＯＰ（＝Ｏ）Ｒ_１Ｒ_２、または一般式（２）で表される単量体単位を含む重合体部位を表す。ここでＲ_１、Ｒ_２はそれぞれ独立に、水素原子、水酸基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基を表し、Ｒ_１とＲ_２は、互いに結合して環を形成しても良い。
一般式（２）中、Ｗは、－ＣＯＮＨ－Ｒ_４－、－ＣＯＯ－Ｒ_５－、－ＣＯＮＨ－Ｒ_６－Ｏ－、－ＣＯＯ－Ｒ_７－Ｏ－を表し、Ｒ_４～Ｒ_７は、炭素原子と炭素原子の間が、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯＮＨ－、または－ＮＨＣＯ－で連結されていても良いアルキレン基もしくはアリーレン基を表す。Ｒ_３は水素原子または、メチル基を表す。＊は、Ａｌとの結合手である。］ <Near-infrared absorbing dye (A1)>
The near-infrared absorbing dye (A) in the present invention preferably contains a near-infrared absorbing dye (A1) represented by the following general formula (3).

[In the general formula (3), Y ₉ to Y ₁₆ and R ₈ to R ₂₁ each independently have a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, or a substituent. Alkyl groups, optionally substituted aryl groups, optionally substituted cycloalkyl groups, optionally substituted heterocyclic groups, optionally substituted alkoxyl groups, aryloxy group optionally having substituent(s), alkylthio group optionally having substituent(s), arylthio group optionally having substituent(s), phthalimidomethyl group optionally having substituent(s), represents an optionally substituted alkylamino group, an optionally substituted arylamino group, or an optionally substituted sulfamoyl group.
Z ₂ represents —OP(=O)R ₁ R ₂ or a polymer moiety containing a monomer unit represented by general formula (2). Here, R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, It represents an aryloxy group which may have a substituent, and R ₁ and R ₂ may combine with each other to form a ring.
In general formula (2), W represents -CONH-R ₄ -, -COO-R ₅ -, -CONH-R ₆ -O-, -COO-R ₇ -O-, and R ₄ to R ₇ , represents an alkylene group or an arylene group in which carbon atoms may be linked by --O--, --CO--, --COO--, --OCO--, --CONH-- or --NHCO--. _R3 represents a hydrogen atom or a methyl group. * is a bond with Al. ]

The near-infrared absorbing dye (A1) is a weight containing a phthalocyanine moiety (PC2) and —OP(=O)R ₁ R ₂ (phosphorus compound moiety), or a monomer unit represented by general formula (2). Consists of united parts. The phthalocyanine moiety (PC2) is preferably made from a phthalocyanine represented by the following general formula (7).

(Phthalocyanine site (PC2))

general formula (7)

In general formula (7), Y ₉ to Y ₁₆ and R ₈ to R ₂₁ have the same meanings as Y ₉ to Y ₁₆ and R ₈ to R ₂₁ in general formula (3).

an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted phthalimide The methyl group or the optionally substituted sulfamoyl group is as described above.

As the near-infrared absorbing dye (A1) represented by the general formula (3), from the viewpoint of dispersibility and color characteristics, Y ₉ to Y ₁₆ and R ₈ to R ₂₁ are hydrogen atoms, halogen atoms, or An alkoxyl group which may have a substituent is preferred.

In the near-infrared absorbing composition of the present invention, the content of the near-infrared absorbing dye (A1) in the near-infrared absorbing dye (A) is preferably 20 to 100% by mass.
The near-infrared absorbing dye (A1) is a 3+1 type asymmetric phthalocyanine in which three units in which pyrrole rings and naphthalene rings are condensed and one isoindole ring unit are bridged with nitrogen. Since the near-infrared absorbing dye (A1) is of an asymmetric type, aggregation due to association of aromatic rings is alleviated, and a near-infrared absorbing composition with good dispersion stability can be obtained. In addition, the absorption spectrum does not have an extreme point at 800 to 900 nm probably due to its asymmetric nature, so a near-infrared absorptive composition with little noise can be obtained. The extremum point is a point at which the absorbance changes from an increase to a decrease or from a decrease to an increase when the absorbance is confirmed from the short wavelength side to the long wavelength side. If there is an extremum point, transmitted light at that wavelength may be detected as noise, so it can be said that near-infrared absorption ability is better when there is no extremum point.

(Method for synthesizing phthalocyanine moiety)
General industrial production methods for the phthalocyanines represented by general formulas (4) and (7) are described below. The method (4) is a method for synthesizing the phthalocyanine represented by the general formula (7). When the methods (1) to (3) are used, the phthalocyanine represented by the general formula (4) contains multiple structures. When the near-infrared absorbing dye (A) contains a plurality of structures, the aggregation due to the association of the aromatic rings is alleviated, and a near-infrared absorbing composition having excellent dispersion stability is obtained, so (1) to (3) ) method is preferred.
(1) Wyler method Substituted or unsubstituted phthalic anhydride and naphthalenedicarboxylic anhydride, or substituted or unsubstituted phthalic anhydride and naphthalenedicarboxylic anhydride are reacted at high temperature in the presence of urea and a metal salt. Method. By using phthalic anhydride and naphthalenedicarboxylic anhydride together, or by using phthalic anhydride and naphthalenedicarboxylic anhydride together, a near-infrared absorbing dye represented by general formula (1) can be obtained.
(2) Phthalodinitrile method A substituted or unsubstituted phthalodinitrile and 2,3-dicyanonaphthalene are treated in an alcoholic solvent such as n-amyl alcohol, n-hexyl alcohol, 1-methoxyethanol and 1-ethoxyethanol. , DBU (1,8-diazabicyclo[5,4,0]undecene-7), DBN (1,5-diazabicyclo[4,3,0]nonene-5), or strong bases such as (metal)alkoxides. A method of reacting with a metal salt in the presence. By using phthalodinitrile and 2,3-dicyanonaphthalene together, a near-infrared absorbing dye represented by general formula (1) can be obtained.
(3) Diiminoisoindoline method Substituted or unsubstituted 1,3-diiminoisoindoline and 1,3-diiminobenzo[f]isoindoline are combined with 2-dimethylaminoethanol, quinoline, DBU (1,8-diazabicyclo[ A method of reacting with a metal salt in the presence of a strong base such as 5,4,0]undecene-7). By using 1,3-diiminoisoindoline and 1,3-diiminobenzo[f]isoindoline together, a near-infrared absorbing dye represented by general formula (1) can be obtained.
(4) Subphthalocyanine ring-opening method (asymmetric phthalocyanine synthesis method from subphthalocyanine)
A method of synthesizing a compound represented by the general formula (8) from boron SUB-2,3-naphthalocyanine chloride and substituted or unsubstituted 1,3-diiminoisoindoline, followed by reaction with a metal salt.

general formula (8)

In general formula (8), Y ₉ to Y ₁₆ and R ₈ to R ₂₁ have the same meanings as Y ₉ to Y ₁₆ and R ₈ to R ₂₁ in general formula (3).

Examples of the phthalocyanine compound represented by formula (4) in the present invention include the following compounds, but the present invention is not limited thereto.

(Method for synthesizing near-infrared absorbing dye (A) or near-infrared absorbing dye (A1))
The near-infrared absorbing dye (A) or the near-infrared absorbing dye (A1) is, for example, a phthalocyanine moiety (PC1) or a phthalocyanine moiety (PC2) and a phosphorus compound represented by general formula (5) or general formula (6 ) is synthesized by reacting a polymer (hereinafter also referred to as a polymer) obtained by vinyl polymerization of a monomer containing a monomer represented by Simultaneous or sequential reactions may be carried out.

Synthesis of the near-infrared absorbing dye (A) or the near-infrared absorbing dye (A1) is performed, for example, by adding a phthalocyanine moiety, a phosphorus compound or a polymer to an organic solvent and heating and stirring for several hours. Then, the reaction solution is poured into water, and the precipitated product is filtered, washed with water, and dried.

Regarding the ratio of the phthalocyanine site and the polymer site, the molar ratio of the phosphoric acid group derived from the monomer represented by general formula (6) among the phthalocyanine site and the polymer site is expressed as phthalocyanine site/general formula (6). Phosphate group derived from the monomer to be used is preferably 0.5 to 1.5, preferably 0.8 to 1.2. When used in an appropriate ratio, the absorption due to association of aromatic rings becomes very weak, and the transmittance in the region of high relative luminosity from 480 nm to 650 nm becomes high.

Regarding the ratio of the phthalocyanine moiety and the phosphorus compound moiety, the amount of the phosphorus compound represented by the general formula (5) to be added ranges from 0.8 to 2.0 molar equivalents relative to the phthalocyanine moiety from the viewpoint of dispersibility and color characteristics. 0 molar equivalents are preferred, and 1.0 to 1.5 molar equivalents are more preferred.

(Crystal form control of near-infrared absorbing dye (A) or near-infrared absorbing dye (A1))
The near-infrared absorbing dye (A) or the near-infrared absorbing dye (A1) is subjected to heat treatment at 150 ° C. or higher, pressure treatment, acid pasting method, acid slurry method, dry milling method, salt milling method, solvent salt milling A desired crystal form can be controlled by a method, a solvent method (heat treatment in a high-boiling solvent such as an alcohol or an aromatic solvent), or a combination thereof. In the present invention, heat treatment at 150° C. or higher, pressure treatment, solvent salt milling method, solvent method, or a combination thereof is preferred. By using the above method, it is possible to obtain the effect of controlling the desired crystal type and having high dispersibility and dispersion stability. However, the near-infrared absorbing dye (A) and the near-infrared absorbing dye (A1) of the present invention are not limited by these production methods.

Examples of the heat treatment include a method of heat-drying the dye after synthesis in a dryer having an internal temperature of 150° C. or higher, a method of drying at 100° C. or lower and then heat-treating at 150° C. or higher for several hours. It is not limited. The temperature of the heat treatment is preferably 150° C. or higher, more preferably 200° C. or higher. The heat treatment time is preferably 1 to 24 hours.

Examples of the pressure treatment include, but are not limited to, a method of heating and stirring at 100° C. or higher in a pressure synthesizing apparatus. The pressurization time is preferably 1 to 24 hours.

As an example of the solvent salt milling method, a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is subjected to a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, a planetary mixer, and a Hoover Mahler. After mechanical kneading while heating using a kneader such as a kneader, the mixture is washed with water, methanol, 2-methylpyrrolidone or the like to remove inorganic salts and easily soluble organic substances. The kneading temperature for the salt milling treatment is preferably 20 to 150°C, more preferably 100°C or higher. The kneading time is preferably 1 to 24 hours. The amount of the alkaline earth metal salt to be mixed with the pigment is 0.01 to 70% by mass, more preferably 1.0 to 50% by mass, relative to the co-acid paste processed product of the pigment. be.

As the water-soluble inorganic salt, sodium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of price. The water-soluble inorganic salt is preferably used in an amount of 50 to 2,000% by mass, most preferably 300 to 1,000% by mass, based on the total mass of the pigment (100% by mass), from both processing efficiency and production efficiency.

The water-soluble organic solvent has the function of moistening the dye and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible in) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by mass, most preferably 50 to 500% by mass, based on the total mass of the pigment (100% by mass).

As an example of the solvent method, there is a method in which a dye and a solvent are mixed and solvent treatment is performed. Examples of solvents used for solvent treatment include aromatic solvents such as toluene, xylene, and methoxybenzene; acetic acid ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; Propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Solvents, aliphatic hydrocarbon solvents such as hexane, and the like are included.

The solvent treatment temperature is 10 to 1200° C., preferably 100° C. or higher, depending on the boiling point of the solvent, and the solvent treatment time is preferably 30 minutes to 24 hours.

<Green pigment (G)>
The near-infrared absorbing composition of the present invention includes a near-infrared absorbing dye (A) represented by the general formula (1) and a green dye (G ). The green dye (G) having a phthalocyanine skeleton plays the same role as the dye derivative with respect to the near-infrared absorbing dye (A), and has great effects on miniaturization during dispersion, prevention of aggregation, and dispersion stability. In addition, since the green dye (G) has strong resistance derived from its skeleton, it does not interfere with the good light resistance and heat resistance of the near-infrared absorbing dye (A) and improves its fastness. Moreover, since it is green, it has the characteristic that it has little influence on the spectral spectrum of the near-infrared absorbing dye (A). Therefore, a near-infrared absorptive composition having high near-infrared transmittance in a specific region (900 nm to 1200 nm), excellent near-infrared cutting ability of 700 nm to 800 nm, good dispersion stability, light resistance and heat resistance is provided. be able to.

[一般式（１０１）および（１０２）中、Ｒ_２７～Ｒ_４２は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、ニトリル基、置換基を有してもよいアルキル基、置換基を有してもよいシクロアルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいアルキルアミノ基、または、置換基を有してもよいアリールアミノ基を表す。Ｍ_１は、銅（Ｃｕ）、亜鉛（Ｚｎ）を表す。Ｍ_２は、アルミニウム（Ａｌ）を表す。
一般式（１０２）中、Ｚ_３は、－ＯＰ（＝Ｏ）Ｒ_１Ｒ_２、または一般式（２）で表される単量体単位を含む重合体部位を表す。ここでＲ_１、Ｒ_２はそれぞれ独立に、水素原子、水酸基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基を表し、Ｒ_１とＲ_２は、互いに結合して環を形成しても良い。］

[In general formulas (101) and (102), R ₂₇ to R ₄₂ each independently represent a hydrogen atom, a halogen atom, a nitro group, a nitrile group, an optionally substituted alkyl group, or a substituted optionally substituted cycloalkyl group, optionally substituted heterocyclic group, optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted It represents an alkylthio group, an arylthio group which may have a substituent, an alkylamino group which may have a substituent, or an arylamino group which may have a substituent. _M1 represents copper (Cu) and zinc (Zn). _M2 represents aluminum (Al).
In general formula (102), Z ₃ represents —OP(=O)R ₁ R ₂ or a polymer moiety containing a monomer unit represented by general formula (2). Here, R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, It represents an aryloxy group which may have a substituent, and R ₁ and R ₂ may combine with each other to form a ring. ]

The green dye (G) preferably has a transmittance of 85% or more at 550 nm in the spectral transmittance spectrum of the coating film from 380 to 1000 nm when the minimum transmittance is defined as 1%.

As the green dye (G), 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, and C.I. I. It is more preferable to contain at least one selected from the group consisting of Pigment Green 63.

The green dye (G) preferably contains a pigment having an acidic group amount of 100-600 μmol. When dispersing using a pigment dispersant (resin type dispersant), the adsorption of the pigment dispersant (resin type dispersant) to the surface of the pigment tends to progress, resulting in high transmission of near infrared rays (900 nm to 1200 nm) in a specific area. It is possible to realize excellent dispersion stability by preventing rate and increase in viscosity over time.

Specific examples of pigments having an acidic group amount of 100 to 600 μmol/g include C.I. I. Pigment Green 58 is more preferred.

Moreover, even a pigment having an acid group content of less than 100 μmol/g can be used by increasing the acid group content by performing a surface treatment using an acid substance such as an acid derivative.

The amount of acidic groups in the present invention is determined by the adsorption amount of amine measured using n-hexylamine as the adsorbed amine substance according to the method described in Shikizai, 67[9], 547-554 (1994). Defined.

The mass ratio of the near-infrared absorbing dye (A) and the green dye (G) in the near-infrared absorbing composition of the present invention is preferably 95/5 to 60/40. From the point of view, it is more preferably 85/15 to 75/25.

The near-infrared absorptive composition of the present invention has high transmittance in the region of high relative luminosity of 480 nm to 650 nm, and excellent absorption of near infrared rays in the range of 700 nm to 800 nm. This remarkably appears when the substrate is coated to form a film. When applying to a substrate, it may be used after being dissolved in a solvent or the like, or may be used after obtaining a dispersion using a dispersant or the like. A binder resin can also be added and used.

<Other near-infrared absorbing dyes>
The near-infrared absorbing composition of the present invention can contain other near-infrared absorbing dyes in addition to the near-infrared absorbing dye (A) or the near-infrared absorbing dye (A1). Thereby, the spectrum can be appropriately adjusted. Other near-infrared absorbing dyes include, for example, cyanine compounds, squarylium compounds, phthalocyanine compounds (excluding near-infrared absorbing dye (A) or near-infrared absorbing dye (A1)), naphthalocyanine compounds (near-infrared absorbing dye (A)), anthraquinone compounds, aminium compounds, diimmonium compounds, croconium compounds, azo compounds, quinoid complex compounds, dithiol metal complex compounds, and the like.

The content of the near-infrared absorbing dye in the near-infrared absorbing composition 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). preferable. Further, when the near-infrared absorbing dye (A) or the near-infrared absorbing dye (A1) and other near-infrared absorbing dyes are used in combination as the near-infrared absorbing dye, the other near-infrared absorbing dye/near The weight ratio of the infrared absorbing dye (A) or the near infrared absorbing dye (A1) is preferably in the range of 5/95 to 50/50.

<Organic dye having absorption at 400 nm to 700 nm>
The near-infrared absorptive composition of the present invention can contain an organic dye having absorption in the range of 400 nm to 700 nm (excluding the green dye (G)) other than the near-infrared absorptive dye. The near-infrared absorbing dye (A) or the near-infrared absorbing dye (A1) contained in the near-infrared absorbing composition of the present invention has strong absorption at 700 nm to 800 nm, for example, a black organic dye, a plurality of organic dyes can be used as a near-infrared transmitting composition that blocks light of 400 nm to 800 nm and transmits light of 800 nm or more by including an organic dye that exhibits a black color in combination. 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 800 nm or more, it is necessary to use an organic dye that absorbs little at 800 nm or more.

Examples of organic dyes having absorption in the range of 400 nm to 700 nm include blue dyes, green dyes (excluding green dyes (G)), yellow dyes, purple dyes, and red dyes.
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 pigments such as thorone, pyranthrone, or violanthrone, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, phthalocyanine pigments, threne pigments, or Metal complex pigments and the like are included.
Dyes may also 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.

(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 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 above dyes have good spectral characteristics and excellent color development, they have problems with light resistance and heat resistance, and their characteristics may not be sufficient for use in near-infrared cut 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 sexuality.
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.

<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 pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, benzoiso Indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, phthalocyanine pigments, metal complex pigments, azo pigments such as azo, disazo, polyazo, etc. are mentioned. Among these, it is preferable to use dye derivatives having substituents of phthalocyanine pigments and quinophthalone pigments.

Specifically, diketopyrrolopyrrole-based dye derivatives, JP 2001-220520, WO2009/081930, WO2011/052617, WO2012/102399, JP 2017-156397, phthalocyanine Dye derivatives, JP-A-2007-226161, WO2016/163351 pamphlet, JP-A-2017-165820, Japanese Patent No. 5753266, anthraquinone-based dye derivatives, JP-A-63-264674, 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.

The near-infrared absorbing composition of the present invention preferably contains a resin-type dispersant (basic resin-type dispersant) having a basic group as a pigment affinity site. The basic resin-type dispersant has an amino group, and the amino group forms a salt with at least one selected from the group consisting of alkyl halides, aryl halides, and aralkyl halides. Among the amino groups, 20 to 90 mol % of the amino groups are preferably salt-formed, and more preferably 40 to 80 mol % of the amino groups are salt-formed. Within this range, the basic resin-type dispersant efficiently adsorbs to the near-infrared absorptive dye, thereby improving the dispersibility.

The amine value of the basic resin type dispersant is preferably 3 to 70 mgKOH/g, more preferably 5 to 50 mgKOH/g.

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 weight, more preferably 0.1 to 150 parts by weight, per 100 parts by weight 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 can contain 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. In addition, 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 step in manufacturing an optical filter, 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 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. and more preferably glycerol mono(meth)acrylate.

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 exposure 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, resulting in poor pattern linearity. 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 a thermosetting compound is further included in combination with the thermoplastic resin as the binder resin. 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 region 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 parts by mass, more preferably 1.0 to 50 parts by mass, per 100 parts 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 parts by mass, respectively, for 100 parts by mass of the thermosetting compound.

<Polymerizable compound>
A photosensitive near-infrared absorptive composition can be obtained by including the near-infrared absorptive composition of the present invention, 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, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, 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 (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, 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 the non-volatile matter of 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 radical polymerization process 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- Examples include triazines, 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 parts 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.

Further, 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. 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 thermal curing 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 photopolymerization initiator are taken, resulting in strong 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 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 auxiliary to the leveling agent include, 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>
A near-infrared absorptive composition contains 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, Dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, cyclopentanone, 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 and the like are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate 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 adjusted 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 obtained 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.

<Specific metal atom in near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention includes a near-infrared absorbing dye represented by general formula (1) or general formula (3), a green dye represented by general formula (101) or general formula (102), In some cases, metal components including a small amount of Li, Na, K, Cs, Mg, Ca, Fe and Zr (hereinafter also referred to as specific metal atoms) may be present in addition to the constituent components of the organic dye. If there are many metal components containing these specific metal atoms, the storage stability may be impaired, the heat resistance may be lowered, and the sensitivity may be lowered when the composition is prepared in the form of a photosensitive near-infrared absorptive composition. be.
Moreover, 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, and as a result, tends to cause 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.

Further, a near-infrared absorbing dye represented by general formula (1) or general formula (3), Al in a green dye represented by general formula (102), and a green dye represented by general formula (101) When metal atoms such as Ni, Zn, Cu, Fe, Pt, Mn, and Co are included in Cu, Zn, or part of the organic dye structure in the These metal atoms that are not present may be present. The smaller the number of such metal atoms, the better, and they can be removed in the same manner as the specific metal atoms by the following method. Furthermore, it is preferable that the concentration of Cs, Ti, Si, Pd, and the like mixed with materials (for example, catalysts) used in the manufacturing process of various raw materials of the near-infrared absorbing composition is low.

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).

<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 content of toluene is preferably 0.1 to 10 mass ppm based on the entire near-infrared absorbing composition. 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 example, for the following applications.

<<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 electrical signals, a near-infrared cut filter can be used to block them. 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 absorptive composition of the present invention has low absorption in the visible region and high invisibility, it has little adverse effect on the color recognition of photodiodes.

<<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 pigment, 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 850 nm, 900 nm, 940 nm, etc. have become widespread, and distance measurement and biometric authentication (fingerprint authentication, iris authentication, face authentication, vein authentication, etc., or their combination) in automatic driving, light detection in various sensors used for 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 composition of the present invention with a blue pigment and a yellow pigment, or a red or purple pigment. 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 pigment 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.

[Method for producing an optical filter]
The optical filter of the present invention can be manufactured by a printing method or a photolithographic method. Formation of the filter segment by the printing method enables patterning by printing and drying the near-infrared absorptive 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 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 composition of the present invention can also be used for molding purposes. 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. Further, 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. It is therefore 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 in 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 diluent resin (thermoplastic resin) to prepare a molded body, the near-infrared absorbing composition of the present invention is compared with a molded body manufactured without the masterbatch. can be easily dispersed uniformly in the molded article, and aggregation of the near-infrared absorbing dye can be suppressed. 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 other resins, 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 "parts by weight". "PGMAC" means propylene glycol monomethyl ether acetate.

(Method for identifying phthalocyanine pigment)
A MALDI TOF-MS spectrum was used to identify the phthalocyanine pigment used in the present invention. The MALDI TOF-MS spectrum was obtained using a MALDI mass spectrometer autoflex III manufactured by Bruker Daltonics, and the compound obtained was identified by the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The composition was determined by calculating the peak intensity (relative intensity) of each molecular ion with respect to the sum of all molecular ion peak intensities in the obtained mass spectrum, and considering the relative intensity ratio as the molar ratio.
The phthalocyanine pigment is a compound in which one of X ₁ and X ₂ , X ₃ and X ₄ , X ₅ and X ₆ , and X ₇ and X ₈ are bonded to each other to form an aromatic ring in general formula (1). A compound in which two points are bonded to each other to form an aromatic ring is n2, a compound in which three points are bonded to each other to form an aromatic ring is n3, and a compound in which all four points are bonded to each other to form an aromatic ring n4 body. A compound that does not form an aromatic ring at any of the four positions was designated as n0.

(Powder X-ray diffraction measurement method for near-infrared absorbing dye)
The powder X-ray diffraction measurement was carried out in accordance with Japanese Industrial Standards JIS K0131 (general rules for X-ray diffraction analysis) with a diffraction angle (2θ) in the range of 3° to 35°.

The measurement conditions were as follows.
X-ray diffractometer: RINT2100 manufactured by Rigaku Corporation
Sampling width: 0.02°
Scan speed: 2.0°/min
Divergence slit: 1°
Divergence longitudinal limiting slit: 10mm
Scattering slit: 2°
Light receiving slit: 0.3 mm
Tube: Cu
Tube voltage: 40kV
Tube current: 40mA

1 to 3 show examples of diffraction patterns obtained by powder X-ray diffraction of near-infrared absorbing dyes. 1 to 3, the X-axis is the Bragg angle (2θ) and the Y-axis is the diffraction peak intensity (count).

(Acidic group amount of green pigment (G))
The amount of amine adsorption was measured as the amount of acidic groups of the green dye (G). As for the measurement method, 1 g of the pigment was weighed into a sealable glass container, and 30 ml of a propylene glycol monomethyl ether acetate solution of 0.02 mol/l n-hexylamine (adsorptive substance) was added. The container was stoppered and placed in an ultrasonic cleaner for 1 hour to adsorb to the surface of the dye, followed by centrifugation to sediment the pigment and obtain a supernatant. 15 ml of the supernatant was collected, and residual n-hexylamine was back-titrated with a 0.02 mol/l perchloric acid dioxane solution using a potentiometric titrator. The value obtained by measuring the blank and quantifying it was taken as the amine adsorption amount of the pigment.

(Acid value of resin type dispersant and binder resin)
The acid value of the resin-type dispersant and the binder resin was obtained 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.
<Production of near-infrared absorbing dye>
(Synthesis of phthalocyanine pigment (a-1))
In a reaction vessel, 64 parts of phthalonitrile, 89 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) and three 34 parts of aluminum chloride was mixed and stirred, and after the temperature was raised, the mixture was refluxed at 136° C. for 5 hours. The reaction solution cooled to 30° C. while being stirred was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 140 parts of phthalocyanine pigment (1-1) (represented by the following chemical formula (1-1) mixture of compounds). As a result of mass spectrometry by TOF-MS, the obtained compound was identified by the agreement between the molecular ion peak of the mass spectrum obtained and the mass number obtained by calculation.

Phthalocyanine pigment (1-1)
Chemical formula (1-1)

Next, 140 parts of the phthalocyanine pigment (1-1) was added to 1500 parts of concentrated sulfuric acid in a reaction vessel under an ice bath, and the mixture was stirred for 1 hour. Subsequently, this sulfuric acid solution is poured into 1000 parts of cold water at 3° C., and the precipitate formed is filtered, washed with water, washed with a 2.5% sodium hydroxide aqueous solution, washed with water in that order, dried, and dried to 120 parts. to obtain a phthalocyanine pigment (a-1). As a result of mass spectrometry by TOF-MS, the obtained compound was identified by the agreement between the molecular ion peak of the mass spectrum obtained and the mass number obtained by calculation. The phthalocyanine pigment (a-1) was a mixture having the following structure, and the main component was the n2 form.

Phthalocyanine pigment (a-1)

(Synthesis of phthalocyanine pigment (a-2))
Instead of 64 parts of phthalonitrile and 89 parts of 2,3-dicyanonaphthalene used in the synthesis of phthalocyanine pigment (a-1), 26 parts of phthalonitrile and 143 parts of 2,3-dicyanonaphthalene were used, respectively. 147 parts of phthalocyanine pigment (a-2) was obtained by performing the same operation as in the synthesis of phthalocyanine pigment (a-1). As a result of mass spectrometry by TOF-MS, the obtained compound was identified by the agreement between the molecular ion peak of the mass spectrum obtained and the mass number obtained by calculation. The main component of the phthalocyanine pigment (a-2) was n3 having the following structure.

Main component (n3 body) of phthalocyanine pigment (a-2)

(Synthesis of phthalocyanine pigment (a-3))
Instead of 64 parts of phthalonitrile and 89 parts of 2,3-dicyanonaphthalene used in the synthesis of phthalocyanine pigment (a-1), 13 parts of phthalonitrile and 160 parts of 2,3-dicyanonaphthalene were used, respectively. 147 parts of phthalocyanine pigment (a-3) was obtained by performing the same operation as in the synthesis of phthalocyanine pigment (a-1). As a result of mass spectrometry by TOF-MS, the obtained compound was identified by the agreement between the molecular ion peak of the mass spectrum obtained and the mass number obtained by calculation. The main component of the phthalocyanine pigment (a-3) was the n3 body having the following structure.

Main component (n3 body) of phthalocyanine pigment (a-3)

(Synthesis of phthalocyanine pigment (a-4))
Instead of 64 parts of phthalonitrile and 89 parts of 2,3-dicyanonaphthalene used in the synthesis of phthalocyanine pigment (a-1), 102 parts of phthalonitrile and 36 parts of 2,3-dicyanonaphthalene were used, respectively. 147 parts of phthalocyanine pigment (a-4) was obtained by performing the same operation as in the synthesis of phthalocyanine pigment (a-1). As a result of mass spectrometry by TOF-MS, the obtained compound was identified by the agreement between the molecular ion peak of the mass spectrum obtained and the mass number obtained by calculation. The main component of the phthalocyanine pigment (a-4) was the n1 body having the following structure.

Main component (n1 body) of phthalocyanine pigment (a-4)

(Synthesis of phthalocyanine pigment (a-9))
In a reactor, 700 parts of dimethylsulfoxide, 200 parts of 1-chloronaphthalene, 100 parts of boron sub-2,3-naphthalocyanine chloride and 30 parts of 1,3-diiminoisoindoline were mixed and stirred. The temperature was raised and the mixture was heated and stirred at 150° C. for 5 hours. The reaction solution cooled to 30° C. while being stirred was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 110 parts of phthalocyanine pigment (9-1).
Next, 900 parts of quinoline, 110 parts of phthalocyanine pigment (9-1) and 28 parts of aluminum chloride anhydride were mixed and stirred. The temperature was raised and the mixture was heated and stirred at 150° C. for 4 hours. The reaction solution cooled to 30° C. while being stirred was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 100 parts of phthalocyanine pigment (9-2).

Next, 100 parts of the phthalocyanine pigment (9-2) was added to 1500 parts of concentrated sulfuric acid in a reaction vessel under an ice bath, and the mixture was stirred for 1 hour. Subsequently, this sulfuric acid solution is poured into 15,000 parts of cold water at 3° C., and the precipitate formed is filtered, washed with water, washed with an aqueous 2.5% sodium hydroxide solution, washed with water in this order, dried, and dried to obtain 90 parts. A phthalocyanine pigment (a-9) was obtained. As a result of mass spectrometry by TOF-MS, the resulting compound was identified by the agreement between the molecular ion peak of the mass spectrum obtained and the mass number obtained by calculation. The phthalocyanine pigment (a-9) was only n3 having the following structure.

Phthalocyanine pigment (a-9) (n3 body)

(Synthesis of phthalocyanine pigment (a-10))
100 parts of phthalocyanine pigment (a-2) was added to 1500 parts of concentrated sulfuric acid in an ice bath. After that, 151 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added and stirred at 25° C. for 6 hours. Subsequently, this sulfuric acid solution is poured into 9000 parts of cold water at 3° C., and the precipitate formed is filtered, washed with water, washed with a 1% sodium hydroxide aqueous solution, washed with water in that order, dried, and dried to obtain 165 parts of phthalocyanine. A pigment (a-10) was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified by the agreement between the molecular ion peak of the mass spectrum obtained and the mass number obtained by calculation. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (a-10), it was found to be 8 on average, and a peak corresponding to the same molecular weight was also confirmed from the mass spectrum, thus identifying the objective compound. The main component of the phthalocyanine pigment (a-10) was n3 having the following structure.

Main component (n3 body) of phthalocyanine pigment (a-10)

(Synthesis of phthalocyanine pigment (a-12))
The same operation as in the synthesis of the phthalocyanine pigment (a-2) was performed except that 33 parts of 4-chlorophthalodinitrile was used instead of the 26 parts of phthalonitrile used in the synthesis of the phthalocyanine pigment (a-2), 140 parts of phthalocyanine pigment (a-12) were obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified by the agreement between the molecular ion peak of the mass spectrum obtained and the mass number obtained by calculation. The main component of the phthalocyanine pigment (a-8) was the n3 body having the following structure.

Main component (n3 body) of phthalocyanine pigment (a-12)

(Synthesis of phthalocyanine pigment (a-22))
In a reaction vessel, 178 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene), 40 parts of anhydrous aluminum chloride were mixed and stirred, and after the temperature was raised, the mixture was refluxed at 136° C. for 5 hours. The reaction solution cooled to 30° C. while being stirred was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 125 parts of chloroaluminum phthalocyanine represented by the following chemical formula (1-3). As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified by the agreement between the molecular ion peak of the mass spectrum obtained and the mass number obtained by calculation.

Chloroaluminum phthalocyanine pigment chemical formula (1-3)

Next, 10 parts of the above chloroaluminum naphthalocyanine was added to 100 parts of concentrated sulfuric acid in a reaction vessel under an ice bath, and the mixture was stirred for 1 hour. Subsequently, this sulfuric acid solution is poured into 1000 parts of cold water at 3° C., and the precipitate formed is filtered, washed with water, washed with a 2.5% aqueous sodium hydroxide solution, washed with water in that order, dried, and dried to obtain 8 parts. of the phthalocyanine pigment (a-22) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified by the agreement between the molecular ion peak of the mass spectrum obtained and the mass number obtained by calculation. The molecular weight was 756.75.

Phthalocyanine pigment (a-22)

(Synthesis of phthalocyanine pigment (a-23))
100 parts of the phthalocyanine pigment (a-22) was added to 1500 parts of concentrated sulfuric acid in an ice bath. After that, 151 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added and stirred at 25° C. for 6 hours. Subsequently, this sulfuric acid solution is poured into 9,000 parts of cold water at 3° C., and the precipitate formed is filtered, washed with water, washed with a 1% sodium hydroxide aqueous solution, washed with water in that order, dried, and dried to obtain 170 parts of phthalocyanine. A pigment (a-23) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, the obtained compound was identified by the agreement between the molecular ion peak of the mass spectrum obtained and the mass number obtained by calculation. When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (a-23), it was found to be 8.4 on average. A peak corresponding to the same molecular weight was also confirmed from the mass spectrum, and the desired compound was identified. The molecular weight was 1419.51.

Phthalocyanine pigment (a-23)

Table 1 shows the composition of the obtained phthalocyanine pigment. The n3 form corresponds to the near-infrared absorbing dye (A1).

<Method for producing resin (B)>
(Synthesis of resin (B-1))
100 parts of PGMAc and methyl 4-cyano-4-(dodecylthiocarbonothioylthio)pentanoate (hereinafter abbreviated as "BM1448") were added to a reactor equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube. After charging 3 parts and heating to 80 ° C. in a nitrogen atmosphere, 48 parts of methyl methacrylate, 29 parts of ethyl methacrylate, 19 parts of tertiary butyl acrylate, 2,2'-azobis (2,4-dimethylvaleronitrile) ( Hereinafter, abbreviated as "V65".) 1 part of the mixture was added dropwise over 4 hours. After completion of the dropwise addition, the mixture was held at 90° C. for 2 hours, and then a mixture of 5 parts of 2-methacryloyloxyethyl acid phosphate (hereinafter abbreviated as “P-1M”; molecular weight of 228) and 100 parts of PGME was added dropwise over 1 hour. bottom. After holding at 90° C. for 12 hours, PGME was added to obtain a 30 mass % solution of resin (B-1). The Tg of this resin (B-1) was 37°C.

<Method for producing near-infrared absorbing dye>
(Production of near-infrared absorbing dye (AA-1))
A near-infrared absorbing dye (A-1) comprising a phthalocyanine pigment (a-1) and a phosphorus compound was produced by the following procedure. 5 parts of diphenylphosphoric acid was added to 200 parts of N-methylpyrrolidone, and the mixture was sufficiently stirred and mixed, and then heated to 50°C. 10 parts of the phthalocyanine pigment (a-1) was gradually added to this solution, and the mixture was stirred at 90° C. for 120 minutes. For confirmation of the end point of the reaction, for example, the reaction liquid was dropped onto a filter paper, and the end point was set at the point where the bleeding disappeared. Subsequently, this reaction solution is poured into 2000 parts of water, and the resulting precipitate is filtered, washed with water, and dried at 80° C. to remove 12 parts of the near-infrared absorbing dye (A-1). Obtained. Next, (A-1) was heat-treated at 200° C. for 6 hours as a crystal control treatment to obtain a near-infrared absorbing dye (AA-1).

(Production of near-infrared absorbing dyes (AA-2) to (AA-40) and (AA-49) to (AA-63))
Except that the phthalocyanine pigment, phosphorus compound, and crystal control treatment were changed as described in Table 2-1, the same operation as in the production of the near-infrared absorbing dye (AA-1) was performed, and the near-infrared absorbing dye (AA -2) ~ (AA-40), (AA-49) ~ (AA-63) were obtained.

(Production of near-infrared absorbing dye (AA-47))
A near-infrared absorbing dye (A-47) comprising a phthalocyanine pigment (a-2) and a resin (B-1) was produced by the following procedure. 65 parts of resin (B-1) was added to 200 parts of N-methylpyrrolidone, thoroughly stirred and mixed, and then heated to 50°C. 10 parts of the phthalocyanine pigment (a-2) was gradually added to this solution, and the mixture was stirred at 90° C. for 120 minutes. For confirmation of the end point of the reaction, for example, the reaction liquid was dropped onto a filter paper, and the end point was set at the point where the bleeding disappeared. Subsequently, this reaction solution was poured into 2000 parts of water, and the precipitate formed was filtered, washed with water, and dried to obtain 24 parts of a near-infrared absorbing dye (A-47).
At this time, the molar ratio of the phthalocyanine pigment (a-2) and P-1M contained in the resin (B-1) is phthalocyanine pigment (a-2) / P-1M contained in the resin (B-1) = It was 0.9/1.
Next, as a crystal control treatment, 300 parts of the near-infrared absorbing dye (A-47), 1500 parts of sodium chloride, and 400 parts of diethylene glycol are charged into a 3 L double-arm kneader to form a dough, which is then kneaded at a material temperature of 100° C. for 6 hours. bottom. The resulting dough was taken out, reslurried in water of about 10 times the weight of the dough, stirred at 70°C for 1.5 hours, and filtered. Further, it was reslurried again, filtered and washed with water to obtain a paste pigment, and dried in a heating oven at 80° C. to obtain a near-infrared absorbing dye (AA-47).

(Production of near-infrared absorbing dye (AA-64))
Instead of 10 parts of the phthalocyanine pigment (a-2) used in the production of the near-infrared absorbing dye (A-47), a near-infrared absorbing dye except that 10 parts of the phthalocyanine pigment (a-22) were used. A near-infrared absorbing dye (AA-64) was obtained by performing the same operation as in the production of (AA-47).

(Production of near-infrared absorbing dye composition (AA-2′))
A near-infrared absorbing dye (A-2) comprising a phthalocyanine pigment (a-2) and a phosphorus compound was produced by the following procedure. 5 parts of diphenylphosphoric acid was added to 200 parts of N-methylpyrrolidone, and the mixture was sufficiently stirred and mixed, and then heated to 50°C. 10 parts of the phthalocyanine pigment (a-2) was gradually added to this solution, and the mixture was stirred at 90° C. for 120 minutes. For confirmation of the end point of the reaction, for example, the reaction liquid was dropped onto a filter paper, and the end point was set at the point where the bleeding disappeared. Subsequently, this reaction solution is poured into 2,000 parts of water, and the resulting precipitate is filtered, washed with water, and dried at 80° C. to remove 12 parts of the near-infrared absorbing dye (A-2). Obtained. Next, 12 parts of (A-2) and 3 parts of green pigment (G-1) were added to 150 g of diethylene glycol for crystal control treatment, and the mixture was heated and stirred at 150° C. for 3 hours. Filtration, washing with warm water, and drying at 80° C. gave a near-infrared absorbing dye composition (AA-2′). The near-infrared absorbing dye composition (AA-2') is a near-infrared absorbing dye composition containing the near-infrared absorbing dye (AA-2) and the green dye (G-1) at a ratio of 8:2. . The green dye (G-1) will be described later.

(Production of near-infrared absorbing dye composition (AA-49′))
Instead of the phthalocyanine pigment (a-2) used in the production of the near-infrared absorbing dye composition (AA-2'), the near-infrared absorbing dye composition ( AA-2') was performed to obtain a near-infrared absorbing dye composition (AA-49'). The near-infrared absorbing dye composition (AA-49') is a near-infrared absorbing composition containing the near-infrared absorbing dye (AA-49) and the green dye (G-1) at a ratio of 8:2.

Table 2-1 shows the compositions of the near-infrared absorbing dyes (AA-1) to (AA-64) and the method of crystal control treatment.

The main structural components of the near-infrared absorbing dyes (A-1) to (AA-40) and (AA-49) to (AA-63) are shown below.

Table 2-2 shows the X-ray diffraction peaks of the near-infrared absorbing dyes (AA-1) to (AA-64). 1 to 3 show the X-ray diffraction patterns of the near-infrared absorbing dyes (AA-1), (AA-49), and reference material 1', which will be described later.

<Green pigment (G)>
The following (G-1) to (G-6) were used as green dyes (G). In addition, the measurement result of the amount of acidic radicals is as follows.
(G-1) C.I. I. Pigment Green 58 (acidic group content: 530 µmol/g)
(G-2) C.I. I. Pigment Green 59 (acidic group content: 570 µmol/g)
(G-3) C.I. I. Pigment Green 62 (acidic group amount: 17 µmol/g)
(G-4) C.I. I. Pigment Green 63 (acidic group content: 90 µmol/g)
(G-5) C.I. I. Pigment Green 7 (acidic group amount: 50 µmol/g)
(G-6) C.I. I. Pigment Green 36 (acidic group content: 57 µmol/g)

<Method for producing binder resin solution>
(Adjustment of binder resin 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 solution was prepared by adding acetate. The weight average molecular weight (Mw) was 19,000.

<Method for producing resin-type dispersant>
(Resin type dispersant 1 solution):
[Synthesis of monomer (b-1)]
A reaction vessel equipped with a stirrer and a thermometer was charged with 60 parts of 2-isocyanatoethyl methacrylate, 29 parts of 3-(dimethylamino)propylamine, and 120 parts of THF, and stirred at room temperature for 5 hours. After confirming that the reaction was completed by FT-IR, the solvent was distilled off with a rotary evaporator to obtain 73 parts of the following monomer (b-1) as a pale yellow transparent liquid (yield 82% ). Identification of the obtained compounds was carried out by 1H-NMR.

Monomer (b-1)

[Synthesis of monomer (b-2)]
In a reaction vessel equipped with a stirrer and a thermometer, 6.6 parts of the monomer (b-1) obtained in the synthesis of the monomer (b-1) and 5 parts of ion-exchanged water were charged and stirred at room temperature. % hydrochloric acid aqueous solution was added dropwise. Completion of the reaction was confirmed by amine value measurement, and 20 parts of an aqueous monomer (b-2) solution was obtained as a pale yellow transparent liquid. Identification of the obtained compounds was carried out by 1H-NMR.

Monomer (b-2)

17.7 parts of methyl methacrylate, 53.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction tank equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer. 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 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, 20 parts of PGMAc, 21.2 parts of monomer (b-1) as a second block monomer, and 27 parts of monomer (b-2) aqueous solution (38% non-volatile content) were added to the reactor, and The reaction was continued while stirring while maintaining the atmosphere. After 2 hours, the polymerization solution was sampled and the non-volatile content was measured to confirm that the polymerization conversion rate of the second block was 98% or more in terms of the non-volatile content, and the reaction solution was cooled to room temperature to stop the polymerization. bottom.
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 having an amine value per non-volatile content of 50 mg KOH / g, a quaternary ammonium salt value of 20 mg KOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by mass A Dispersant 1 solution was obtained.

(Resin type dispersant 5 solution)
50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate and 45.4 parts of PGMAc were introduced into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and the contents were purged with nitrogen gas. The inside of the reaction vessel was heated to 70° C., 6 parts of 3-mercapto-1,2-propanediol was added, and 0.12 part of AIBN (azobisisobutyronitrile) was further added and reacted for 12 hours. It was confirmed by measuring the non-volatile content that 95% had reacted. Next, add 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst, and heat at 120°C. was reacted for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%. Thus, an acidic resin-type dispersant 5 solution having an acid value of 43, a weight average molecular weight of 9000, a poly(meth)acrylate skeleton and an aromatic carboxyl group was obtained.

(Resin type dispersant 11 solution)
31 parts of methyl methacrylate, 62 parts of n-butyl methacrylate, and 6.5 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas inlet pipe, condenser, stirring blade, and 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 7.0 parts of 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, and it was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of the nonvolatile content.
Further, 3.3 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 mass. Thus, the amine value per non-volatile content is 10.1 mgKOH / g, the quaternary ammonium salt value is 14.2 mgKOH / g, the weight average molecular weight is 20000, and the non-volatile content is 40% by mass. , to obtain a basic resin-type dispersant 11 solution.

(Resin type dispersant 12 solution)
Except that the amounts of 62 parts of n-butyl methacrylate, 7.0 parts of DM, and 3.3 parts of benzyl chloride added to the resin type dispersant 11 solution were changed to 53 parts, 15 parts, and 6.9 parts, respectively. In the same manner as the resin type dispersant 11 solution,
An amine value per non-volatile content of 20.4 mgKOH / g, a quaternary ammonium salt value of 28.5 mgKOH / g, a weight average molecular weight of 19800, a non-volatile content of 40% by mass A poly (meth) acrylate skeleton, a tertiary amino group A solution of basic resin type dispersant 12 was obtained.

(Resin type dispersant 13 solution)
In the resin type dispersant 12 solution, instead of 15 parts of DM and 6.9 parts of benzyl chloride, 15 parts of N-(3-dimethylaminopropyl) methacrylamide and 6.5 parts of benzyl chloride were used. Poly(meth)acrylate having an amine value per nonvolatile content of 20.6 mgKOH/g, a quaternary ammonium salt value of 27.2 mgKOH/g, a weight average molecular weight of 19700, and a nonvolatile content of 40% by mass in the same manner as the agent 12 solution A solution of basic resin-type dispersant 13, which is a skeleton and has a tertiary amino group, was obtained.

(Resin type dispersant 14 solution)
Resin type dispersant except that the amount of N-(3-dimethylaminopropyl) methacrylamide 15 parts and benzyl chloride 6.5 parts added to the resin type dispersant 13 solution was changed to 18 parts and 2.6 parts, respectively. Poly(meth)acrylate having an amine value per nonvolatile content of 50.1 mgKOH/g, a quaternary ammonium salt value of 11.3 mgKOH/g, a weight average molecular weight of 19800, and a nonvolatile content of 40% by mass in the same manner as agent 13. A solution of basic resin-type dispersant 12, which is a skeleton and has a tertiary amino group, was obtained.

<Production of near-infrared absorbing composition>
[Example 1-1]
(Near-infrared absorbing composition (DD'-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. .
Near-infrared absorbing dye (AA-1): 8.0 parts Green dye (G-1): 2.0 parts Resin type dispersant 11 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.0 parts 5 copies

[Examples 1-2 to 1-11, 1-13 to 1-26, 1-28 to 1-57]
(Near-infrared absorbing compositions (DD'-2) to (DD'-11), (DD'-13) to (DD'-26), (DD'-28) to (DD'-57))
Below, the near-infrared absorbing composition except that the near-infrared absorbing dye, the green dye (G), the resin-type dispersant solution, the binder resin solution, and the solvent are changed to the compositions and amounts shown in Tables 3-1 and 3-2. In the same manner as (DD'-1), near-infrared absorbing compositions (DD'-2) to (DD'-11), (DD'-13) to (DD'-26), (DD'-28 ) to (DD′-57) were adjusted.

[Example 1-12]
(Near-infrared absorbing composition (DD'-12))
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. .
Near-infrared absorbing composition (AA-2'): 10.0 parts Resin type dispersant 11 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

[Example 1-27]
(Near-infrared absorbing composition (DD'-27))
In the same manner as the near-infrared absorbing composition (DD'-12) except that the near-infrared absorbing composition (AA-2') was changed to (AA-49'), a near-infrared absorbing composition (DD' -27) was adjusted.

[Example 1-58]
(Near-infrared absorbing composition (DD'-58))
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. .
Near-infrared absorbing dye (AA-2): 5.6 parts Other near-infrared absorbing dye (X-1): 2.4 parts Green dye (G-1): 2.0 parts Resin type dispersant 11 solution : 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

[Examples 1-59 to 1-85]
(Near-infrared absorbing composition (DD'-59) to (DD'-85))
Hereinafter, the near-infrared absorbing composition (DD'-58) except that the near-infrared absorbing dye, resin-type dispersant solution, binder resin solution, and solvent are changed to the compositions and amounts shown in Table 3-2. , near-infrared absorbing compositions (DD'-59) to (DD'-85) were prepared. (X-1) to (X-14) are other near-infrared absorbing dyes shown below.

[Example 1-86]
(Near-infrared absorbing composition (DD'-86))
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. .
Near-infrared absorbing dye (AA-2): 8.0 parts Green dye (G-1): 1.0 parts Dye derivative (DE-1): 1.0 parts Resin type dispersant 11 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

[Examples 1-87 to 1-93]
(Near-infrared absorbing composition (DD'-87) to (DD'-93))
Hereinafter, near-infrared absorbing composition (DD'-86) except that the near-infrared absorbing dye, resin-type dispersant solution, binder resin solution, and solvent are changed to the compositions and amounts shown in Table 3-3. , near-infrared absorbing compositions (DD'-87) to (DD'-93) were prepared. (DE-1) to (DE-4) are dye derivatives shown below.

(DE-1) solsperse 5000 (manufactured by Lubrizol)

(DE-2)

(DE-3)

(DE-4)

[Comparative Examples 1-1 to 1-4]
Comparative compositions 1' to 4' in the same manner as in Example 1-1, except that the near-infrared absorbing dye (AA-1) and the green dye (G) were changed to the compositions and amounts shown in Table 3-3. adjusted. The comparative materials 1' and 2' used near-infrared absorbing dyes shown below.

Comparative material 1': other near-infrared absorbing dye (X-14)
Comparative material 2': other near-infrared absorbing dye (X-2)

[Reference Examples 1-1 to 1-4]
Reference compositions 1' to 4' were prepared in the same manner as in Example 1-1, except that the near-infrared absorbing dye (AA-1) was changed to the composition and amount shown in Table 3-3. Reference materials 1' to 3' used near-infrared absorbing dyes shown below. Note that Reference Compositions 1' to 4' do not contain a green dye (G).
Reference material 1': near-infrared absorbing dye (A-2)
Reference material 2': near-infrared absorbing dye (AA-2)
Reference material 3': near-infrared absorbing dye (AA-49)

<Evaluation of near-infrared absorbing composition>
Dispersibility and dispersion stability for the near-infrared absorbing compositions (DD'-1 to DD'-93) obtained in Examples, comparative compositions 1' to 4', and reference compositions 1' to 4' , spectral characteristics, and resistance (light resistance and heat resistance) were tested by the following methods. 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. The results are shown in Tables 4-1, 4-2 and 4-3.

(Dispersibility: evaluation of filterability)
The dispersibility of the obtained near-infrared absorbing composition was evaluated by filterability.
10 g of the obtained near-infrared absorbing composition was passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number: 39115221) under nitrogen pressure (0.3 MPa), and the amount obtained through the filter was measured and judged as follows. evaluated according to the standard.
◎: Filtration amount is 9.0 g or more ○: Filtration amount is 5.0 g or more and less than 9.0 g △: Filtration amount is 3.0 g or more and less than 5.0 g ×: Filtration amount is 3.0 g or less

(Evaluation of dispersion stability 1)
The viscosity of the obtained near-infrared absorbing composition was measured and taken as the initial viscosity. Further, an accelerated test was performed at 40° C. for 7 days to measure accelerated viscosity over time.
As the rate of change due to acceleration, accelerated viscosity/initial viscosity was calculated and evaluated according to the following criteria.
◎: less than 1.05 ○: 1.05 or more and less than 1.10 △: 1.10 or more and less than 1.3 ×: 1.3 or more

(Evaluation of dispersion stability 2)
The viscosity of the obtained near-infrared absorbing composition was measured and taken as the initial viscosity. Further, an accelerated test was conducted with one cycle of 40° C. for 7 days, 13° C. for 7 days, and 40° C. for 7 days to measure accelerated viscosity over time.
As the rate of change due to acceleration, accelerated viscosity/initial viscosity was calculated and evaluated according to the following criteria.
◎: less than 1.05 ○: 1.05 or more and less than 1.10 △: 1.10 or more and less than 1.3 ×: 1.3 or more

(Evaluation of spectral characteristics 1)
The obtained near-infrared absorbing composition was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater so that the film thickness after drying was 1.0 μm, and dried at 60° C. for 5 minutes. , and heated at 230° C. for 5 minutes to fabricate a substrate. The absorption spectrum of the resulting substrate was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation) in the wavelength range of 300 to 1200 nm. The ratio (W/X) of the maximum absorbance value (W) at 700 to 800 nm and the minimum absorbance value (X) at 480 to 650 nm was determined for the obtained substrate and evaluated according to the following criteria. Incidentally, the larger this ratio (W / X), the less absorption at the wavelength with the lowest absorption in the region with high relative luminosity (480 nm to 650 nm) for the absorption in the near infrared, and the maximum transmittance at the wavelength It can be said that the permeability is high.
◎: 30 or more ○: 15 or more and less than 30 △: 5 or more and less than 15 ×: less than 5

(Evaluation of spectral characteristics 2)
Regarding the substrate obtained above, the ratio (W/Y) of the maximum absorbance value (W) at 700 to 800 nm and the maximum absorbance value (Y) at 480 to 650 nm was determined and evaluated according to the following criteria. It should be noted that the greater the ratio (W/Y), the less the absorption in the near-infrared region (480 nm to 650 nm) with high relative luminosity, and the higher the transmittance in the region perceived brighter by the human eye. I can say
◎: 4 or more ○: 3 or more, less than 4 △: 2 or more, less than 3 ×: less than 2

(Evaluation of spectral characteristics 3)
It was evaluated whether or not the absorption spectrum of the obtained substrate had an extreme point at 800 to 900 nm. The extremum point is a point at which the absorbance changes from an increase to a decrease or from a decrease to an increase when the absorbance is confirmed from the short wavelength side to the long wavelength side. If there is an extremum point, transmitted light at that wavelength may be detected as noise, so it can be said that near-infrared absorption ability is better when there is no extremum point.
Yes : Has extreme points No : Does not have extreme points

(Light resistance test)
A test substrate was prepared in the same procedure as the spectral characteristic evaluation, placed in a light resistance tester ("SUNTEST CPS+" manufactured by TOYOSEIKI), and left for 24 hours. The absorbance at the spectral maximum absorption wavelength of the near-infrared absorbing film was measured, the residual ratio to that before light irradiation was determined, and the light resistance was evaluated according to the following criteria. The residual ratio was calculated using the following formula.
Residual rate = (absorbance after irradiation) / (absorbance before irradiation) x 100
◎: Residual rate is 95% or more ○: Residual rate is 90% or more and less than 95% ×: Residual rate is less than 90%

(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 of Tables 4-1, 4-2, and 4-3, Examples 1-1 to 1-93 have low absorption at 480 nm to 650 nm, which has high relative luminosity, good dispersibility and dispersion stability, and It has excellent near-infrared absorptivity, as well as excellent light resistance and heat resistance.

<Production of photosensitive near-infrared absorbing composition>
[Example 2-1]
(Photosensitive near-infrared absorbing composition (RR'-1))
After the following mixture was uniformly stirred and mixed, the mixture was filtered through a 1.0 μm filter to obtain a photosensitive near-infrared absorbing composition (RR'-1).
Near-infrared absorbing composition (DD'-2): 50.0 parts Binder resin 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 2-2 to 2-35, Comparative Examples 2-1 to 2-4, Reference Examples 2-1 to 2-4]
(Photosensitive near-infrared absorbing compositions (RR′-2) to (RR′-35), comparative photosensitive compositions 1 to 4, reference photosensitive compositions 1 to 4)
Hereinafter, photosensitive near-infrared absorbing composition in the same manner as the photosensitive near-infrared absorbing composition (RR'-1) except that the near-infrared absorbing composition was changed to the type of near-infrared absorbing composition shown in Table 5. Compositions (RR'-2) to (RR'-35), comparative photosensitive compositions 1' to 4', and reference photosensitive compositions 1' to 4' were obtained.

<Evaluation of photosensitive near-infrared absorbing composition>
The photosensitive near-infrared absorbing compositions obtained in Examples (RR'-2) to (RR'-35), comparative photosensitive compositions 1 to 4, and reference photosensitive compositions 1 to 4 were dispersible. , dispersion stability, spectral characteristics, and resistance (heat resistance, light resistance) were tested by the following methods. 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. Table 5 shows the results.

(Dispersibility: evaluation of filterability)
The dispersibility of the resulting photosensitive near-infrared absorptive composition was evaluated by filterability.
10 g of the resulting photosensitive near-infrared absorbing composition is passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number: 39115221) under nitrogen pressure (0.3 MPa), and the amount obtained through the filter is measured, Evaluation was made according to the following criteria.
◎: Filtration amount is 9.0 g or more ○: Filtration amount is 5.0 g or more and less than 9.0 g △: Filtration amount is 3.0 g or more and less than 5.0 g ×: Filtration amount is 3.0 g or less

(Evaluation of dispersion stability 1)
The viscosity of the resulting photosensitive near-infrared absorptive composition was measured and taken as the initial viscosity. Further, an accelerated test was performed at 40° C. for 7 days to measure accelerated viscosity over time.
As the rate of change due to acceleration, accelerated viscosity/initial viscosity was calculated and evaluated according to the following criteria.
◎: less than 1.05 ○: 1.05 or more and less than 1.10 △: 1.10 or more and less than 1.3 ×: 1.3 or more

(Evaluation of dispersion stability 2)
The viscosity of the resulting photosensitive near-infrared absorptive composition was measured and taken as the initial viscosity. Further, an accelerated test was conducted in which one cycle was 40° C. for 7 days, 13° C. for 7 days, and 40° C. for 7 days, and accelerated viscosity over time was measured.
As the rate of change due to acceleration, accelerated viscosity/initial viscosity was calculated and evaluated according to the following criteria.
◎: less than 1.05 ○: 1.05 or more and less than 1.10 △: 1.10 or more and less than 1.3 ×: 1.3 or more

(Evaluation of spectral characteristics 1)
The resulting photosensitive near-infrared absorbing composition was spin-coated on a glass substrate having a thickness of 1.1 mm using a spin coater so that the film thickness after drying was 1.0 μm, and dried at 60° C. for 5 minutes. After that, it was heated at 230° C. for 5 minutes to prepare a substrate. The absorption spectrum of the resulting substrate was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation) in the wavelength range of 300 to 1200 nm. The ratio (W/X) of the maximum absorbance value (W) at 700 to 800 nm and the minimum absorbance value (X) at 480 to 650 nm was determined for the obtained substrate and evaluated according to the following criteria. Incidentally, the larger this ratio (W / X), the less absorption at the wavelength with the lowest absorption in the region with high relative luminosity (480 nm to 650 nm) for the absorption in the near infrared, and the maximum transmittance at the wavelength It can be said that the permeability is high.
◎: 30 or more ○: 15 or more and less than 30 △: 5 or more and less than 15 ×: less than 5

(Evaluation of spectral characteristics 2)
Regarding the substrate obtained above, the ratio (W/Y) of the maximum absorbance value (W) at 700 to 800 nm and the maximum absorbance value (Y) at 480 to 650 nm was determined and evaluated according to the following criteria. It should be noted that the greater the ratio (W/Y), the less the absorption in the near-infrared region (480 nm to 650 nm) with high relative luminosity, and the higher the transmittance in the region perceived brighter by the human eye. I can say
◎: 4 or more ○: 3 or more, less than 4 △: 2 or more, less than 3 ×: less than 2

(Evaluation of spectral characteristics 3)
The substrate obtained above was evaluated as to whether it had an extreme point at 800 to 900 nm. The extremum point is a point at which the absorbance changes from an increase to a decrease or from a decrease to an increase when the absorbance is confirmed from the short wavelength side to the long wavelength side. If there is an extremum point, transmitted light at that wavelength may be detected as noise, so it can be said that near-infrared absorption ability is better when there is no extremum point.
Yes : Has extreme points No : Does not have extreme points

(Light resistance test)
A test substrate was prepared in the same procedure as the spectral characteristic evaluation, placed in a light resistance tester ("SUNTEST CPS+" manufactured by TOYOSEIKI), and left for 24 hours. The absorbance at the spectral maximum absorption wavelength of the near-infrared absorption film was measured, the residual ratio to that before light irradiation was determined, and the light resistance was evaluated according to the following criteria. The residual ratio was calculated using the following formula.
Residual rate = (absorbance after irradiation) / (absorbance before irradiation) x 100
◎: Residual rate is 95% or more ○: Residual rate is 90% or more and less than 95% ×: Residual rate is less than 90%

(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 of Table 5, Examples 2-1 to 2-35 have low absorption at 480 nm to 650 nm, which has high relative luminosity, and excellent near-infrared absorption, no noise, and further dispersibility, dispersion stability, Excellent light resistance and heat resistance.

<Production of near-infrared cut filter>
[Examples 3-1 to 3-11]
(Near infrared absorption cut filter (FF'-1) to (FF'-11))
The photosensitive near-infrared absorbing composition (RR'-1) of the present invention was applied onto a 1.1 mm thick glass substrate by a spin coater, and pre-baked by heating 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 (FF'-1) after the heat treatment was 1.0 μm.
Hereinafter, the near-infrared cut filter in the same manner as the near-infrared cut filter (FF'-1) except that the photosensitive near-infrared absorptive composition was changed to the type of photosensitive near-infrared absorptive composition shown in Table 6. (FF'-2) to (FF'-11) were obtained.

<Evaluation of near-infrared cut filter>
Near-infrared cut filters (FF'-1) to (FF'-11) were tested for spectral characteristics and durability (heat resistance, light resistance) in the same manner as the evaluation of the photosensitive near-infrared absorbing composition. . Table 6 shows the results.

From the results in Table 6, Examples 3-1 to 3-11 were excellent in spectral characteristics. It has little absorption in the range of 480 nm to 650 nm, which has high relative luminosity, and is excellent in near-infrared absorption, as well as excellent light resistance and 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 2 solution: 7.5 parts Binder resin 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 2 solution: 7.5 parts Binder resin 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 2 solution: 7.5 parts Binder resin solution: 35.0 parts PGMAc: 47.5 parts

[Example 4-1]
(Visible light region absorbing composition (VV'-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 (VV'-1).
Near-infrared absorbing composition (DD'-2): 10.0 parts Blue pigment composition: 20.0 parts Purple pigment composition: 10.0 parts Yellow pigment composition: 10.0 parts Binder resin 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 4-2 to 4-11]
(Visible light region absorbing compositions (VV'-2) to (VV'-11))
Hereinafter, a visible light absorbing composition was prepared in the same manner as the visible light absorbing composition (VV'-1) except that the near infrared absorbing composition was changed to the type of near infrared absorbing composition shown in Table 7. (VV'-2) to (VV'-11) 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 900 to 1200 nm and the absorption in the wavelength range of 400 to 800 nm were evaluated.
Table 7 shows the results.

(400-800 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 800 nm.
○: transmittance of less than 2% in the entire region of 400 to 800 nm △: transmittance of 2% or more in a partial region of 400 to 800 nm ×: transmittance of 2% or more in the entire region of 400 to 800 nm

(900-1200 nm transparency)
Using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation), the obtained substrate was measured for transmittance at 900 nm to 1200 nm.
○: Transmittance of 80% or more in the entire region of 900 to 1200 nm △: 40% or more and less than 80% in the partial region of 900 to 1200 nm ×: Less than 40% in the partial region of 900 to 1200 nm

(Light resistance test)
The resulting substrate was placed in a light resistance tester ("SUNTEST CPS+" manufactured by TOYOSEIKI) and left for 24 hours. At this time, the test was performed with an irradiance of 47 mW/cm 2 and broadband light of 300 to 800 nm. After that, a transmission spectrum in a wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
○: transmittance of less than 2% in the entire region of 400 to 800 nm △: transmittance of 2% or more in a partial region of 400 to 800 nm ×: transmittance of 2% or more in the entire region of 400 to 800 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 800 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
○: transmittance of less than 2% in the entire region of 400 to 800 nm △: transmittance of 2% or more in a partial region of 400 to 800 nm ×: transmittance of 2% or more in the entire region of 400 to 800 nm

From the results of Table 7, Examples 4-1 to 4-11 contain both the near-infrared absorbing composition of the present invention and a dye that absorbs visible light of 400 to 700 nm, so that light in the entire range of 400 to 800 nm and transmit near-infrared rays from 900 nm to 1200 nm. Furthermore, it has excellent light resistance and 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 5-1]
(Manufacturing of masterbatch)
0.8 parts of the near-infrared absorbing dye (AA-2), 0.2 parts of the green dye (G), and 99 parts of the thermoplastic resin (E-1) are fed from the same supply port into two with a screw diameter of 30 mm. The mixture was put into a screw extruder (manufactured by Japan Steel Works, Ltd.), melted and kneaded at 300° C., and cut into pellets using a pelletizer to prepare a masterbatch (MM′-1).

(Film molding)
Mix 5 parts of the obtained masterbatch ((MM'-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) to adjust the temperature They were melt mixed at 300° C. to form a film (QQ′-1) with a thickness of 250 μm.

[Examples 5-2 to 5-56, Comparative Examples 5-1 to 5-4, Reference Examples 5-1 to 5-4]
In the same manner as in Example 5-1, using the materials listed in Table 8, films (QQ'-2) to (QQ'-56) with a thickness of 250 μm, comparative resin compositions 1' to 4', and reference resin compositions Items 1' to 4' were molded.

<Evaluation of film>
Films (QQ'-1) to (QQ'-56) obtained in Examples, comparative resin compositions 1' to 4', and reference resin compositions 1' to 4', dispersibility, spectral characteristics, transparency , haze value, and light resistance were tested by the following methods. 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.
Table 9 shows the results.

(Dispersibility: evaluation of particles)
0.1 g of the resulting film was cut, pressed into a film by a slide, and then observed with an optical microscope (magnification: 200) to obtain a particle image, and randomly selected at least 1000 particles (primary particles). The particle diameter (equivalent circle diameter) was measured for each of the particles, which may contain secondary particles, and was evaluated according to the following criteria.
◎: 1 or less particles of 20 μm or more ○: More than 1 and 5 or less particles of 20 μm or more △: More than 5 and 20 or less particles of 20 μm or more ×: More than 20 particles of 20 μm or more and one or more particles of 45 μm or more

(Evaluation of spectral characteristics 1)
The absorption spectrum in the wavelength range of 300 to 1200 nm was measured for the obtained film using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). For the obtained substrate, the ratio (W/X) of the maximum absorbance (W) at 700-800 nm and the minimum absorbance (X) at 480-650 nm was determined and evaluated according to the following criteria. Incidentally, the larger this ratio (W / X), the less absorption at the wavelength with the lowest absorption in the region with high relative luminosity (480 nm to 650 nm) for the absorption in the near infrared, and the maximum transmittance at the wavelength It can be said that the permeability is high.
◎: 30 or more ○: 15 or more and less than 30 △: 5 or more and less than 15 ×: less than 5

(Evaluation of spectral characteristics 2)
The ratio (W/Y) of the maximum absorbance value (W) at 700 to 800 nm and the maximum absorbance value (Y) at 480 to 650 nm of the obtained film was determined and evaluated according to the following criteria.
◎: 4 or more ○: 3 or more, less than 4 △: 2 or more, less than 3 ×: less than 2

(Evaluation of spectral characteristics 3)
The films obtained were evaluated for the presence of extreme points at 800-900 nm. The extremum point is a point at which the absorbance changes from an increase to a decrease or from a decrease to an increase when the absorbance is confirmed from the short wavelength side to the long wavelength side. If there is an extremum point, transmitted light at that wavelength may be detected as noise, so it can be said that near-infrared absorption ability is better when there is no extremum point.
Yes : Has extreme points No : Does not have extreme points

(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.

(haze value)
The haze value of the obtained film was measured with a haze meter (“300A” manufactured by Nippon Denshoku Co., Ltd.) and evaluated according to the following criteria.
◎ +: Less than 0.2 Very good ◎: 0.2 or more and less than 0.5 Very good ○: 0.5 or more and less than 2 Good △: 2 or more and less than 5 Good ×: 5 or more Not practical

(light resistance)
A test film was prepared in the same procedure as the near-infrared absorption evaluation, placed in a light resistance tester ("SUNTEST CPS+" manufactured by TOYOSEIKI), and irradiated with broadband light at an irradiance of 47 mW/cm ² and 300 to 800 nm. , left for 24 hours. Next, the test film was taken out, the absorbance at the maximum absorption wavelength of the test film was measured, the residual ratio to the absorbance before light irradiation was determined, and the light resistance was evaluated according to the following criteria. The residual ratio was calculated using the following formula.
Residual rate = (absorbance after irradiation) / (absorbance before irradiation) x 100
○: Residual rate is 90% or more △: Residual rate is 85% or more and less than 90% ×: Residual rate is less than 85%,

From the results of Table 9, Examples 5-1 to 5-56 have low absorption at 480 nm to 650 nm, which has high relative luminosity, and excellent near-infrared absorption, further dispersibility, transparency, and excellent light resistance. there is

<Production of visible light region absorbing composition for molding>
[Example 6-1]
(Manufacturing of masterbatch)
0.8 parts of near-infrared absorbing dye (AA-2), 0.2 parts of green dye (G), 1 part of Pigment Blue 15:3, 1 part of Pigment Yellow 147, 1 part of Solvent Red 52, 96 parts of the thermoplastic resin (E-1) is charged from the same supply port into a twin-screw extruder with a screw diameter of 30 mm (manufactured by Japan Steel Works, Ltd.), melt-kneaded at 300 ° C., and pelletized using a pelletizer. A masterbatch (MV'-1) was prepared by cutting into a shape.

(Film molding)
Mix 5 parts of the obtained masterbatch (MV'-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 (QV'-1) having a thickness of 250 .mu.m.

[Examples 6-2 to 6-23]
Films (QV'-2) to (QV'-23) with a thickness of 250 μm were formed using the materials listed in Table 10 in the same manner as in Example 6-1.

<Evaluation of film>
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 900 to 1200 nm and the absorption in the wavelength range of 400 to 800 nm were evaluated.
Table 11 shows the results.

(400-800 nm absorption)
Using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation), the transmission spectrum of the obtained film was measured in a wavelength range of 400 to 800 nm.
○: transmittance of less than 2% in the entire region of 400 to 800 nm △: transmittance of 2% or more in a partial region of 400 to 800 nm ×: transmittance of 2% or more in the entire region of 400 to 800 nm

(900-1200 nm transparency)
The transmittance of the obtained film at 900 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 900 to 1200 nm △: 40% or more and less than 80% in the partial region of 900 to 1200 nm ×: Less than 40% in the partial region of 900 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.

(light resistance)
The resulting film was placed in a light resistance tester ("SUNTEST CPS+" manufactured by TOYOSEIKI) and left for 24 hours. At this time, the test was performed with an irradiance of 47 mW/cm 2 and broadband light of 300 to 800 nm. After that, a transmission spectrum in a wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).
○: transmittance of less than 2% in the entire region of 400 to 800 nm △: transmittance of 2% or more in a partial region of 400 to 800 nm ×: transmittance of 2% or more in the entire region of 400 to 800 nm

From the results of Table 11, Examples 6-1 to 6-23 absorb light in the entire range of 400 to 800 nm by containing both a near-infrared absorbing dye and a dye that absorbs visible light of 400 to 700 nm, It can transmit near infrared rays from 900 to 1200 nm. Furthermore, it is excellent in transparency and light resistance.

Claims (8)

characterized by comprising a near-infrared absorbing dye (A) represented by the following general formula (1) and a green dye (G) represented by the following general formula (101) or general formula (102) A near-infrared absorbing composition.

[In general formula (1), X ₁ to X ₈ and Y ₁ to Y ₈ each independently have a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, or a substituent. Alkyl groups, optionally substituted aryl groups, optionally substituted cycloalkyl groups, optionally substituted heterocyclic groups, optionally substituted alkoxyl groups, aryloxy group optionally having substituent(s), alkylthio group optionally having substituent(s), arylthio group optionally having substituent(s), phthalimidomethyl group optionally having substituent(s), represents an optionally substituted alkylamino group, an optionally substituted arylamino group, or an optionally substituted sulfamoyl group. In addition, X ₁ to X ₈ may each independently combine with each other to form an aromatic ring which may have a substituent. However, one or more pairs of X ₁ and X ₂ , X ₃ and X ₄ , X ₅ and X ₆ , and X ₇ and X ₈ are bonded to each other to form an aromatic ring which may have a substituent.
Z ₁ represents —OP(=O)R ₁ R ₂ or a polymer moiety containing a monomer unit represented by general formula (2). Here, R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, It represents an aryloxy group which may have a substituent, and R ₁ and R ₂ may combine with each other to form a ring.
In general formula (2), W represents -CONH-R ₄ -, -COO-R ₅ -, -CONH-R ₆ -O-, -COO-R ₇ -O-, and R ₄ to R ₇ , represents an alkylene group or an arylene group in which carbon atoms may be linked by --O--, --CO--, --COO--, --OCO--, --CONH-- or --NHCO--. _R3 represents a hydrogen atom or a methyl group. * is a bond with Al. ]

[In general formulas (101) and (102), R ₂₇ to R ₄₂ each independently represent a hydrogen atom, a halogen atom, a nitro group, a nitrile group, an optionally substituted alkyl group, or a substituted optionally substituted cycloalkyl group, optionally substituted heterocyclic group, optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted It represents an alkylthio group, an arylthio group which may have a substituent, an alkylamino group which may have a substituent, or an arylamino group which may have a substituent. _M1 represents copper (Cu) and zinc (Zn). _M2 represents aluminum (Al).
In general formula (102), Z ₃ represents —OP(=O)R ₁ R ₂ or a polymer moiety containing a monomer unit represented by general formula (2). Here, R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, It represents an aryloxy group which may have a substituent, and R ₁ and R ₂ may combine with each other to form a ring. ] 2. The near-infrared absorbing composition according to claim 1, wherein the near-infrared absorbing dye (A) contains a near-infrared absorbing dye (A1) represented by the following general formula (3).

[In the general formula (3), Y ₉ to Y ₁₆ and R ₈ to R ₂₁ each independently have a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, or a substituent. Alkyl groups, optionally substituted aryl groups, optionally substituted cycloalkyl groups, optionally substituted heterocyclic groups, optionally substituted alkoxyl groups, aryloxy group optionally having substituent(s), alkylthio group optionally having substituent(s), arylthio group optionally having substituent(s), phthalimidomethyl group optionally having substituent(s), represents an optionally substituted alkylamino group, an optionally substituted arylamino group, or an optionally substituted sulfamoyl group.
Z ₂ represents —OP(=O)R ₁ R ₂ or a polymer moiety containing a monomer unit represented by general formula (2). Here, R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, It represents an aryloxy group which may have a substituent, and R ₁ and R ₂ may combine with each other to form a ring.
In general formula (2), W represents -CONH-R ₄ -, -COO-R ₅ -, -CONH-R ₆ -O-, -COO-R ₇ -O-, and R ₄ to R ₇ , represents an alkylene group or an arylene group in which carbon atoms may be linked by --O--, --CO--, --COO--, --OCO--, --CONH-- or --NHCO--. _R3 represents a hydrogen atom or a methyl group. * is a bond with Al. ] The green dye (G) is 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, and C.I. I. 3. The near-infrared absorbing composition according to claim 1, comprising at least one selected from the group consisting of Pigment Green 63. 4. The near-infrared absorbing composition according to any one of claims 1 to 3, wherein the green pigment (G) contains a pigment having an acidic group amount of 100 to 600 µmol. Any one of claims 1 to 4, wherein the mass ratio of the near-infrared absorbing dye (A) and the green dye (G) in the near-infrared absorbing composition is 95/5 to 60/40. The near-infrared absorbing composition according to . 6. The near-infrared absorbing composition according to any one of claims 1 to 5, further comprising a photopolymerizable monomer and/or a photopolymerization initiator. 7. The near-infrared absorptive composition according to any one of claims 1 to 6, further comprising an organic dye having absorption at 400 nm to 700 nm (excluding green dye (G)). An optical filter comprising a film formed from the near-infrared absorbing composition according to any one of claims 1 to 7.

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